CN112280286B - Water-absorbing porous composite material with integrated structure and function and preparation method thereof - Google Patents
Water-absorbing porous composite material with integrated structure and function and preparation method thereof Download PDFInfo
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- CN112280286B CN112280286B CN202011184014.5A CN202011184014A CN112280286B CN 112280286 B CN112280286 B CN 112280286B CN 202011184014 A CN202011184014 A CN 202011184014A CN 112280286 B CN112280286 B CN 112280286B
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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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
- C08J2205/00—Foams characterised by their properties
- C08J2205/10—Rigid foams
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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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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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
- C08J2433/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/24—Homopolymers or copolymers of amides or imides
- C08J2433/26—Homopolymers or copolymers of acrylamide or methacrylamide
Abstract
The invention provides a preparation method of a water-absorbing porous composite material with integrated structure and function, which comprises the following steps: (1) mixing the polyurethane rigid foam combined polyether, polyacrylamide water-absorbing resin and a polar solvent to obtain a polyurethane rigid foam combined polyether mixture; (2) adding an isocyanate component into the polyurethane rigid foam combined polyether mixture obtained in the step (1), and uniformly stirring to obtain a reaction foaming liquid; (3) and adding the reaction foaming liquid into a mould and foaming to prepare the water-absorbing porous composite material. The invention also provides a water-absorbent porous composite material prepared by the method. The water-absorbing porous composite material prepared by the method realizes the fixation of water by combining with water molecules, and has good water locking performance; the surface is smooth, and the porosity and the pore size are uniformly distributed; the combination of the dissimilar materials is stable, and the dissimilar materials are not separated and fall off in the multiple circulation process.
Description
Technical Field
The invention relates to the technical field of water-absorbing porous composite materials, in particular to a structure-function integrated porous water-absorbing composite material and a preparation method thereof.
Background
The water-absorbing porous composite material with integrated structure and function is a high-molecular porous material containing high-water-absorbing resin, can realize the fixation of water molecules by utilizing the high-water-absorbing resin, and can realize the interpenetrating network structure and dimensional effect with the water-absorbing resin by utilizing the hole structure of the high-molecular material, thereby achieving the integrated design of the structure and function.
The water-absorbent resin is a functional polymer which contains strong hydrophilic groups and has a certain degree of crosslinking, is insoluble in water and organic solvents, can absorb hundreds to thousands of times of weight of water per se, has good water-locking property, and has good water retention property, deformability and weather resistance after water swelling.
The water-absorbent resin swells into a hydrogel state after absorbing water, and the liquid is kept in a non-flowable state, and the liquid is hardly separated therefrom even when pressurized. However, the water-absorbent resin has low strength after swelling after absorbing water, and cannot be dimensionally deformed and uniformly attached to other support structures, and structural and functional integration cannot be achieved.
In the prior art, when the water-absorbent resin and other materials are compounded to solve the problems that the properties of the water-absorbent resin cannot be maintained when the water-absorbent resin is used alone, the obtained composite material is easy to have the problems of uneven surface, poor dimensional stability and consistency and uneven pore diameter, and particularly the problem that the combination of different materials between the water-absorbent resin and other composite raw materials is unstable, so that the water-absorbent resin and other composite raw materials are separated and fall off in the process of multiple cycles.
Disclosure of Invention
Technical problem to be solved
The invention aims to provide a water-absorbent resin for realizing the functions of fixing water and storing water; the polyurethane porous material is utilized to achieve the shape maintaining effect, so that the preparation of the integrated material with the shape maintaining and water absorbing functions is realized, and the following problems are solved: when the water-absorbent resin is compounded with other materials to solve the above problems that the properties of the water-absorbent resin cannot be maintained when the water-absorbent resin is used alone, the obtained composite material is prone to have uneven surface, poor dimensional stability and consistency and uneven pore size, and particularly has the problem that the combination of different materials between the water-absorbent resin and other composite raw materials is unstable, so that the water-absorbent resin and other composite raw materials are separated and fall off in the process of multiple cycles.
(II) technical scheme
The present invention provides in a first aspect a process for the preparation of a structurally and functionally integrated water-absorbent porous composite material, said process comprising the steps of:
(1) mixing the polyurethane rigid foam combined polyether, polyacrylamide water-absorbing resin and a polar solvent to obtain a polyurethane rigid foam combined polyether mixture;
(2) adding an isocyanate component into the mixture obtained in the step (1), and uniformly stirring to obtain a reaction foaming liquid;
(3) and adding the reaction foaming liquid into a mould and foaming to prepare the water-absorbing porous composite material.
In a second aspect, the present invention provides a structurally and functionally integrated water-absorbent porous composite material prepared by the preparation method according to the first aspect of the present invention.
(III) advantageous effects
1. The combination mode of the water-absorbent resin and water is different from the physical adsorption effect of the traditional capillary action, the water can be fixed by combining with water molecules, and the water-absorbent resin has good water locking performance.
2. The water-absorbent resin does not have strength, and the resin cannot be subjected to dimension maintenance due to volume expansion after water absorption, so that the resin is more stable by combining the resin with polyurethane, uniform distribution of porosity and pore size is realized, and the problem that the water-absorbent resin cannot be subjected to dimension maintenance due to low strength of the water-absorbent resin is solved.
3. The water-absorbent porous composite material prepared by the invention has the advantages of smooth surface, stable and consistent size and uniform pore diameter, can realize stable combination of dissimilar materials, and ensures that the water-absorbent resin and the polyurethane porous material are not separated and fall off in the process of multiple cycles; meanwhile, the preparation of the integrated material with dimensional and water absorption functions can be realized by utilizing the material characteristics.
Drawings
FIG. 1 shows a process according to the invention for the production of a water-absorbent porous composite.
FIG. 2 is a graph showing the total amount of water absorbed during 10 times of repeated use of the water-absorbent porous composites obtained in examples 1 to 4.
FIG. 3 is a graph showing the total amount of water absorption during 10 times of repeated use of the water-absorbent porous composite materials obtained in comparative examples 1 to 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
As described above, the first aspect of the present invention provides a method for producing a structure-function integrated water-absorbent porous composite material, comprising the steps of: (1) mixing polyurethane rigid foam composite polyether, polyacrylamide water-absorbing resin and a polar solvent to obtain a polyurethane A material mixture; (2) adding an isocyanate component into the mixture obtained in the step (1), and uniformly stirring to obtain a reaction foaming liquid; (3) and adding the reaction foaming liquid into a mould and foaming to prepare the water-absorbing porous composite material.
The polyurethane porous material consists of a plurality of holes, the porosity can reach more than 90 percent, and the interpenetrating network structure with the water-absorbent resin can be realized by utilizing the holes; more importantly, the water-absorbing porous composite material prepared from the polyurethane porous material and the water-absorbing resin does not separate or fall off in the process of multiple recycling.
In some preferred embodiments, the preparation method further comprises the steps of: (4) and (4) a step of taking out the foam from the mold and cutting the foam into a composite material having a target size as needed after foaming to fill the mold in the step (3).
In other preferred embodiments, the raw materials are added in the following amounts by weight: 50-125 parts (such as 50, 55, 65, 75, 85, 95, 105, 115 and 125 parts) of polyurethane rigid foam combined polyether, 10-40 parts (such as 10, 15, 20, 25, 30, 35 and 40 parts) of polyacrylamide water-absorbing resin, 0.5-10 parts (such as 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 parts) of polar solvent and 65-130 parts (such as 65, 75, 85, 95, 105, 115, 125 and 130 parts) of isocyanate component.
In other preferred embodiments, the polar solvent is a mixed solution of formamide and water. Preferably, the volume ratio of formamide to water in the mixed solution is (0-10):1, for example 0.1:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10: 1.
In other preferred embodiments, in step (2), the stirring time of the stirring is 5 to 60s, such as 5, 10, 20, 30, 40, 50, 60 s.
In other preferred embodiments, in step (2), the stirring speed of the stirring is 40 to 450rpm (e.g., 100, 200, or 300 rpm).
In other preferred embodiments, in step (2), the viscosity of the reactive foaming liquid at 20 ℃ is from 0.11 to 6.05 pas (e.g., 0.5, 1.0, 2.0, or 5.0 pas).
In other preferred embodiments, in step (3), the foaming temperature of the foaming is 15 to 150 ℃ and the foaming time is 1 to 60 min.
In some more specific embodiments, the preparation method comprises the steps of:
(1) mixing the polyurethane rigid foam combined polyether, polyacrylamide water-absorbing resin and a polar solvent to obtain a polyurethane rigid foam combined polyether mixture;
(2) adding isocyanate component into the polyurethane rigid foam combined polyether mixture, stirring at high speed for 5-60s at the rotating speed of 40-450rpm, and uniformly mixing the water-absorbing polyurethane prepolymer to prepare a reaction foaming liquid with the viscosity of 0.11-6.05 Pa.s at 20 ℃;
(3) casting the reaction foaming liquid into a mold, covering the mold, and standing in a drying oven at the temperature of 15-150 ℃ for 1-60min for foaming;
(4) and taking the foaming body out of the mold after the mold is full of the foaming body.
In other more specific embodiments, the foam is processed, e.g., cut, into a water-absorbent porous composite having a target size.
In a second aspect, the present invention provides a structurally and functionally integrated water-absorbent porous composite material prepared by the preparation method according to the first aspect of the present invention.
The water-absorbing porous composite material prepared by the method is prepared by polymerizing water-absorbing resin and polyurethane. Among them, the polyurethane material containing the super absorbent resin has good water retention, deformability and weather resistance after absorbing water and swelling, and simultaneously utilizes the physical characteristics of the polyurethane material to improve the problem that the water absorbent resin is difficult to maintain due to low strength of the water absorbent resin, thereby realizing integration of the maintenance and the water absorption functions. More importantly, the prepared water-absorbent porous composite material has a smooth surface, stable and consistent size and uniform pore diameter, can realize stable combination of dissimilar materials, and ensures that the water-absorbent resin and the polyurethane porous material are not separated and fall off in the process of multiple cycles.
Examples
The present invention will be further illustrated by the following examples, which are provided for illustrative purposes and are not intended to be limiting, and the scope of the present invention is not limited to these examples.
Example 1
The embodiment prepares a water-absorbing porous composite material with integrated structure and function, and the preparation process comprises the following steps:
(1) 50 parts by weight of polyurethane rigid foam combined polyether, 10 parts by weight of polyacrylamide water-absorbing resin and 0.5 part by weight of mixed solution of formamide and deionized water in a volume ratio of 0:1 (namely deionized water without formamide) are mixed to obtain a mixture containing the polyurethane rigid foam combined polyether.
(2) Adding 65 parts by weight of isocyanate component into the obtained mixture, stirring at a high speed of 255rpm for 30s, and uniformly mixing the water-absorbing polyurethane prepolymer to obtain the reaction foaming liquid. The viscosity of the reaction foam liquid was measured to be 0.13 pas at 20 ℃.
(3) Covering the mold, and standing in a drying oven at 25 deg.C for 30min for foaming.
(4) Cutting the porous composite material into corresponding sizes according to the target size to obtain the water-absorbing porous composite material, wherein the porosity and the pore size of the porous composite material are uniformly distributed, and the porous composite material has the advantages of smooth surface, high size stability and high consistency.
Performance detection
Testing the water absorption performance: under the condition of room temperature, the water-absorbing porous composite material is completely immersed into 1L of deionized water, absorbs water and swells for 4 hours so as to reach a saturated swelling state. The water-absorbent composite material in a saturated state of water absorption was filtered with a 100-mesh screen until no water droplets dropped, and then the water on the surface of the resin was wiped off with a water-absorbent paper, and the mass of the water-absorbent composite material in a saturated state at this time was weighed. Calculated, the water absorption amount is about 30 times of the self mass.
And (3) testing the reusability: in order to verify the reusability of the water-absorbent porous composite material, the prepared water-absorbent composite material was subjected to a repeated water absorption-evaporation test. As shown in FIG. 2, the water absorption capacity of 1g of the water-absorbent porous composite material was maintained at 200g or more through 10 repeated tests, and no significant change in appearance was observed, and no failure behavior occurred under repeated use conditions.
Therefore, the embodiment prepares the water-absorbing porous composite material with good dimensional property, water retention property and weather resistance, realizes the integration of dimensional property and water absorbing function, and has stable combination of the water-absorbing resin and the polyurethane material, and the water-absorbing resin and the polyurethane material are not separated and fall off after being recycled for a plurality of times.
Example 2
The embodiment prepares a water-absorbing porous composite material with integrated structure and function, and the preparation process comprises the following steps:
(1) 85 parts by weight of polyurethane rigid foam composite polyether, 25 parts by weight of polyacrylamide water-absorbing resin (the water absorption multiple is 30 times), and 5 parts by weight of formamide and deionized water in a mixing ratio of 4:1 are mixed, and the mixture is blended to obtain a mixture containing a polyurethane A material.
(2) And adding 95 parts by weight of isocyanate component into the obtained mixture, stirring at a high speed of 255rpm for 30s, and uniformly mixing the water-absorbing polyurethane prepolymer to obtain the reaction foaming liquid. The viscosity of the reaction foam liquid was measured to be 3.05 pas at 20 ℃.
(3) Covering the mould, and standing in a drying oven at 60 deg.C for 30min for foaming;
(4) and cutting into corresponding sizes according to the target size to obtain the water-absorbent porous composite material.
Example 3
The embodiment prepares a water-absorbing porous composite material with integrated structure and function, and the preparation process comprises the following steps:
(1) 125 parts by weight of polyurethane rigid foam combined polyether, 40 parts by weight of polyacrylamide water-absorbing resin and 10 parts by weight of mixture of formamide and deionized water with the mixing ratio of 9:1 are mixed and blended to obtain a mixture containing the polyurethane rigid foam combined polyether.
(2) Adding 130 parts by weight of isocyanate component into the obtained mixture, stirring at a high speed of 450rpm for 60s, and uniformly mixing the water-absorbing polyurethane prepolymer to obtain the reaction foaming liquid. The reaction foaming liquid was measured to have a mixed liquid viscosity of 6.03 pas at 20 ℃.
(3) Covering the mold, and standing in a drying oven at 100 deg.C for 60min for foaming.
(4) And cutting into corresponding sizes according to the target size to obtain the water-absorbent porous composite material.
Example 4
The embodiment prepares a water-absorbing porous composite material with integrated structure and function, and the preparation process comprises the following steps:
(1) 85 parts by weight of polyurethane rigid foam combined polyether, 40 parts by weight of polyacrylamide water-absorbing resin and 5 parts by weight of mixture of formamide and deionized water in a mixing ratio of 4:1 are mixed and blended to obtain a mixture containing the polyurethane rigid foam combined polyether.
(2) And adding 95 parts by weight of isocyanate component into the obtained mixture, stirring at a high speed of 355rpm for 45s, and uniformly mixing the water-absorbing polyurethane prepolymer to obtain the reaction foaming liquid. The reaction foaming liquid was measured to have a mixed liquid viscosity of 4.12 pas at 20 ℃.
(3) Covering the mold, and standing in a drying oven at 75 deg.C for 45min for foaming.
(4) And cutting into corresponding sizes according to the target size to obtain the water-absorbent porous composite material.
Comparative example 1
In substantially the same manner as in example 1 except that no water-absorbent resin was added, a polyurethane porous material having a porosity of 91.4% was produced.
Comparative example 2
Substantially the same procedure as in example 1 was conducted except that copper metal foam having a porosity of 90% by mass as the polyurethane porous material obtained in comparative example 1 was compounded with 40 parts by weight of a polyacrylamide water-absorbent resin in place of the polyurethane of example 1.
Comparative example 3
Substantially the same procedure as in example 1 was conducted except that a high molecular foam (available from Haoyu foam New Material Co., Ltd.) having a porosity of 90% by mass as that of the polyurethane porous material obtained in comparative example 1 was compounded with 40 parts by weight of the polyacrylamide water-absorbent resin in place of the polyurethane of example 1.
TABLE 1 raw materials used in examples and comparative examples and Properties of the materials obtained
From the above examples, it can be seen that the method of the present invention can produce a water-absorbent porous composite material with integrated structure and function, which utilizes the good water retention, deformability and weather resistance of the water-absorbent resin after water absorption and expansion, and utilizes the physical properties of the polyurethane porous material to improve the problem that the water-absorbent resin is difficult to maintain due to low strength of the water-absorbent resin; and more importantly, the water-absorbent resin and the polyurethane porous material can be prevented from separating and falling off in the process of multiple cycles through the cross-linking polymerization of the two materials, so that the preparation of the dimensional and water-absorbing integrated material is realized.
The invention has not been described in detail and is in part known to those of skill in the art.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A method for preparing a water-absorbing porous composite material with integrated structure and function is characterized by comprising the following steps:
(1) mixing polyurethane rigid foam composite polyether, polyacrylamide water-absorbing resin and a polar solvent to obtain a polyurethane A material mixture; the polar solvent is formamide aqueous solution; in the formamide aqueous solution, the volume ratio of formamide to water is (0-10) to 1;
(2) adding an isocyanate component into the polyurethane A material mixture obtained in the step (1), and uniformly stirring to obtain a reaction foaming liquid;
(3) and adding the reaction foaming liquid into a mould and foaming to prepare the water-absorbing porous composite material.
2. The method of manufacturing according to claim 1, further comprising:
(4) and (4) a step of taking out the foam from the mold and cutting the foam into a composite material having a target size as needed after foaming to fill the mold in the step (3).
3. The preparation method according to claim 1, characterized in that the raw materials are added in the following amounts by weight: 50-125 parts of polyurethane rigid foam combined polyether, 10-40 parts of polyacrylamide water-absorbing resin, 0.5-10 parts of polar solvent and 65-130 parts of isocyanate component.
4. The production method according to claim 1, wherein in the step (2), the stirring time of the stirring is 5 to 60 seconds.
5. The production method according to claim 1, wherein in the step (2), the stirring rotation speed of the stirring is 40 to 450 rpm.
6. The production method according to claim 1, wherein in the step (2), the viscosity of the reaction foaming liquid at 20 ℃ is 0.11 to 6.05Pa · s.
7. The method according to claim 1, wherein in the step (3), the foaming temperature of the foaming is 15 to 150 ℃ and the foaming time is 1 to 60 min.
8. The structure-function integrated water-absorbent porous composite material produced by the production method according to any one of claims 1 to 7.
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| CN113736058B (en) * | 2021-09-27 | 2023-01-31 | 航天特种材料及工艺技术研究所 | Water-absorbing foam material and preparation method thereof |
| CN113912817A (en) * | 2021-11-18 | 2022-01-11 | 中电保力（北京）科技有限公司 | Water-swelling and water-blocking filling material and preparation method thereof |
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