CN117165064A - Water-swelling self-repairing elastomer material and preparation method and application thereof - Google Patents
Water-swelling self-repairing elastomer material and preparation method and application thereof Download PDFInfo
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- Sealing Material Composition (AREA)
Abstract
The invention relates to a water-swelling elastomer material, a preparation method and application thereof, wherein the preparation method comprises the following steps: firstly, reacting perfluoropolyether glycol with isophorone diisocyanate to obtain a prepolymer; then carrying out chain extension reaction on the prepolymer and 2, 6-diaminopyridine to obtain a PU-DAP prepolymer; finally, the PU-DAP prepolymer and Fe 3+ High suctionMixing and reacting the water resin filler, and curing to obtain the water-swelling self-repairing elastomer material; the obtained material can be used for preparing an underwater self-repairing expansion sealing structure. Compared with the prior art, the preparation process is economical and practical, has simple preparation process and low cost, does not need special equipment and harsh conditions, is convenient for large-scale production, and has extremely high practical value.
Description
Technical Field
The invention belongs to the technical field of sealing structures, and relates to a water-absorbing expansion elastomer material, a preparation method thereof and application thereof in an underwater self-repairing expansion sealing structure.
Background
In some engineering manufacturing fields, especially construction sites related to water such as river-sea engineering, underground water engineering, deep sea engineering and the like, the water cannot be artificially and regularly intervened by substances such as soil, sand, trees and the like. The water consists of a plurality of molecules with extremely small volumes, and is characterized in that the molecules are acted by gravity to perform the action of flowing water downwards, no matter how small pores exist, only the gaps exist to pass through water molecules, the infiltration over a long period of time results in large areas of water penetration, which is very unfriendly to some machines requiring a dry working environment and also very unfriendly to some metal devices.
In large-scale construction works, most of the machines are made of metal and alloy materials, and the surfaces of the machines are coated with anti-corrosion coatings, so that the machines are easy to rub with rock, soil, stones and the like when in use, and the coatings have extremely low service lives under the dual effects of corrosion and scratch, so that the sealing materials are particularly important in the aspect of isolating water interference. The simple sealing material is still not ideal in service life when being subjected to long-time soaking erosion of natural water, so the idea of 'controlling water by water' is adopted, and the water absorption expansion mode of the elastomer material is utilized, because the material is in a water environment for a long time, the material is in a water absorption saturated state for a long time, and the volume expansion is carried out in a fixed space to achieve the effect of water absorption sealing.
The elastomer material is added with a certain water-absorbing filler to add performance to the whole material, and the most common water-absorbing filler such as super absorbent resin (SAP) or cross-linked sodium polyacrylate (PAANa) is added, wherein the common water-absorbing resin has good water-absorbing effect, such as sodium polyacrylate, polyacrylamide and the like, and can absorb hundreds of times of water under the condition of full water absorption. When the water-absorbing material has defects such as fracture and cavity, the fracture is further expanded after repeated water-absorbing expansion, and the sealing performance of the water-absorbing elastomer material is obviously reduced.
Disclosure of Invention
The invention aims to provide a water-swelling self-repairing elastomer material, a preparation method thereof and application thereof in an underwater self-repairing swelling sealing structure.
The aim of the invention can be achieved by the following technical scheme:
a self-repairing water-swelling elastomer material is prepared from the prepolymer prepared from perfluoro polyether glycol (PFPE) and isophorone diisocyanate (IPDI) through chain extension reaction with 2, 6-Diaminopyridine (DAP) and Fe 3+ Synthesizing a self-repairing material, and adding an elastomer material generated by a super absorbent resin filler (SAP); the SAP is synthesized by Acrylic Acid (AA), acrylamide (AM) and sodium hydroxide (NaOH) in a reverse suspension polymerization mode.
Specifically, the preparation method of the material comprises the following steps:
s1: reacting perfluoropolyether diol (PFPE) with isophorone diisocyanate (IPDI) to obtain a prepolymer;
s2: carrying out chain extension reaction on the prepolymer and 2, 6-Diaminopyridine (DAP) to obtain a PU-DAP prepolymer;
s3: the PU-DAP prepolymer and Fe 3+ And mixing and reacting the super absorbent resin filler (SAP) and curing to obtain the water-swelling self-repairing elastomer material.
Further, in step S1, the reaction process includes: the perfluoropolyether glycol is mixed with isophorone diisocyanate, and stirred for 2 to 6 hours at 50 to 70 ℃ in an inert gas atmosphere to obtain the prepolymer.
In some specific embodiments, the inert gas used includes nitrogen or an inert gas of helium, neon, argon, krypton, xenon, or the like.
Further, in the step S1, the mass ratio of the perfluoropolyether glycol to isophorone diisocyanate is (20-45): 3-8.
Further, the reaction process also comprises the step of adding dibutyl tin dilaurate, wherein the adding amount of the dibutyl tin dilaurate is 1 drop/(12-20 g of perfluoropolyether glycol).
Further, in the step S2, the dosage of the 2, 6-diaminopyridine is 1-2 g/(18-24 g) of perfluoropolyether glycol; the reaction conditions of the chain extension reaction include: the reaction temperature is 40-80 ℃ and the reaction time is 10-20 min.
Further, in step S3, the Fe 3+ The addition amount of (2) is 0.005-0.007 mol/(18-24 g) of perfluor polyether glycol, and the perfluor polyether glycol is added in the form of ferric salt; the super absorbent resin filler is prepared from Acrylic Acid (AA), acrylamide (AM) and NaOH by adopting a reverse suspension polymerization method, and the preparation method comprises the following steps: adding acrylic acid and sodium hydroxide sodium acrylate solution after reaction into oil phase (cyclohexane, dispersant span60, acrylamide, ammonium persulfate and cross-linking agent-N, N-methylene bisacrylamide), stirring at a rate of 3-4 drops per second for reaction for 3 hours at 70 ℃, adding acetone 1 hour before the reaction is finished, washing the obtained product with absolute ethyl alcohol, and drying to obtain super absorbent resin (SAP); wherein, the feeding ratio of cyclohexane, dispersant span60, acrylamide, ammonium persulfate, cross-linking agent, acrylic acid, sodium hydroxide and acetone is 150-200mL:1-2g:3-5g:0.01-1g:0.004-0.011g:5-15mL:3-8g:3-8mL.
The amount of the Gao Xishui resin filler is 2-3 g/(18-24 g) of the perfluoropolyether glycol.
Further, in step S3, the reaction conditions of the mixing reaction include: the reaction temperature is 40-80 ℃ and the reaction time is 30-60 min.
Further, in step S3, the curing conditions include: vacuum drying at 60-80deg.C.
A self-repairing water-swelling elastomer material is prepared by the method.
The application of the water-swelling self-repairing elastomer material comprises the step of using the material to prepare an underwater self-repairing swelling sealing structure.
The invention provides a self-repairing water-absorbing expansion material, which is characterized in that in a specific volume space, the material undergoes water absorption expansion, the volume is greatly changed, the general volume expansion rate is 200% -600%, at the moment, the base materials at two ends of a fracture can stress and squeeze the fracture, external force can be applied to the two ends of the fracture, and then the defects of the material can be self-repaired under the action of the external force. The repair efficiency of the polyurethane material is larger than that of the rubber elastomer material, and particularly the repair efficiency of the common self-repair rubber material is generally proportional to the temperature, for example, the natural rubber self-repair temperature is 30-40 ℃, the epoxy natural rubber self-repair temperature is generally maintained at 40-80 ℃ when the epoxy degree is increased, and the silicon rubber self-repair temperature is relatively suitable but the mechanical property is generally poor.
The polyurethane material adopts the combination of the polyol and the isocyanate, and has a large selection space, and the polyether type is required to be selected from the polyether type polyol and the polyester type polyol because the application environment of the polyurethane material is the self-repairing water-swelling polyurethane elastomer. The polyether polyols commonly used in the market, such as polyether P123, polyether F127, polyether L64 and the like, are block copolymers composed of polyethylene glycol (PEG) and polypropylene glycol (PPG), wherein hydroxyl (-OH) is enriched, and the hydroxyl has great advantages on the water absorption performance of the elastomer material as a hydrophilic group; the diisocyanates are typically Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI),The linear Hexamethylene Diisocyanate (HDI) used in the invention can better form a linear high polymer due to the linear structure of the linear Hexamethylene Diisocyanate (HDI) and dihydric alcohols such as PEG, PPG and the like; the reaction rate of the IPDI and hydroxyl used in the invention is 4-5 times faster than that of HDI, and the reaction activity is 8-10 times higher than that of HDI. When reacting polyether polyols with diisocyanates to form polyurethane Prepolymers (PU), the prepolymer overall molecular chain is extended with chain extenders, typically amine and alcohol chain extenders, amino (-NH) groups in a hydrophilic comparison 2 ) > hydroxy (-OH), and amino (-NH) groups are also frequently used in the most common metal coordination scheme for repair 2 ) The chain extender adopted by the invention is 2, 6-Diaminopyridine (DAP), and two amino groups contained in the chain extender can perform a good chain extending effect and can also be used as an important participant of self-repairing.
The invention adopts a perfluoro polyether glycol (PFPE) composed of C-F bonds and multiple C-F bonds with dipole-dipole interaction capability. The self-repairing is promoted by adopting the common use of dipole-dipole interaction and metal coordination, the metal coordination is greatly influenced by water under water, the self-repairing efficiency is lower, the dipole-dipole interaction of the C-F bond is slightly influenced by water, and the self-repairing can be carried out even under extremely short severe water quality.
Compared with the prior art, the invention has the following characteristics:
1) The self-repairing water-absorbing sealing material is a fluorinated polyurethane material formed by PFPE, IPDI, DAP reaction and contains FeCl 3 ·6H 2 The organic solvent of O and SAP reacts to obtain the product; the PFPE is used for increasing the hydrophilicity of the polyurethane elastomer, facilitating the polyurethane elastomer to expand after water absorption and utilizing dipole-dipole interaction between C-F bonds to positively promote self-repairing behavior; wherein the SAP is prepared from AA, AM, naOH under ammonium persulfate initiation, span-60 dispersion; wherein Fe is 3+ The metal coordination effect can be formed with the bond in the DAP, so that the remarkable self-repairing effect (80-96%) is achieved; wherein IPDI is used as a hard segment of the diisocyanate polyurethane material to well endow the material with mechanical properties; wherein two amino groups of DAP can beThe two-dimensional chain extender plays a role of the chain extender in the polyurethane synthesis process, and can better show the water swelling performance and the self-repairing performance of polyurethane; in general, the self-repairing water-swelling sealing material has excellent self-repairing performance, tensile performance, mechanical performance, water-swelling performance and sealing effect, and the main outstanding characteristics can be used for underwater self-repairing, so that the self-repairing water-swelling sealing material has a large application prospect in some engineering sealing fields;
2) The preparation process is economical and practical, simple in preparation process, low in cost, free of special equipment and harsh conditions, convenient for large-scale production and high in practical value;
3) Chinese patent CN111826075B discloses self-repairing organic fluorosilicone modified polyurethane waterproof paint and a preparation method thereof, wherein the self-repairing of the paint is carried out by utilizing dipole-dipole interaction of perfluoro polyether C-F bond, compared with the self-repairing of the paint by adopting dipole-dipole interaction and Fe 3+ The metal coordination effect double self-repairing reaction is used for self-repairing, so that the repairing efficiency is greatly ensured, the dipole-dipole interaction is taken as a leading part under water, the metal coordination is taken as an auxiliary part under the water, the metal coordination is taken as a leading part under a dry environment, and the lower limit of the self-repairing efficiency under different environments is ensured. Meanwhile, the patent is mainly focused on modification by utilizing the organosilicon fluorine modified polyurethane, and the invention adopts raw materials capable of promoting a self-repairing network (the soft segment selects perfluoropolyether and the chain extender selects diaminopyridine) on the selection of the soft segment and the chain extender respectively during polyurethane synthesis, so as to achieve a dual self-repairing network. In addition, the waterproof coating is mainly applied to waterproof coatings, the waterproof coating is mainly applied to water-absorbing sealing materials, and can be effectively applied to subway development, tunnel excavation, large-scale shield tunneling machines and the like, and the application fields of the waterproof coating and the waterproof sealing materials are completely different. Finally, the main body of the material is an elastomer material biased to rubber and plastics, and is quite different from the waterproof coating of the patent, including but not limited to aspects of application scenes, physical states, storage modes and the like.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The preparation method of the water-swelling self-repairing elastomer material comprises the following steps:
s1: reacting perfluoropolyether glycol with isophorone diisocyanate in an inert gas atmosphere at 50-70 ℃ under the action of an organotin catalyst for 2-6 hours to obtain a prepolymer;
wherein the inert gas comprises nitrogen or helium, neon, argon, krypton, xenon and other inert gases; the mass ratio of the perfluoropolyether glycol to the isophorone diisocyanate is (20-45): 3-8; the organotin catalyst is dibutyl tin dilaurate, and the dosage is 1 drop/(12-20 g of perfluoropolyether glycol);
in some specific embodiments, the perfluoropolyether diol is pretreated and then reacted, the pretreatment comprising: vacuum dewatering at 120-160 deg.c for 1-3 hr;
s2: carrying out chain extension reaction on the prepolymer and 2, 6-diaminopyridine at 40-80 ℃ for 10-20 min to obtain PU-DAP prepolymer;
wherein, the dosage of the 2, 6-diaminopyridine is 1-2 g/(18-24 g) of perfluoropolyether glycol;
in some specific embodiments, 2, 6-diaminopyridine is first formulated with N, N-Dimethylformamide (DMF) to form a DAP solution, and then mixed with the prepolymer; preferably, the mass ratio of the 2, 6-diaminopyridine to the N, N-dimethylformamide is 1 (10-100), more preferably, the feeding ratio of the 2, 6-diaminopyridine to the N, N-dimethylformamide is (1-6) g (20-50) mL;
in some specific embodiments, the prepolymer is formulated with chloroform to form a mixed system and then mixed with 2, 6-diaminopyridine; the prepolymer is dissolved to achieve better reaction effect, so that the charging ratio can be determined according to the dissolution condition of the solvent; preferably, the mass ratio of the prepolymer to the chloroform is 1 (3-15); more preferably, the feeding ratio of the prepolymer to the chloroform is (40-70) g (300-800) mL;
in some specific embodiments, the mass ratio of the DAP solution to the mixed system is (50-90): 20-60;
s3: the PU-DAP prepolymer and Fe 3+ Mixing the high water absorption resin filler and reacting at 40-80 DEG CThe water-swelling self-repairing elastomer material is obtained after 30 to 60 minutes and then vacuum drying and curing at the temperature of between 60 and 80 ℃;
wherein Fe is 3+ The amount of (2) added is 0.005-0.007 mol/(18-24) g of perfluoropolyether diol, added as iron ion salt, preferably FeCl 3 ·6H 2 O; the super absorbent resin filler is prepared from acrylic acid, acrylamide and NaOH by adopting a reverse suspension polymerization method, and the preparation method (the preparation method can be referred to as intelligent, strict prescription, ji Lincheng, and the like; the influence of the compound pore-forming agent on the liquid absorption performance of the super absorbent resin [ J)]The synthetic resin and plastic, 2022,39 (1): 4.) include: adding acrylic acid and sodium hydroxide sodium acrylate solution after reaction into oil phase (cyclohexane, dispersant span60, acrylamide, ammonium persulfate and cross-linking agent-N, N-methylene bisacrylamide), stirring at a rate of 3-4 drops per second for reaction for 3 hours at 70 ℃, adding acetone 1 hour before the reaction is finished, washing the obtained product with absolute ethyl alcohol, and drying to obtain super absorbent resin (SAP); wherein, the feeding ratio of cyclohexane, dispersant span60, acrylamide, ammonium persulfate, cross-linking agent, acrylic acid, sodium hydroxide and acetone is 150-200mL:1-2g:3-5g:0.01-1g:0.004-0.011g:5-15mL:3-8g:3-8mL.
The dosage of the super absorbent resin filler is 1-10% of the mass of 2-3 g/(18-24 g) of perfluor polyether glycol or polyurethane;
in some specific embodiments, fe 3+ Firstly preparing ferric salt solution, and then mixing with PU-DAP prepolymer and super absorbent resin filler; preferably FeCl in iron salt solution 3 ·6H 2 The mass ratio of O to the solvent methanol is 1 (50-200); still more preferably, feCl 3 ·6H 2 The feeding ratio of O and the solvent methanol is (1-5) g (100-600) mL;
in some specific embodiments, the iron salt solution and the PU-DAP prepolymer are stirred and mixed, and SAP with the mass of 1-5% of the solution is added into the solution, and the solution is introduced into a polytetrafluoroethylene mould for curing, so that the final sealing material is obtained.
The application of the water-swelling self-repairing elastomer material comprises the step of using the material to prepare water sealing structures such as sealing rings, sealing plugs and the like, and particularly to prepare underwater self-repairing swelling sealing structures.
The following examples are given with the above technical solutions of the present invention as a premise, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
In the following examples, the super absorbent resin filler is prepared from Acrylic Acid (AA), acrylamide (AM) and NaOH by a reverse suspension polymerization method, and the preparation method comprises: 10mL of acrylic acid and 4g of sodium hydroxide sodium acrylate solution after reaction are added into oil phase (195 mL of cyclohexane, 1.2g of dispersing agent, 4.5g of acrylamide, 0.1g of ammonium persulfate and 0.008g of cross-linking agent-N, N-methylene bisacrylamide), stirred at the room temperature for 3h at the rate of 3-4 drops per second, 5mL of acetone is quickly added 1h before the reaction is finished, and the obtained product is washed by absolute ethyl alcohol and dried to obtain super absorbent resin (SAP);
PFPE or PFPE-1000 is available from Shanghai Taitan technologies, inc. 4119888FA (trade mark) and PEG or PEG-2000 is available from Shanghai Milin Biochemical technologies, inc. P815609 (trade mark).
When the reagent is added in drops, the volume is generally determined as known in the art, i.e., 20-25 drops are considered to be 1mL.
Example 1
Preparation of self-repairing water-absorbing sealing material:
1) 20g of PFPE-1000 is dehydrated in vacuum at 120 ℃ for 2 hours, 3.164g of IPDI and 1 drop of dibutyltin dilaurate are added under the nitrogen atmosphere at 60 ℃ and stirred for 2 hours to obtain pale yellow colloidal semisolid prepolymer PU; mixing the semi-solid prepolymer PU with TCM (traditional Chinese medicine) at a feeding ratio of 50g to 500mL to obtain a semi-solid prepolymer PU system;
2) 1.09g of DAP was dissolved in 20mL of N, N-dimethylformamide to obtain a DAP solution; adding DAP solution into the semi-solid prepolymer PU system in the step 1), putting into an oven, stirring at 60 ℃ for 10min until the reaction is complete, turning the reaction system from black to yellow, and finally, obtaining PU-DAP after drying;
3) 1.35g FeCl 3 ·6H 2 O was dissolved in 135mL of methanol, 2g of SAP was added thereto, and the mixed solution was added to a solution of 200mL of chloroformIn the dissolved PU-DAP solution system, the reaction is carried out for 30min at 60 ℃, the product is guided into a polytetrafluoroethylene mould, and the self-repairing water-swelling elastomer PFPE-DAP/Fe is obtained by room temperature curing 3+ -SAP。
The data of the tensile strength, the elongation at break, the 24-hour self-healing rate, the water-absorbing volume expansion rate, the water-absorbing expansion rate and the underwater self-repairing efficiency of the self-repairing water-absorbing sealing material prepared in this example are shown in Table 1.
Comparative example 1
Preparation of comparative water-absorbing sealing material:
20g of PEG-2000 were dehydrated in vacuo (the same procedure as in example 1) and reacted with 2.16g of IPDI (reaction temperature 60 ℃ C., nitrogen atmosphere, 2 h) and then uniformly mixed with 3g of DAP, reacted at 60 ℃ C. For 10min, followed by addition of a solution consisting of 1.5g of FeCl 3 ·6H 2 Mixing the compound solution composed of O, 1g SAP and 130mL methanol for 1h, pouring into a polytetrafluoroethylene mould, solidifying and drying at room temperature to obtain the comparative water-absorbing sealing material PEG-DAP/Fe 3+ -SAP。
The tensile strength, elongation at break, 24-hour self-healing rate, water-absorbing volume expansion rate, water-absorbing expansion rate, and underwater self-repairing efficiency data of the comparative water-absorbing sealing material prepared in this comparative example are shown in table 1.
Example 2
Preparation of self-repairing water-absorbing sealing material:
1) Vacuum dehydrating 18g of PFPE at 120 ℃ for 2 hours, adding 2.843g of IPDI and 1 drop of dibutyltin dilaurate under nitrogen atmosphere at 60 ℃ and stirring for reaction for 3 hours to obtain white yellowish colloidal semisolid prepolymer PU; mixing the semi-solid prepolymer PU with TCM (traditional Chinese medicine) at a feeding ratio of 50g to 500mL to obtain a semi-solid prepolymer PU system;
2) 1.17g of DAP was dissolved in 30mL of N, N-dimethylformamide to obtain a DAP solution; adding DAP solution into the semi-solid prepolymer PU system in the step 1), putting into an oven, stirring at 60 ℃ for 10min until the reaction is complete, turning the reaction system from black to yellow, and finally, obtaining the PU-DAP prepolymer after drying;
3) 1.76g FeCl 3 ·6H 2 O was dissolved in 225mL of methanol, to which was addedAdding 2.8g SAP, adding the mixed solution into a PU-DAP solution system dissolved by 260mL chloroform, reacting at 60 ℃ for 50min, introducing the product into a polytetrafluoroethylene mould, and curing at room temperature to obtain the self-repairing water-swelling elastomer PFPE-DAP/Fe 3+ -SAP。
The data of the tensile strength, the elongation at break, the 24-hour self-healing rate, the water-absorbing volume expansion rate, the water-absorbing expansion rate and the underwater self-repairing efficiency of the self-repairing water-absorbing sealing material prepared in this example are shown in Table 1.
Comparative example 2
Preparation of comparative water-absorbing sealing material:
20g of PFPE are dehydrated in vacuo (the same procedure as in example 2) and reacted with 2.4g of Hexamethylene Diisocyanate (HDI) (reaction temperature 60 ℃ C., nitrogen atmosphere, 2 h) and further reacted with 3g of DAP by mixing homogeneously at 60 ℃ C. For 10min, and a reaction mixture of 1.5g of FeCl is added 3 2.0g of SAP and 130mL of methanol are fully stirred for 1h, poured into a polytetrafluoroethylene mould, cured and dried at room temperature to obtain the contrast water-absorbing sealing material HDI-DAP/Fe 3+ -SAP。
The tensile strength, elongation at break, 24-hour self-healing rate, water-absorbing volume expansion rate, water-absorbing expansion rate, and underwater self-repairing efficiency data of the comparative water-absorbing sealing material prepared in this comparative example are shown in table 1.
Example 3
Preparation of self-repairing water-absorbing sealing material:
1) Vacuum dehydrating 24g of PFPE at 140 ℃ for 2 hours, adding 3.2g of IPDI and 2 drops of dibutyltin dilaurate under nitrogen atmosphere at 60 ℃ and stirring for reacting for 2 hours to obtain white yellowish colloidal semi-solid prepolymer PU; mixing the semi-solid prepolymer PU with TCM (traditional Chinese medicine) at a feeding ratio of 50g to 500mL to obtain a semi-solid prepolymer PU system;
2) Dissolving 1.8g of DAP in 36mL of N, N-dimethylformamide, adding the DAP solution into the system in the step 1), putting into a baking oven, stirring at 60 ℃ for 10min until the reaction is complete, turning the reaction system from black to yellow, and finally turning the reaction system into brown, and drying to obtain the PU-DAP prepolymer;
3) 1.68g FeCl 3 ·6H 2 O was dissolved in 200mL of methanol,adding 2.6g SAP into the mixture, adding the mixed solution into a PU-DAP solution system dissolved by 240mL of chloroform, reacting for 1h at 60 ℃, introducing the product into a polytetrafluoroethylene mould, and curing at room temperature to obtain the self-repairing water-swelling elastomer PFPE-DAP/Fe 3+ -SAP。
The data of the tensile strength, the elongation at break, the 24-hour self-healing rate, the water-absorbing volume expansion rate, the water-absorbing expansion rate and the underwater self-repairing efficiency of the self-repairing water-absorbing sealing material prepared in this example are shown in Table 1.
Comparative example 3
Preparation of comparative water-absorbing sealing material:
20g of PEG-PFPE (mass ratio 1:1) were dehydrated in vacuo at high temperature (the same method as in example 3) and reacted with 1.9g of IPDI and then uniformly mixed with 2.4g of DAP, and reacted at 60℃for 10 minutes, followed by addition of a solution consisting of 1.6g of FeCl 3 And 2.2g of SAP (super absorbent polymer) are mixed for 1h, poured into a polytetrafluoroethylene mould, cured and dried at room temperature to obtain the contrast water-absorbing sealing material PEG/PFPE-DAP/Fe 3+ -SAP。
The tensile strength, elongation at break, 24-hour self-healing rate, water-absorbing volume expansion rate, water-absorbing expansion rate, and underwater self-repairing efficiency data of the comparative water-absorbing sealing material prepared in this comparative example are shown in table 1.
TABLE 1 Performance test data for Water-absorbing sealing materials prepared in examples 1-3 and comparative examples 1-3 (GB/T18173.3-2014, water-swelling at 23℃for 72 h)
As can be seen from table 1, the difference between example 1 and comparative example 1: example 1 employed double self-repair while comparative example 1 employed metal coordination single self-repair, there was a large difference in repair efficiency. Differences between example 2 and comparative example 2: the difference between HDI and IPDI which are considered to be better in effect before is mainly compared, the strength is greatly different, and the repair efficiency is also different to a certain extent. Differences between example 3 and comparative example 3: the influence of the content of the perfluoropolyether glycol in the polyurethane soft segment on dipole-dipole interaction is mainly compared, the influence is quite large in the aspect of underwater repair efficiency, and the influence is small in the common environment.
Therefore, the self-repairing water-absorbing sealing material prepared by the invention has excellent self-healing performance, water-absorbing expansion performance, stretchability, water-absorbing rate and underwater self-repairing efficiency, can be used for engineering mechanical sealing in water environment, and has good application prospect in the field of long-time sealing.
TABLE 2 Infrared Spectroscopy test data for Water absorbing sealing materials prepared in examples 1-3 and comparative examples 1-3
As can be seen from Table 2, the shift in the position of the C.ident.N peak can determine Fe 3+ Successfully coordinates with pyridine; the movement of the DAP amide bands I and II can be used as Fe 3+ The successful coordination with the amide group N, O.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The preparation method of the water-swelling self-repairing elastomer material is characterized by comprising the following steps of:
s1: reacting perfluoropolyether glycol with isophorone diisocyanate to obtain a prepolymer;
s2: carrying out chain extension reaction on the prepolymer and 2, 6-diaminopyridine to obtain a PU-DAP prepolymer;
s3: the PU-DAP prepolymer and Fe 3+ Mixing and reacting the super absorbent resin filler, and curing to obtain the self-repairing water-swelling materialA multiple elastomer material.
2. The method for producing a water-swellable self-healing elastomer material according to claim 1, wherein in step S1, the reaction process includes: the perfluoropolyether glycol is mixed with isophorone diisocyanate, and stirred for 2 to 6 hours at 50 to 70 ℃ in an inert gas atmosphere to obtain the prepolymer.
3. The method for producing a water-swellable self-repairing elastomer material according to claim 1, wherein in step S1, the mass ratio of the perfluoropolyether diol to isophorone diisocyanate is (20-45): 3-8.
4. The method for preparing a self-repairing water-swelling elastomer material according to claim 2, wherein the reaction process further comprises adding dibutyl tin dilaurate, wherein the adding amount of the dibutyl tin dilaurate is 1 drop/(12-20 g of perfluoropolyether glycol).
5. The method for producing a water-swellable self-healing elastomer material according to claim 1, wherein in step S2, the amount of 2, 6-diaminopyridine is 1 to 2 g/(18 to 24) g of perfluoropolyether glycol; the reaction conditions of the chain extension reaction include: the reaction temperature is 40-80 ℃ and the reaction time is 10-20 min.
6. The method for producing a water-swellable self-healing elastomer material according to claim 1, wherein in step S2, the Fe 3+ The addition amount of (2) is 0.005-0.007 mol/(18-24 g) of perfluoropolyether glycol; the super absorbent resin filler is prepared from acrylic acid, acrylamide and NaOH by adopting a reverse suspension polymerization method, and the dosage is 2-3 g/(18-24 g) of perfluoropolyether glycol.
7. The method for producing a water-swellable self-healing elastomer material according to claim 1, wherein in step S2, the reaction conditions of the mixing reaction include: the reaction temperature is 40-80 ℃ and the reaction time is 30-60 min.
8. The method of producing a water-swellable self-healing elastomer material according to claim 1, wherein in step S2, the curing conditions include: vacuum drying at 60-80deg.C.
9. A water swellable self-healing elastomeric material prepared by the method of any one of claims 1 to 8.
10. Use of a water-swellable self-healing elastomer material according to claim 9 for the preparation of an underwater self-healing swelling seal.
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