CN107970868B - Externally-repaired and internally-fixed polyurea-based double-wall self-repairing microcapsule and preparation method thereof - Google Patents
Externally-repaired and internally-fixed polyurea-based double-wall self-repairing microcapsule and preparation method thereof Download PDFInfo
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Abstract
The invention provides a double-wall microcapsule system which takes aliphatic isocyanate-amino terminated polyether polymer as a repairing agent and takes an amino chain extender as a curing agent. The externally-repaired and internally-fixed polyurea-based double-wall self-repairing microcapsule comprises an inner-layer capsule wall and an outer-layer capsule wall; the inner layer capsule wall is coated with amino chain extender emulsion, and the outer layer capsule wall is coated with prepolymer emulsion; the inner-layer capsule wall and the outer-layer capsule wall are both polyurea prepared by an interfacial polymerization method, and the inner-layer capsule wall polyurea is obtained by the reaction of amino chain extender emulsion coated on the inner-layer capsule wall and prepolymer emulsion coated on the outer-layer capsule wall; the outer-layer capsule wall polyurea is obtained by the reaction of amino chain extender emulsion and prepolymer emulsion coated by the outer-layer capsule wall. The repairing agent and the curing agent are respectively stored in the inner capsule core and the outer capsule core, so that the problem that the contact rate of the repairing agent and the curing agent is low is solved, the repairing agent and the curing agent react quickly, the cracks are repaired quickly, and the application prospect is wide.
Description
Technical Field
The invention belongs to the field of organic composite materials, relates to a self-repairing material, and particularly relates to an externally-repaired and internally-fixed polyurea-based double-wall self-repairing microcapsule and a preparation method thereof, which are applied to the engineering fields of building disaster prevention and reduction, coating protection and repair and the like.
Background
With the continuous development of society, the building industry is also rapidly developed, and various high-rise buildings, bridges and roads are dug successively. Concrete is widely used in the construction field due to its excellent properties such as wide source, high compressive strength, easy construction, and high durability. However, concrete structures are highly susceptible to cracking during service life. With the change of the load and the passage of time, the cracks gradually expand into cracks and even extend to the surface to cause the cracking of the concrete material. After the through cracks are formed, the concrete is easily corroded and damaged by the external environment and various harmful factors, such as steel bar corrosion, carbonization, chloride ion corrosion, sulfate corrosion and the like, and finally the concrete material is cracked and damaged, so that the durability of the concrete material is seriously influenced, and even the irrecoverable loss of people and property caused by sudden building damage can be caused. Similarly, coatings have been widely used in the fields of infrastructure, aerospace, automotive construction, and the like as the most commonly used protective materials. However, the coating is easily affected by external factors in the service process to cause changes in the internal chemical structure, which causes microcracks with different sizes and local damage and greatly reduces the mechanical property of the coating, and the microcracks in the coating are continuously generated and collected to finally cause the coating to be peeled off, so that the effective protection of the base material cannot be realized. Since these microcrack damage is difficult to detect visually, it is often difficult to achieve the desired results with conventional repair methods. Therefore, the influence of micro-cracks on the service performance of materials is receiving more and more attention. The traditional repair technical method mainly comprises a surface repair method, a local repair method and a grouting method, wherein the surface crack and the local crack are repaired, the internal micro-crack of the matrix cannot be repaired, the temporary solution and the permanent solution are treated, the repair material cannot resist the corrosion of the marine environment, and the regeneration of the crack is difficult to control effectively.
In 2001, White et al first published an article on polymer self-healing technology in the journal of natural science, so that the self-healing technology was widely used. Under the technical background, researchers begin to research self-repairing of concrete structures in an active mode through the principle of bionic self-repairing. When the concrete structure has cracks, the additive is forced to crack under the action of the microcracks by virtue of capillary force to release the repairing agent and enter the cracks, and the cracks are repaired and prevented from further growing, so that an active repairing network system is formed in the concrete. The microcapsule self-repairing technology is an important component of a self-repairing concrete material structure, and has a great application prospect in many aspects of civil engineering construction, repair and the like in the future. The method does not need additional manual monitoring and high cost required by surface maintenance, prolongs the service life of the concrete structure and saves part of the operation expense of the building materials.
Currently, microcapsule self-repair systems mainly include single-wall microcapsule repair systems, single-wall double-microcapsule repair systems, and double-wall microcapsule systems. Early research focused primarily on single-wall microcapsule systems that encapsulated the healing agent in microcapsules with a catalyst in the matrix being healed. The single-wall microcapsule system mainly comprises a DCPD-Grubbs system, a urea-formaldehyde resin (UF) system, an inner-coated dicyclopentadiene (DCPD) system and an epoxy resin curing agent system. However, the above system has the following problems: (1) the thermochemical stability of the microcapsule is poor; (2) the reaction curing film forming speed is slow, and cracks cannot be effectively filled; (3) the catalyst is expensive and easy to deactivate; (4) the self-repairing system has a narrow application range and can only be limited in a certain base material. The invention patent ZL200710044358.4 discloses polyurea microcapsules and a preparation method thereof. The invention provides a polyurea microcapsule and a preparation method thereof, wherein the preparation method comprises the following steps: (1) adding an organic phase containing diphenylmethane diisocyanate into a water phase containing a surfactant, and stirring and emulsifying to obtain emulsion A; (2) adding diethylenetriamine into an aqueous solution containing a surfactant to obtain a continuous phase solution B; (3) and adding the continuous phase solution B into the emulsion A, and initiating an interfacial polymerization reaction on an oil-water interface to obtain a suspension containing the polyurea microcapsules. The polyurea wall material of the microcapsule system is generated by directly carrying out interfacial polymerization reaction on isocyanate and an amino compound, so that the problem of low curing and film forming speed is solved; however, the linear polyurea capsule wall structure obtained by the system has poor performance, and the protection effect on the core material cannot be realized. Secondly, the invention adopts oil-in-water type emulsion in the preparation process of isocyanate emulsion, which leads to premature failure of isocyanate due to the sensitivity of the isocyanate to water, thereby being unfavorable for the subsequent reaction to generate polyurea microcapsule. In addition, the polyurea microcapsule is of a single-wall structure, and the problems of low repair efficiency of a single-wall microcapsule system and the like still exist.
Subsequent studies have shown a single wall double microcapsule system comprising two microcapsules, one coating repair agent and one coating curing agent. The single-wall double-microcapsule system solves the following problems of the single-wall microcapsule system to a certain extent: (1) catalysts need to be added to the substrate to achieve self-healing; (2) the catalyst is easy to deactivate prematurely to bring about poor repairing effect; (3) the production cost is too high. However, the single-wall double-microcapsule system still has the problems that the repairing agent and the curing agent cannot be contacted simultaneously, the repairing cannot be rapidly carried out, the crack response mechanism is complex and the like. In these technical contexts, double-walled microcapsule systems have been reported by researchers. Compared with a single-wall microcapsule system, the double-wall coated microcapsule system has better stability, so that the probability of inactivation of the repairing agent and the curing agent is reduced; meanwhile, the contact probability of the repairing agent and the catalyst is greatly increased, and the adverse effect of excessive adding of the repairing agent and the catalyst on the concrete performance is avoided.
The invention patent ZL201110146711.6 discloses a preparation method of an enhanced epoxy resin/curing agent double-wall microcapsule. The application provides a preparation method of a double-wall self-repairing microcapsule, which compounds epoxy resin or epoxy resin and carbon nano tubes as an inner-layer capsule core repairing agent and takes a curing agent as an outer-layer capsule core. However, the repair agent epoxy resin in the double-wall microcapsule system prepared by the method can only exert good repair effect under the condition of heating, and can not realize quick and effective repair at normal temperature; in addition, the manufacturing process flow of the adopted polyurea-formaldehyde capsule wall is complex, and the cost and the difficulty of practical application are increased.
The invention patent ZL200510014698.3 discloses a preparation method of a polyurea-urea formaldehyde resin double-layer microcapsule. The method adopts an interfacial polymerization method, and takes glutaraldehyde modified polyamine compound and diisocyanate compound as monomers to carry out interfacial polymerization to prepare polyurea microcapsules; the polyurea microcapsule is used as an inner core, urea and formaldehyde are used as monomers, and a urea-formaldehyde resin shell is generated under an acidic condition by adopting an in-situ polymerization method to obtain the polyurea-urea-formaldehyde double-layer microcapsule. In the invention, two different systems of interfacial polymerization and in-situ polymerization are respectively selected in the two preparation processes, and the in-situ polymerization method has certain requirements on the solubility of the core material and the generated capsule wall material, so that the types of reagents are limited, the process is more complicated, and the operation difficulty is increased. Secondly, the invention adopts oil-in-water type emulsion in the preparation process of isocyanate emulsion, which leads to premature failure of isocyanate due to the sensitivity of the isocyanate to water, thereby being unfavorable for the subsequent reaction to generate polyurea microcapsule. In addition, the invention adopts toluene diisocyanate with high toxicity and volatility, which is very easy to cause great pollution to the environment; in addition, in the preparation process, the synthesis of the microcapsule is required to be realized by continuously adjusting the pH value, the excessive dependence on different pH values is shown, and the complexity of the operation is further increased.
Disclosure of Invention
Aiming at the technical problems of the existing self-repairing double-wall microcapsule system, the invention provides the double-wall microcapsule system which takes aliphatic isocyanate-terminated amino polyether polymer as a repairing agent and takes an amino chain extender as a curing agent. The repairing agent and the curing agent are respectively stored in the inner capsule core and the outer capsule core, so that the problem that the contact rate of the repairing agent and the curing agent is low is solved, the repairing agent and the curing agent react quickly, the cracks are repaired quickly, and the application prospect is wide.
The technical scheme of the invention is as follows:
the externally-repaired and internally-fixed polyurea-based double-wall self-repairing microcapsule comprises an inner-layer capsule wall and an outer-layer capsule wall; the inner layer capsule wall is coated with amino chain extender emulsion, and the outer layer capsule wall is coated with prepolymer emulsion; the inner-layer capsule wall and the outer-layer capsule wall are both polyurea prepared by an interfacial polymerization method, and the inner-layer capsule wall polyurea is obtained by the reaction of amino chain extender emulsion coated on the inner-layer capsule wall and prepolymer emulsion coated on the outer-layer capsule wall; the outer-layer capsule wall polyurea is obtained by the reaction of amino chain extender emulsion and prepolymer emulsion coated by the outer-layer capsule wall. The preparation method of the externally-repaired and internally-fixed polyurea-based double-wall self-repairing microcapsule comprises the following steps:
(1) preparing a prepolymer emulsion: uniformly mixing a proper amount of aliphatic isocyanate repairing agent, amino-terminated polyether, emulsifier and solvent under high-speed stirring to prepare prepolymer emulsion; the method specifically comprises the following steps: uniformly mixing the aliphatic isocyanate repairing agent and the amino-terminated polyether according to the mass ratio of 1:1-1:5 to obtain a prepolymer; stirring uniformly at the rotating speed of 2000-3500rmp, adding an emulsifier and a solvent, and keeping the temperature of 60-70 ℃ for 2-3h at the rotating speed of 1500-3500rpm to obtain a prepolymer emulsion; the amount of the emulsifier is 5% -10% of the mass of the prepolymer, and the mass ratio of the emulsifier to the solvent is 1:150-1: 160.
Wherein the NCO group content of the aliphatic isocyanate repairing agent is 3% -12%, and the average functionality is 1.5-5.0; the aliphatic isocyanate repairing agent is an allophanate or HDI trimer system of isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), 1, 4-cyclohexane diisocyanate, cyclohexylmethane-4, 4-diisocyanate and 1, 6-hexamethylene diisocyanate; the amino-terminated polyether is polyether amine D400, polyether amine D230, polyether amine D2000, 3, 5-dimethylthiotoluene-2, 6-diamine, 3, 5-diethyltoluene-2, 4-diamine, 3, 5-dimethylthiotoluene-2, 4-diamine, 1, 4-butanediamine or 1, 6-hexanediamine.
(2) Preparing amino chain extender emulsion: uniformly mixing the amino chain extender, the solvent and the emulsifier under high-speed stirring to prepare amino chain extender emulsion; the method specifically comprises the following steps: taking a proper amount of emulsifier and solvent, and stirring at the rotating speed of 1000-; the mass ratio of the emulsifier to the solvent is 1:40-1: 50; adding an amino chain extender, and stirring at the rotating speed of 1000-; the amount of the emulsifier is 10-20% of the mass of the amino chain extender.
Wherein the amine chain extender is diethyl toluene diamine, dimethyl sulfur toluene diamine, N ' -dialkyl methyl diphenylamine, cyclohexane diamine, chlorinated MDH, ethylene diamine, 1, 3-diaminopropane, 1, 4-diaminobutane, diethylene triamine, pentaethylene hexamine, hexaethylene diamine, tetraethylene pentamine, pentaethylene hexamine, polyether amine D400, polyether amine D230, ethylene diamine or 3,3' -4,4' -diamino-diphenylmethane MOCA.
(3) Preparing polyurea encapsulated double-wall microcapsules: dropwise adding the prepolymer emulsion prepared in the step (1) into the amino chain extender emulsion prepared in the step (2) to synthesize a microcapsule inner wall material to form a single-wall microcapsule emulsion; and then adding an emulsifier, a solvent and an excessive prepolymer emulsion into the emulsion, and dripping an amino chain extender emulsion after emulsification is finished to synthesize a microcapsule outer wall material to form a double-wall microcapsule emulsion. The method specifically comprises the following steps:
① the amino chain extender emulsion and the prepolymer emulsion are mixed evenly according to the mass ratio of 1.5:1-3:1, and the mixture is kept warm for 2-3h at 60-70 ℃ under the rotating speed of 800 plus 2500rmp to form the single-wall microcapsule emulsion, the principle is that the prepolymer emulsion droplets are adsorbed on the surface of the amino chain extender emulsion droplets, and the synthesis of the microcapsule inner wall material is completed through the polymerization reaction of the prepolymer and the amino chain extender to form the single-wall microcapsule emulsion.
② adding a proper amount of emulsifier, solvent and excessive prepolymer emulsion into the system obtained in step ① for emulsification to form a single-wall microcapsule-prepolymer composite emulsified liquid drop system, wherein the mass fraction of the emulsifier in the single-wall microcapsule-prepolymer composite emulsified liquid drop system is 4-6%, and the mass ratio of the emulsifier to the solvent is1:140-1:160(ii) a Dripping amino chain extender emulsion after emulsification is finished, wherein the mass ratio of the amino chain extender emulsion to the prepolymer emulsion is1:1.2-1:3；Keeping the temperature at 60-70 ℃ for 2-3h at the rotating speed of 1000-3500rmp to form double-wall microcapsule emulsion; the principle is as follows: and adsorbing the emulsion droplets of the amino chain extender on the surfaces of the emulsion droplets of the prepolymer, and completing the synthesis of the outer wall material of the microcapsule through the polymerization reaction of the prepolymer and the amino chain extender.
③, centrifuging, drying and washing the double-wall microcapsule emulsion to obtain the polyurea encapsulated external repair internal fixation type polyurea-based double-wall self-repairing microcapsule with the particle size distribution of 10-200 μm, step ②, when preparing the double-wall microcapsule emulsion, adding chain extender emulsion and 1-5 drops of defoaming agent, wherein the defoaming agent is n-butyl alcohol, 1, 4-butanediol, polyoxypropylene polyoxyethylene glycerol ether or polydimethylsiloxane.
The emulsifier in the above step is sodium dodecyl benzene sulfonate, OP-10, octadecyl alcohol polyoxyethylene ether, Arabic gum, polyoxyethylene ether, fatty ammonia polyoxyethylene ether or polyvinyl alcohol; the solvent is ethyl acetate, acetone, cyclohexane, cyclopentane, toluene or chlorobenzene.
The self-repairing system of the polyurea-based double-wall microcapsule is adopted, and the mass fraction of the polyurea-based double-wall microcapsule in the self-repairing system is 5-18%; the self-repairing system is self-repairing concrete or a self-repairing coating. The invention has the beneficial effects that:
(1) by adopting the double-wall microcapsule structure, the repairing agent and the chain extender can simultaneously exist in the microcapsule in a liquid state before microcracks appear on the substrate, so that the problems of poor thermochemical stability, easy inactivation and the like of other microcapsules are effectively solved;
(2) the aliphatic isocyanate-amino terminated polyether polymer adopted by the invention can quickly generate a curing reaction when meeting an amino chain extender, and the problems of low curing film forming speed and incapability of effectively preventing crack propagation are solved;
(3) the capsule wall adopted by the invention is a polyurea shell layer which has excellent physical and chemical properties, the strength of the shell layer can realize effective wrapping of the capsule core material, and the strength of concrete can not be obviously influenced, so that the service life of concrete is prolonged while the repair is realized;
(4) the double-wall microcapsule structure provided by the invention can respond to cracks at normal temperature without heating in application, and can realize self-repairing of concrete.
Drawings
FIG. 1 is a schematic diagram of the structure of a double-walled microcapsule.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
the externally-repaired and internally-fixed polyurea-based double-wall self-repairing microcapsule comprises an inner-layer capsule wall and an outer-layer capsule wall; the inner layer capsule wall is coated with amino chain extender emulsion, and the outer layer capsule wall is coated with prepolymer emulsion; the inner-layer capsule wall and the outer-layer capsule wall are both polyurea prepared by an interfacial polymerization method, and the polyurea is obtained by the reaction of amino chain extender emulsion coated on the inner-layer capsule wall and prepolymer emulsion coated on the outer-layer capsule wall.
The preparation method of the externally-repaired and internally-fixed polyurea-based double-wall self-repairing microcapsule comprises the following steps:
(1) preparing a prepolymer emulsion: uniformly mixing an aliphatic isocyanate repairing agent isophorone diisocyanate (IPDI) and amino-terminated polyether amine D400 according to a mass ratio of 1:1 to obtain a prepolymer; stirring uniformly at the rotating speed of 2200rmp, adding an emulsifier and a solvent, and keeping the temperature at 65 ℃ for 2-3h at the rotating speed of 2000rpm to obtain a prepolymer emulsion; the amount of the emulsifier is 10% of the mass of the prepolymer, and the mass ratio of the emulsifier to the solvent is 1: 150.
(2) Preparing amino chain extender emulsion: taking a proper amount of emulsifier and solvent, and stirring at the rotating speed of 1200rmp until the emulsifier and the solvent are uniformly mixed; the mass ratio of the emulsifier to the solvent is 1: 44; adding amino chain extender diethyl toluene diamine, stirring at the rotating speed of 2500rmp until the mixture is uniformly mixed to prepare amino chain extender emulsion; the amount of the emulsifier is 18% of the mass of the amino chain extender.
(3) ①, evenly mixing the amino chain extender emulsion and the prepolymer emulsion according to the mass ratio of 3:1, and keeping the temperature at 62 ℃ for 2-3h at the rotating speed of 800rmp to form the single-wall microcapsule emulsion, wherein the principle is that the prepolymer emulsion droplets are adsorbed on the surface of the amino chain extender emulsion droplets, and the synthesis of the inner wall material of the microcapsule is completed through the polymerization reaction of the prepolymer and the amino chain extender to form the single-wall microcapsule emulsion.
② adding appropriate amount of emulsifier, solvent and excessive prepolymer emulsion into the system obtained in step ①, emulsifying to form single-wall microcapsule-prepolymer composite emulsified liquid drop system, wherein the mass fraction of the emulsifier in the single-wall microcapsule-prepolymer composite emulsified liquid drop system is 5%, and the mass ratio of the emulsifier to the solvent is1:160(ii) a After emulsification is finished, dripping amino chain extender emulsion and 1-5 drops of defoaming agent, wherein the defoaming agent is 1, 4-butanediol, and the mass ratio of the amino chain extender emulsion to the prepolymer emulsion is 1: 3; keeping the temperature at 62 ℃ for 2-3h at the rotating speed of 1000rmp to form double-wall microcapsule emulsion; the principle is as follows: and adsorbing the emulsion droplets of the amino chain extender on the surfaces of the emulsion droplets of the prepolymer, and completing the synthesis of the outer wall material of the microcapsule through the polymerization reaction of the prepolymer and the amino chain extender.
③ the double-wall microcapsule emulsion is centrifugated, dried and washed to obtain the polyurea encapsulated external-repair and internal-fixation type polyurea double-wall self-repairing microcapsule.
The emulsifier in the above step is sodium dodecyl benzene sulfonate; the solvent is ethyl acetate.
The prepolymer emulsion and the amino chain extender emulsion are respectively used as a repairing agent and a curing agent, and react with each other to generate an inner capsule wall and an outer capsule wall, so that the utilization rate is high, and the process flow is greatly simplified. Under the action of the crack tip, the prepolymer and the amino chain extender can quickly generate a curing reaction, so that the interaction mechanism of the repairing agent and the curing agent is simplified, the crack is quickly repaired, and the repairing efficiency is improved.
The self-repairing concrete adopting the polyurea-based double-wall microcapsule has the advantage that the mass fraction of the polyurea-based double-wall microcapsule in the self-repairing concrete is 8%.
Example 2:
in contrast to the embodiment 1, the process of the invention,
the preparation method of the externally-repaired and internally-fixed polyurea-based double-wall self-repairing microcapsule comprises the following steps:
(1) preparing a prepolymer emulsion: uniformly mixing aliphatic isocyanate repairing agent 1, 4-cyclohexane diisocyanate and amino-terminated polyether 3, 5-dimethylthiotoluene-2, 6-diamine according to the mass ratio of 1:2 to obtain a prepolymer; stirring uniformly at the rotating speed of 2000rmp, adding an emulsifier and a solvent, and keeping the temperature at 68 ℃ for 2-3h at the rotating speed of 2300rpm to obtain a prepolymer emulsion; the amount of the emulsifier is 9% of the mass of the prepolymer, and the mass ratio of the emulsifier to the solvent is 1: 154.
(2) Preparing amino chain extender emulsion: taking a proper amount of emulsifier and solvent, and stirring at the rotating speed of 1000rmp until the emulsifier and the solvent are uniformly mixed; the mass ratio of the emulsifier to the solvent is 1: 46; adding amino chain extender cyclohexane diamine, and stirring at the rotating speed of 2000rmp until the mixture is uniformly mixed to prepare amino chain extender emulsion; the amount of the emulsifier is 20% of the mass of the amino chain extender.
(3) ①, uniformly mixing the amino chain extender emulsion and the prepolymer emulsion according to the mass ratio of 1.5:1, and keeping the temperature at 65 ℃ for 2-3h at the rotating speed of 1000rmp to form single-wall microcapsule emulsion;
② adding appropriate amount of emulsifier, solvent and excessive prepolymer emulsion into the system obtained in step ①, emulsifying to form single-wall microcapsule-prepolymer composite emulsified liquid drop system, wherein the mass fraction of the emulsifier in the single-wall microcapsule-prepolymer composite emulsified liquid drop system is 5.5%, and the mass ratio of the emulsifier to the solvent is1:155(ii) a After emulsification, dripping amino chain extender emulsion and 1-5 drops of defoaming agent; the defoaming agent is n-butyl alcohol, and the mass ratio of the amino chain extender emulsion to the prepolymer emulsion is1:1.2；Keeping the temperature at 65 ℃ for 2-3h at the rotating speed of 3500rmp to form double-wall microcapsule emulsion.
③ the double-wall microcapsule emulsion is centrifugated, dried and washed to obtain the polyurea encapsulated external-repair and internal-fixation type polyurea double-wall self-repairing microcapsule.
The emulsifier in the above step is octadecyl alcohol polyoxyethylene ether; the solvent is acetone.
The self-repairing coating of the polyurea-based double-wall microcapsule is adopted, and the mass fraction of the polyurea-based double-wall microcapsule in the self-repairing epoxy coating is 10%.
Example 3:
in contrast to the embodiment 1, the process of the invention,
the preparation method of the externally-repaired and internally-fixed polyurea-based double-wall self-repairing microcapsule comprises the following steps:
(1) preparing a prepolymer emulsion: uniformly mixing allophanate of aliphatic isocyanate repairing agent 1, 6-hexamethylene diisocyanate and amino-terminated polyether 1, 4-butanediamine according to the mass ratio of 1:3 to obtain prepolymer; stirring uniformly at the rotating speed of 3000rmp, adding an emulsifier and a solvent, and keeping the temperature at 70 ℃ for 2-3h at the rotating speed of 3000rpm to obtain a prepolymer emulsion; the amount of the emulsifier is 6% of the mass of the prepolymer, and the mass ratio of the emulsifier to the solvent is 1: 158.
(2) Preparing amino chain extender emulsion: taking a proper amount of emulsifier and solvent, and stirring at the rotating speed of 1600rmp until the emulsifier and the solvent are uniformly mixed; the mass ratio of the emulsifier to the solvent is 1: 48; adding amino chain extender ethylenediamine, and stirring at the rotating speed of 1000rmp until the mixture is uniformly mixed to prepare amino chain extender emulsion; the amount of the emulsifier is 10% of the mass of the amino chain extender.
(3) ①, evenly mixing amino chain extender emulsion and prepolymer emulsion according to the mass ratio of 1.8:1, keeping the temperature for 2-3h at 68 ℃ at the rotating speed of 2500rmp to form single-wall microcapsule emulsion, ② adding a proper amount of emulsifier, solvent and excessive prepolymer emulsion into the system obtained in the step ① for emulsification to form a single-wall microcapsule-prepolymer composite emulsified liquid drop system, wherein the mass fraction of the emulsifier in the single-wall microcapsule-prepolymer composite emulsified liquid drop system is 4.5%, and the mass ratio of the emulsifier to the solvent is that1:150(ii) a After emulsification, amine is added dropwiseThe mass ratio of the amino chain extender emulsion to the prepolymer emulsion is1:2；Keeping the temperature at 68 ℃ for 2-3h at the rotating speed of 1500rmp to form double-wall microcapsule emulsion.
③ the double-wall microcapsule emulsion is centrifugated, dried and washed to obtain the polyurea encapsulated external-repair and internal-fixation type polyurea double-wall self-repairing microcapsule.
The emulsifier in the above step is polyoxyethylene ether; the solvent is cyclohexane.
The self-repairing concrete adopting the polyurea-based double-wall microcapsule has the advantages that the mass fraction of the polyurea-based double-wall microcapsule in the self-repairing concrete is 12%.
Example 4:
in contrast to the embodiment 1, the process of the invention,
the preparation method of the externally-repaired and internally-fixed polyurea-based double-wall self-repairing microcapsule comprises the following steps:
(1) preparing a prepolymer emulsion: uniformly mixing aliphatic isocyanate repairing agent Hexamethylene Diisocyanate (HDI) and amino-terminated polyether amine D230 according to the mass ratio of 1:4 to obtain a prepolymer; stirring uniformly at the rotating speed of 2800rmp, adding an emulsifier and a solvent, and keeping the temperature at 60 ℃ for 2-3h at the rotating speed of 3500rpm to obtain a prepolymer emulsion; the amount of the emulsifier is 7% of the mass of the prepolymer, and the mass ratio of the emulsifier to the solvent is 1: 156.
(2) Preparing amino chain extender emulsion: taking a proper amount of emulsifier and solvent, and stirring at the rotating speed of 1800rmp until the emulsifier and the solvent are uniformly mixed; the mass ratio of the emulsifier to the solvent is 1: 50; adding amino chain extender 1, 4-diaminobutane, stirring at the rotating speed of 1500rmp until the mixture is uniformly mixed to prepare amino chain extender emulsion; the amount of the emulsifier is 12% of the mass of the amino chain extender.
(3) ① mixing the amine chain extender emulsion and the prepolymer emulsion uniformly according to the mass ratio of 2.8:1, keeping the temperature at 70 ℃ for 2-3h at the rotating speed of 1500rmp to form single-wall microcapsule emulsion, ② adding a proper amount of emulsifier, solvent and excessive prepolymer emulsion into the system obtained in the step ① for emulsification to form the polyurea encapsulated double-wall microcapsuleA single-wall microcapsule-prepolymer composite emulsion droplet system; the mass fraction of the emulsifier in the single-wall microcapsule-prepolymer composite emulsion droplet system is 4%; the mass ratio of the emulsifier to the solvent is1:140(ii) a After emulsification, dripping amino chain extender emulsion and adding 1-5 drops of defoaming agent; the defoaming agent is polyoxypropylene polyoxyethylene glycerol ether, and the mass ratio of the amino chain extender emulsion to the prepolymer emulsion is1:2.8；Keeping the temperature at 70 ℃ for 2-3h at the rotating speed of 2200rmp to form double-wall microcapsule emulsion.
③ the double-wall microcapsule emulsion is centrifugated, dried and washed to obtain the polyurea encapsulated external-repair and internal-fixation type polyurea double-wall self-repairing microcapsule.
The emulsifier in the above step is polyoxyethylene ether; the solvent is cyclopentane.
The self-repairing coating of the polyurea-based double-wall microcapsule is adopted, and the mass fraction of the polyurea-based double-wall microcapsule in the self-repairing epoxy coating is 15%.
Example 5:
in contrast to the embodiment 1, the process of the invention,
the preparation method of the externally-repaired and internally-fixed polyurea-based double-wall self-repairing microcapsule comprises the following steps:
(1) preparing a prepolymer emulsion: uniformly mixing aliphatic isocyanate repairing agent cyclohexylmethane-4, 4-diisocyanate and amino-terminated polyether 3, 5-diethyltoluene-2, 4-diamine according to the mass ratio of 1:5 to obtain a prepolymer; stirring uniformly at the rotating speed of 2600rmp, adding an emulsifier and a solvent, and keeping the temperature at 62 ℃ for 2-3h at the rotating speed of 1500rpm to obtain a prepolymer emulsion; the amount of the emulsifier is 8% of the mass of the prepolymer, and the mass ratio of the emulsifier to the solvent is 1: 152.
(2) Preparing amino chain extender emulsion: taking a proper amount of emulsifier and solvent, and stirring at the rotating speed of 2000rmp until the emulsifier and the solvent are uniformly mixed; the mass ratio of the emulsifier to the solvent is 1: 40; adding an amino chain extender tetraethylenepentamine, and stirring at the rotating speed of 1400rmp until the mixture is uniformly mixed to prepare an amino chain extender emulsion; the amount of the emulsifier is 14% of the mass of the amine chain extender.
(3) ①, evenly mixing amino chain extender emulsion and prepolymer emulsion according to the mass ratio of 2.5:1, keeping the temperature at 60 ℃ for 2-3h at the rotating speed of 1800rmp to form single-wall microcapsule emulsion, ② adding a proper amount of emulsifier, solvent and excessive prepolymer emulsion into the system obtained in the step ① for emulsification to form a single-wall microcapsule-prepolymer composite emulsified liquid drop system, wherein the mass fraction of the emulsifier in the single-wall microcapsule-prepolymer composite emulsified liquid drop system is 6%, and the mass ratio of the emulsifier to the solvent is 6%1:145(ii) a Dripping amino chain extender emulsion after emulsification is finished, wherein the mass ratio of the amino chain extender emulsion to the prepolymer emulsion is1:1.5；Keeping the temperature at 60 ℃ for 2-3h at the rotating speed of 3000rmp to form double-wall microcapsule emulsion.
③ the double-wall microcapsule emulsion is centrifugated, dried and washed to obtain the polyurea encapsulated external-repair and internal-fixation type polyurea double-wall self-repairing microcapsule.
The emulsifier in the above step is fatty ammonia polyoxyethylene ether; the solvent is toluene.
The self-repairing coating of the polyurea-based double-wall microcapsule is adopted, and the mass fraction of the polyurea-based double-wall microcapsule in the self-repairing epoxy coating is 18%.
Example 6:
in contrast to the embodiment 1, the process of the invention,
the preparation method of the externally-repaired and internally-fixed polyurea-based double-wall self-repairing microcapsule comprises the following steps:
(1) preparing a prepolymer emulsion: uniformly mixing an aliphatic isocyanate repairing agent HDI trimer system and amino-terminated polyether 1,6 hexamethylene diamine according to the mass ratio of 1:3.5 to obtain a prepolymer; stirring uniformly at the rotation speed of 3500rmp, adding an emulsifier and a solvent, and keeping the temperature of 65 ℃ for 2-3h at the rotation speed of 2600rpm to obtain a prepolymer emulsion; the amount of the emulsifier is 5% of the mass of the prepolymer, and the mass ratio of the emulsifier to the solvent is 1: 160.
(2) Preparing amino chain extender emulsion: taking a proper amount of emulsifier and solvent, and stirring at the rotating speed of 2500rmp until the emulsifier and the solvent are uniformly mixed; the mass ratio of the emulsifier to the solvent is 1: 42; adding an amino chain extender polyether amine D400, and stirring at the rotating speed of 1200rmp until the mixture is uniformly mixed to prepare an amino chain extender emulsion; the amount of the emulsifier is 16% of the mass of the amino chain extender.
(3) ①, evenly mixing amino chain extender emulsion and prepolymer emulsion according to the mass ratio of 2:1, keeping the temperature at 65 ℃ for 2-3h at the rotating speed of 2000rmp to form single-wall microcapsule emulsion, ② adding a proper amount of emulsifier, solvent and excessive prepolymer emulsion into the system obtained in the step ① for emulsification to form a single-wall microcapsule-prepolymer composite emulsified liquid drop system, wherein the mass fraction of the emulsifier in the single-wall microcapsule-prepolymer composite emulsified liquid drop system is 5%, and the mass ratio of the emulsifier to the solvent is that1:155(ii) a After emulsification, dripping amino chain extender emulsion and 1-5 drops of defoaming agent; the defoaming agent is polydimethylsiloxane, and the mass ratio of the amino chain extender emulsion to the prepolymer emulsion is1:2.4；And (2) keeping the temperature of 65 ℃ for 2-3h at the rotating speed of 1200rmp to form double-wall microcapsule emulsion, and performing centrifugation, drying and washing treatment on the double-wall microcapsule emulsion by ③ to obtain the polyurea encapsulated externally-repaired and internally-fixed polyurea-based double-wall self-repairing microcapsule.
The emulsifier in the above step is polyvinyl alcohol; the solvent is chlorobenzene.
The mass fraction of the polyurea-based double-wall microcapsule in the self-repairing concrete is 6.5%.
Table 1 micro-morphological characterization of microcapsules prepared in examples 1-6
Table 2 examples 1-6 mechanical property testing of microcapsules prepared
As is apparent from the characterization results in tables 1 and 2, the microcapsules prepared in examples 1 to 6 have a particle size of 10 to 200 μm, a tensile strength of 10.47 to 13.55MPa, an elongation at break of 242 to 330%, and a Shore hardness (A) of 40 to 52. Compared with the microcapsule in the prior art, the invention can realize the control of the particle size of the microcapsule through different preparation process preparation conditions so as to meet the requirements of different base materials; meanwhile, the prepared double-wall microcapsule shows better mechanical property, effectively avoids the failure of the microcapsule in the stirring process of adding the base material, and ensures that the microcapsule can stably play a repairing role.
The microcapsules prepared in examples 1,3 and 6 were incorporated into cement for the preparation of self-healing concrete. After 28 days of maintenance, taking a group of self-repairing concrete (each group contains 3 test blocks) to test the initial compressive strength; and (3) lightly pressing the self-repairing concrete by using a pressure testing machine to generate cracks in the self-repairing concrete by using another group (each group contains 3 test blocks), and testing the compressive strength of the self-repairing concrete after half a month. The microcapsules prepared in examples 2,4 and 5 were incorporated into epoxy coatings for the preparation of self-healing epoxy coatings. One group (each group contains 3 coatings) of self-repairing coatings is taken to test the initial tensile strength, the other group (each group contains 3 coatings) of self-repairing coatings is taken to stretch the self-repairing epoxy coatings by adopting a tensile testing machine to enable the self-repairing epoxy coatings to generate cracks inside, and after half a month, the tensile strength of the group of self-repairing epoxy coatings is tested to obtain the data shown in the table 3.
Table 3 determination of repair Strength of self-healing systems of microcapsules prepared in examples 1 to 6
In conclusion, the externally-repaired and internally-fixed polyurea-based double-wall self-repairing microcapsule prepared by the interfacial polymerization method has good shape in microscopic shape, and the particle size is mainly distributed between 10 and 200 mu m; mechanical tests show that the cured polyurea microcapsule is an elastic material (elongation at break 242-330%) with certain strength (tensile strength 10.47-13.91MPa) and hardness (Shore A40-52). The polyurea microcapsules are doped into the concrete and the epoxy coating for pre-pressing crack experiments, and the polyurea microcapsules have a certain repairing effect on cracks, the improvement rate of the compressive strength of the repaired concrete is 6.71%, and the improvement rate of the tensile strength of the repaired epoxy coating is 16.09%.
Claims (9)
1. The preparation method of the externally-repaired and internally-fixed polyurea double-wall self-repairing microcapsule is characterized by comprising the following steps of (1) preparing prepolymer emulsion, uniformly mixing a proper amount of aliphatic isocyanate repairing agent, amino-terminated polyether, emulsifier and solvent under high-speed stirring to prepare prepolymer emulsion, (2) preparing amino chain extender emulsion, uniformly mixing amino chain extender, solvent and emulsifier under high-speed stirring to prepare amino chain extender emulsion, (3) preparing polyurea-encapsulated double-wall microcapsule, ① uniformly mixing amino chain extender emulsion and prepolymer emulsion according to the mass ratio of 1.5:1-3:1, keeping the temperature of 60-70 ℃ for 2-3h at the rotating speed of 800-2500rpm to form single-wall microcapsule emulsion, ② adding a proper amount of emulsifier, solvent and excessive prepolymer emulsion into the polyurea-encapsulated double-wall self-repairing microcapsule emulsion system obtained in the step ① to form a single-wall microcapsule-prepolymer composite emulsified liquid drop system, wherein the mass ratio of the emulsifier in the polyurea-prepolymer composite emulsified liquid drop system is 4-6%, the mass ratio of the emulsifier to the solvent is 1:140-1:160, adding the emulsifier into the polyurea-encapsulated double-wall self-repairing microcapsule emulsion after completing the chain extension, and carrying out centrifugal treatment, wherein the single-wall microcapsule emulsion is carried out the centrifugal treatment, the single-wall microcapsule emulsion, the single-encapsulated double-wall microcapsule emulsion is carried out at the rotating speed of 3500-encapsulated double-wall microcapsule emulsion, and the rotating speed of the centrifugal treatment, and the centrifugal treatment, wherein the emulsion.
2. The preparation method of the externally-repaired and internally-cured polyurea-based double-wall self-repairing microcapsule according to claim 1, which is characterized in that: the preparation of the prepolymer emulsion in the step (1) comprises the following specific steps: uniformly mixing the aliphatic isocyanate repairing agent and the amino-terminated polyether according to the mass ratio of 1:1-1:5 to obtain a prepolymer; stirring uniformly at the rotation speed of 2000-3500rpm, adding an emulsifier and a solvent, and keeping the temperature of 60-70 ℃ for 2-3h at the rotation speed of 1500-3500rpm to obtain a prepolymer emulsion; the amount of the emulsifier is 5% -10% of the mass of the prepolymer, and the mass ratio of the emulsifier to the solvent is 1:150-1: 160.
3. The preparation method of the externally-repaired and internally-cured polyurea-based double-wall self-repairing microcapsule according to claim 1, which is characterized in that: the preparation of the amino chain extender emulsion in the step (2) is specifically as follows: taking a proper amount of emulsifier and solvent, and stirring at the rotating speed of 1000-; the mass ratio of the emulsifier to the solvent is 1:40-1: 50; adding an amino chain extender, and stirring at the rotating speed of 1000-; the amount of the emulsifier is 10-20% of the mass of the amino chain extender.
4. The preparation method of the externally-repaired and internally-cured polyurea-based double-wall self-repairing microcapsule according to any one of claims 2 to 3, wherein the preparation method comprises the following steps: the content of NCO groups of the aliphatic isocyanate repairing agent in the step (1) is 3% -12%, and the average functionality is 1.5-5.0; the aliphatic isocyanate repairing agent is an allophanate or HDI trimer system of isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), 1, 4-cyclohexane diisocyanate, cyclohexylmethane-4, 4-diisocyanate and 1, 6-hexamethylene diisocyanate; the amino-terminated polyether is polyether amine D400, polyether amine D230, polyether amine D2000, 3, 5-dimethylthiotoluene-2, 6-diamine, 3, 5-diethyltoluene-2, 4-diamine, 3, 5-dimethylthiotoluene-2, 4-diamine, 1, 4-butanediamine or 1, 6-hexanediamine.
5. The preparation method of the externally-repaired and internally-cured polyurea-based double-wall self-repairing microcapsule according to any one of claims 2 to 3, wherein the preparation method comprises the following steps: the amino chain extender in the step (2) is diethyl toluene diamine, dimethyl sulfur toluene diamine, N ' -dialkyl methyl diphenylamine, cyclohexane diamine, chlorinated MDH, ethylene diamine, 1, 3-diaminopropane, 1, 4-diaminobutane, diethylene triamine, pentaethylene hexamine, hexaethylene diamine, tetraethylene pentamine, pentaethylene hexamine, polyether amine D400, polyether amine D230, ethylene diamine or 3,3' -4,4' -diamino-diphenylmethane MOCA.
6. The preparation method of the externally-repaired and internally-cured polyurea-based double-wall self-repairing microcapsule according to any one of claims 2 to 3, wherein the preparation method comprises the following steps: the emulsifier in the steps (1) - (3) is sodium dodecyl benzene sulfonate, OP-10, octadecyl alcohol polyoxyethylene ether, Arabic gum, polyoxyethylene ether, fatty ammonia polyoxyethylene ether or polyvinyl alcohol; the solvent is ethyl acetate, acetone, cyclohexane, cyclopentane, toluene or chlorobenzene.
7. The method for preparing the external repair and internal fixation type polyurea-based double-wall self-repairing microcapsule according to any one of claims 2 to 3, wherein when the ② is used for preparing the double-wall microcapsule emulsion in the step (3), 1 to 5 drops of a defoaming agent can be added at the same time when the chain extender emulsion is added, wherein the defoaming agent is n-butyl alcohol, 1, 4-butanediol, polyoxypropylene polyoxyethylene glycerol ether or polydimethylsiloxane.
8. Double-walled self-healing microcapsules prepared according to the process of any one of claims 1 to 7 comprising an inner wall and an outer wall; the method is characterized in that: the inner layer capsule wall is coated with amino chain extender emulsion, and the outer layer capsule wall is coated with prepolymer emulsion; the inner-layer capsule wall and the outer-layer capsule wall are both polyurea prepared by an interfacial polymerization method, the inner-layer capsule wall polyurea is obtained by the reaction of amino chain extender emulsion coated on the inner-layer capsule wall and prepolymer emulsion coated on the outer-layer capsule wall, and the outer-layer capsule wall polyurea is obtained by the reaction of amino chain extender emulsion and prepolymer emulsion coated on the outer-layer capsule wall; the preparation method of the prepolymer emulsion comprises the following steps: and (2) uniformly mixing a proper amount of aliphatic isocyanate repairing agent, amino-terminated polyether, emulsifier and solvent under high-speed stirring to obtain prepolymer emulsion.
9. The self-repairing system of the externally-repairing and internally-fixing polyurea-based double-wall self-repairing microcapsule according to claim 8 is characterized in that: the mass fraction of the polyurea-based double-wall microcapsule in a self-repairing system is 5-18%; the self-repairing system is self-repairing concrete or a self-repairing coating.
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