CN113755102A - Self-repairing acrylic acid bonding polymer and preparation method thereof - Google Patents
Self-repairing acrylic acid bonding polymer and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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Abstract
The invention aims to provide an acrylic acid bonding polymer with a self-repairing function and a preparation method thereof. The invention firstly prepares the amphiphilic chain segment microcapsule, and the molecular chain of the microcapsule has the amphiphilic chain segment, so that the interface needing to be bonded can be quickly wetted. The amphiphilic segment microcapsules are then used as an important component of the self-healing acrylic binding polymer. Tests show that the self-repairing acrylic acid bonding polymer prepared by the invention not only improves the bonding force between the interfaces of bonding objects, but also can realize the repair of microcracks through self microcapsules when a bonding coating is damaged by external force to generate the microcracks, and the self-repairing rate reaches 72 percent through the observation of a scanning electron microscope.
Description
Technical Field
The invention belongs to the field of high molecular polymer materials, and relates to an acrylic acid adhesive polymer with a self-repairing function and a preparation method thereof.
Background
Bonding refers to the close and close bonding of two heterogeneous objects, generally, the substance used to bond two heterogeneous objects together is called adhesive, and the intermolecular attraction force between the two is called cohesive force. Bonding techniques have been developed with the development of adhesives. At the end of the 20 th century, adhesives have evolved from natural adhesives to solvent-based, emulsion-based synthetic adhesives, to 100% solid adhesives (hot melt adhesives, light-cured adhesives, etc.), to engineering-structural adhesives. With the development of material science, the performance of the adhesive is also greatly improved. The method improves the bonding strength and the rapid curing performance of the coating, develops a novel nano adhesive with environmental protection, high temperature resistance, long service life, high strength and special function, and is the main development direction of the bonding technology.
In the practical application process, the bond coating inevitably faces various damage problems, namely small internal micro cracks and large-scale fracture. In fact, most bond coats fail because the early internal microcracks are difficult to detect and cannot be effectively remedied, resulting in further propagation of microcracks into cracks and ultimately loss of bond coat adhesion. Based on this, inspired by the fact that the organism can repair some injured tissues by oneself so as to maintain self life and health, the self-repairing adhesive coating with the self-detecting and damage repairing capabilities is produced, and the self-repairing adhesive coating becomes a research hotspot in the field of novel intelligent materials once coming out, and attracts the attentive attention of more and more researchers.
In 2001, White and its team were the first time to introduce a self-repairing concept based on a microcapsule model into a polymer material, and microcapsules using a uric acid resin (PUF) as a capsule wall and dicyclopentadiene (dicyclopentadiene DCPA) as a self-repairing monomer were successfully implanted into an epoxy resin matrix together with a Grubbs catalyst, thereby successfully obtaining 67% self-repairing efficiency. The early self-repairing research is mainly aimed at solving the problem that the implanted self-repairing material cannot be repeatedly repaired, so that a microvascular self-repairing system capable of being repeatedly repaired is developed, and researchers define the system which realizes the repairing function by implanting a repairing agent as an external aid type self-repairing system. In order to overcome the defects, researchers begin to look at an intrinsic self-repairing system for repairing by virtue of self-reversible chemical or physical actions, and develop a series of self-repairing materials based on different reversible actions.
The acrylate adhesive has good weather resistance, water resistance and wide adhesion, and is not selected
The same common components can obtain a series of adhesive main body resins with different application values. The invention firstly prepares the microcapsule by an in-situ polymerization method, and the molecular chain of the microcapsule has an amphiphilic chain segment which can quickly wet the interface needing to be bonded. The addition of microcapsules to acrylic binding polymers was found to increase the shear strength of the bound objects by 35% as measured. The fatigue period of repeated stress is prolonged by 50 percent. The observation of a scanning electron microscope shows that after the adhesive coating has microcracks, the self-repairing efficiency is obvious, and the self-repairing rate reaches 72 percent.
Disclosure of Invention
The invention aims to provide a self-repairing bonding polymer, in particular to an acrylic bonding polymer with a self-repairing function and a preparation method thereof.
The self-repairing acrylic acid bonding polymer mainly comprises the following components: amphiphilic segment microcapsule, (methyl) acrylate copolymer, nanometer filler, acrylic acid hydroxyl compound and other assistants. The amounts of the components are as follows, calculated on the basis of 100 parts of the (meth) acrylate copolymer: 1.5-15 parts of amphiphilic chain segment microcapsule, 3-12 parts of nano filler, 0.8-6 parts of acrylic hydroxyl compound and 0-2 parts of other auxiliary agents.
The amphiphilic chain segment microcapsule is prepared from a urea resin prepolymer, a mixture of acrylic acid and styrene, an emulsifier and an initiator. Calculated by 100 parts of deionized water, the dosage of each component is as follows: 5-10 parts of urea-formaldehyde resin prepolymer, 18-32 parts of acrylic acid and styrene mixture, 0.8-3.6 parts of emulsifier, 0.9-2.1 parts of initiator and the balance of deionized water.
The emulsifier is as follows: one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, ethylene maleic anhydride copolymer, span 80, Tween 60 and Tween 80.
The initiator is one or more of benzoyl peroxide, ammonium persulfate, potassium persulfate and azobisisobutyronitrile.
The preparation method of the urea resin prepolymer comprises the following steps: adding 37% of formaldehyde and urea into a reaction vessel, stirring and mixing to fully dissolve the urea in the formaldehyde. Adding sodium hydroxide to adjust the pH value to 8-10, and reacting at the temperature of 60-85 ℃ for 1-3 h to obtain the urea-formaldehyde resin prepolymer. The mass ratio of the 37 percent of formaldehyde to the urea is 6: (1.5 to 3).
The preparation method of the acrylic acid and styrene mixture comprises the following steps: taking acrylic acid and styrene, adding a reaction promoter, and stirring and mixing uniformly. The mass ratio of the acrylic acid to the styrene is as follows: 10: (0.5 to 1.5). The reaction accelerator comprises: one or more of N, N-Dimethylaniline (DMA), N-dimethyl-p-toluidine, N-di-2-hydroxyethylaniline, N-di (2-hydroxyethyl) p-toluidine and N, N-di (2-hydroxypropyl) p-toluidine (DHPT), and the amount of the composition is 0.8-2.1% of the total amount of acrylic acid and styrene.
The preparation method of the amphiphilic chain segment microcapsule comprises the following steps: (1) adding deionized water and an emulsifier into a reaction vessel, and stirring and dispersing uniformly. And adding a mixture of acrylic acid and styrene, dropwise adding 1/2 initiator under a stirring state, and stirring for reacting for 1-3 h. The reaction temperature is 55-85 ℃, and the stirring speed is 200-750 r/min.
(2) Adding the urea-formaldehyde resin prepolymer, stirring and dispersing, dropwise adding 1/2 initiator, stirring and reacting for 2-4 h to form stable emulsion. The reaction temperature is 55-85 ℃, and the stirring speed is 200-750 r/min.
(3) And (3) adding hydrochloric acid to adjust the pH value to 3-4 to form a suspension, repeatedly filtering and washing the suspension for 3-5 times by using deionized water, and drying the suspension in a drying oven at the temperature of 50-60 ℃ for 24 hours to obtain the amphiphilic chain segment microcapsule.
The (meth) acrylate copolymer is composed of the following components: the acrylic acid modified methyl group. The dosage of each component is calculated by taking the solvent as 100 parts: 25-35 parts of methyl-containing acrylic monomer, 20-40 parts of acrylic monomer, 5-12 parts of vinyl silane and 0.9-3 parts of initiator.
The acrylic monomer containing methyl is one or more of methyl methacrylate, ethyl methacrylate, methacrylic acid and butyl methacrylate.
The acrylic monomer is one or a composition of more than one of acrylic acid, ethyl acrylate and butyl acrylate.
The vinyl silane is vinyl trimethoxy silane and vinyl triethoxy silane.
The solvent is one or more of toluene, xylene, ethanol, ethyl acetate and methanol.
The initiator is one or a composition of more than one of ammonium persulfate, potassium persulfate, sodium persulfate and benzoyl peroxide.
The preparation method of the (meth) acrylate copolymer comprises the following steps: (1) a solvent was added to a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen-introducing tube, and the temperature was raised while stirring. (2) Adding a methyl-containing acrylic monomer, an acrylic monomer, vinyl silane and an initiator into a reaction vessel according to the component proportion, and stirring for reaction for 3-6 h to obtain the (methyl) acrylate copolymer. The reaction temperature is 55-85 ℃, the stirring speed is 200-650 r/min, and nitrogen is adopted for protection in the reaction process.
The nano filler is one or more of fumed silica, talcum powder and mica powder, wherein the specific surface area of the fumed silica, the talcum powder and the mica powder is more than 1000 meshes.
The acrylic hydroxyl compound is one or a composition of more than one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate.
Such other adjuvants include, but are not limited to: pigments, defoamers, flame retardants, thickeners, and the like.
The preparation method of the self-repairing acrylic acid bonding polymer comprises the following steps:
(1) firstly, preparing the amphiphilic segment microcapsule and the (methyl) acrylate copolymer for later use.
(2) Weighing the amphiphilic chain segment microcapsule, (methyl) acrylate copolymer, nano filler, acrylic hydroxyl compound and other auxiliary agents according to the proportion, adding the mixture into a star-shaped stirring container, stirring and mixing the mixture evenly, and vacuumizing and degassing to obtain the repair acrylic adhesive polymer. The reaction temperature is room temperature, the stirring speed is 200-600 r/min, and the reaction is kept for 5-10min when the vacuum is pumped to-0.1 MPa.
The method of making a self-healing acrylic adhesive polymer described herein does not represent the only form in which the present invention may be made or utilized. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The self-repairing acrylic acid bonding polymer prepared by the invention not only improves the bonding force between bonded objects, but also can realize the repair of microcracks through self microcapsules when a bonding coating is damaged by external force to generate the microcracks, and the self-repairing rate reaches 72 percent through the observation of a scanning electron microscope. By testing the tensile property and the fracture toughness of the 3mm coating, the self-repairing acrylic acid bonding polymer coating is shown to have improved mechanical properties and obviously improved fatigue resistance.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1
Preparing the amphiphilic chain segment microcapsule: (1) 600g of 37% formaldehyde and 200g of urea are added to a reaction vessel, and the mixture is stirred and mixed until the urea is sufficiently dissolved in the formaldehyde. NaOH is added to adjust the pH value to 9, and the urea-formaldehyde resin prepolymer is obtained after the reaction for 3 hours at the temperature of 60 ℃. (2) 600g of acrylic acid and 60g of styrene are weighed, 9g of N, N-Dimethylaniline (DMA) is added, and the mixture is stirred and mixed uniformly for later use. (3) 20g of sodium dodecyl benzene sulfonate and 10g of Tween 60 are weighed and added into 1KG ionized water, and stirred and dispersed until the sodium dodecyl benzene sulfonate and the Tween 60 are completely dissolved. 200g of a mixture of acrylic acid and styrene was added thereto, and 8g of a benzoyl peroxide solution was added dropwise with stirring, followed by reaction with stirring for 1.5 hours. Adding 80g of urea-formaldehyde resin prepolymer, stirring and dispersing, dropwise adding 8g of benzoyl peroxide solution, stirring and reacting for 3 hours to form stable emulsion. The reaction temperature is 65 ℃, and the stirring speed is controlled between 200 and 750 r/min. And (3) adding hydrochloric acid to adjust the pH value to 3.5 to form a suspension, repeatedly filtering and washing the suspension for 3-5 times by using deionized water, and drying the suspension in a drying oven at the temperature of 50-60 ℃ for 24 hours to obtain the amphiphilic chain segment microcapsule.
Preparation of a (meth) acrylate copolymer: (1) in a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen inlet tube, nitrogen was introduced for protection, 500g of toluene and 500g of ethanol were added, and the temperature was raised to 60 ℃ while stirring. (2) Adding 280g of methyl methacrylate, 200g of acrylic acid, 60g of vinyl trimethoxy silane and 10g of ammonium persulfate, and stirring for reacting for 4 hours, wherein the stirring speed is controlled between 200 and 650 r/min.
Preparation of self-repairing acrylic adhesive polymer: 200g of (methyl) acrylate copolymer, 4g of amphiphilic segment microcapsule, 8g of silicon dioxide, 2g of talcum powder, 3g of hydroxyethyl methylacrylate and 1g of blue pigment are weighed and added into a star-shaped stirring container, and the materials are stirred at room temperature until the materials are uniformly mixed, wherein the stirring speed is controlled to be 200-600 r/min. Vacuum degassing was performed, and when the vacuum gauge was set to-1 Mpa, the vacuum was maintained for 6min, resulting in the repair of the acrylic binding polymer. According to tests, the shear strength of the bonding polypropylene material and the ceramic surface reaches 710MPa, the tensile strength reaches 802MPa, the scratch resistance of the surface of the coating with the thickness of 3mm reaches 2H, and the self-repairing rate of the coating under the condition of microcracks reaches 74%.
Example 2
Preparing the amphiphilic chain segment microcapsule: (1) 600g of 37% formaldehyde and 150g of urea are added into a reaction vessel, and stirred and mixed until the urea is fully dissolved in the formaldehyde. NaOH is added to adjust the pH value to 8, and the urea-formaldehyde resin prepolymer is obtained after the reaction for 1h at the temperature of 85 ℃. (2) 600g of acrylic acid and 30g of styrene are weighed, 3g of N, N-Dimethylaniline (DMA) and 2.04g of N, N-dimethyl-p-toluidine are added, stirred and mixed uniformly for later use. (3) 5g of sodium dodecyl sulfate and 3g of Tween 80 are weighed and added into 1KG ionized water, and stirred and dispersed until the sodium dodecyl sulfate and the Tween 80 are completely dissolved. 180g of a mixture of acrylic acid and styrene was added thereto, and 4.5g of potassium persulfate was added dropwise with stirring, followed by reaction with stirring for 2 hours. Adding 50g of urea-formaldehyde resin prepolymer, stirring and dispersing, dropwise adding 4.5g of potassium persulfate solution, stirring and reacting for 4 hours to form stable emulsion. The reaction temperature is 55 ℃, and the stirring speed is controlled between 200 and 750 r/min. And (3) adding hydrochloric acid to adjust the pH value to 3 to form a suspension, repeatedly filtering and washing the suspension for 3-5 times by using deionized water, and drying the suspension in a drying oven at the temperature of 50-60 ℃ for 24 hours to obtain the amphiphilic chain segment microcapsule.
Preparation of a (meth) acrylate copolymer: (1) a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen inlet tube was purged with nitrogen, and 600g of toluene and 400g of methanol were added to raise the temperature to 55 ℃ while stirring. (2) Adding 250g of methacrylic acid, 400g of ethyl acrylate, 50g of vinyl trimethoxy silane and 30g of ammonium persulfate, and stirring for reacting for 6 hours, wherein the stirring speed is controlled between 200 and 650 r/min.
Preparation of self-repairing acrylic adhesive polymer: 400g of (methyl) acrylate copolymer, 6g of amphiphilic segment microcapsule, 48g of silicon dioxide, 3.2g of hydroxypropyl methacrylate, 2g of blue pigment and 2g of defoaming agent are weighed and added into a star-shaped stirring container, the mixture is stirred at room temperature until the mixture is uniformly mixed, and the stirring speed is controlled between 200 and 600 r/min. Vacuum degassing was performed, and when the vacuum gauge was set to-1 Mpa, the vacuum was maintained for 5min, resulting in the repair of the acrylic binding polymer. The test shows that the shear strength of the bonding polypropylene material and the ceramic surface reaches 720Mpa, the tensile strength reaches 772Mpa, the scratch resistance of the surface of the coating with the thickness of 3mm reaches 3H, and the self-repairing rate of the coating under the condition of microcracks reaches 72%.
Example 3
Preparing the amphiphilic chain segment microcapsule: (1) 600g of 37% formaldehyde and 300g of urea are added into a reaction vessel, and stirred and mixed until the urea is fully dissolved in the formaldehyde. NaOH is added to adjust the pH value to 10, and the urea-formaldehyde resin prepolymer is obtained after the reaction for 3 hours at the temperature of 60 ℃. (2) 600g of acrylic acid and 90g of styrene are weighed, 10g of N, N-bis (2-hydroxyethyl) p-toluidine and 4.49g of N, N-dimethyl p-toluidine are added, stirred and mixed evenly for later use. (3) 20g of sodium dodecyl sulfate and 16g of Tween 80 are weighed and added into 1KG ionized water, and stirred and dispersed until the sodium dodecyl sulfate and the Tween 80 are completely dissolved. 320g of a mixture of acrylic acid and styrene was added thereto, and 10.5g of an ammonium persulfate solution was added dropwise with stirring, followed by reaction with stirring for 3 hours. Adding 100g of urea-formaldehyde resin prepolymer, stirring and dispersing, dropwise adding 10.5g of potassium persulfate solution, stirring and reacting for 4 hours to form stable emulsion. The reaction temperature is 85 ℃, and the stirring speed is controlled to be 200-750 r/min. And (3) adding hydrochloric acid to adjust the pH value to 4 to form a suspension, repeatedly filtering and washing the suspension for 3-5 times by using deionized water, and drying the suspension in a drying oven at the temperature of 50-60 ℃ for 24 hours to obtain the amphiphilic chain segment microcapsule.
Preparation of a (meth) acrylate copolymer: (1) a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen inlet tube was purged with nitrogen, and 300g of xylene, 400g of toluene and 300g of ethanol were added to raise the temperature to 55 ℃ while stirring. (2) 350g of butyl methacrylate, 240g of acrylic acid, 120g of vinyl triethoxysilane and 30g of ammonium persulfate are added, and the mixture is stirred and reacted for 5.5 hours, wherein the stirring speed is controlled between 200 and 650 r/min.
Preparation of self-repairing acrylic adhesive polymer: 300g of (methyl) acrylate copolymer, 45g of amphiphilic segment microcapsule, 9g of silicon dioxide, 4g of hydroxyethyl methylacrylate and 2g of defoaming agent are weighed and added into a star-shaped stirring container, the mixture is stirred at room temperature until the mixture is uniformly mixed, and the stirring speed is controlled between 200 and 600 r/min. Vacuum degassing was performed, and when the vacuum gauge was set to-1 Mpa, the vacuum was maintained for 8min, resulting in the repair of the acrylic binding polymer. The test shows that the shear strength of the bonding polypropylene material and the ceramic surface reaches 734Mpa, the tensile strength reaches 813Mpa, the scratch resistance of the surface of the coating with the thickness of 3mm reaches H, and the self-repairing rate of the coating under the condition of microcrack reaches 76%.
Example 4
Preparing the amphiphilic chain segment microcapsule: the product obtained was prepared using example 1.
Preparation of a (meth) acrylate copolymer: (1) in a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen-introducing tube, nitrogen was introduced under protection, 500g of toluene, 200g of methanol and 300g of ethanol were added, and the temperature was raised to 75 ℃ while stirring. (2) 230g of methyl methacrylate, 210g of acrylic acid, 90g of vinyl trimethoxy silane and 9g of ammonium persulfate are added, and the mixture is stirred and reacted for 6 hours, wherein the stirring speed is controlled between 200 and 650 r/min.
Preparation of self-repairing acrylic adhesive polymer: 300g of (methyl) acrylate copolymer, 24g of amphiphilic segment microcapsule, 12g of silicon dioxide, 12g of mica powder, 18g of hydroxyethyl methylacrylate and 3g of flame retardant are weighed and added into a star-shaped stirring container, and the mixture is stirred at room temperature until the mixture is uniformly mixed, wherein the stirring speed is controlled between 200 and 600 r/min. Vacuum degassing was performed, and when the vacuum gauge was set to-1 Mpa, the vacuum was maintained for 7min, resulting in the repair of the acrylic binding polymer. The test shows that the shearing strength of the bonding polypropylene material and the ceramic surface reaches 695MPa, the tensile strength reaches 785MPa, the scratch resistance of the surface of the coating with the thickness of 3mm reaches 2H, and the self-repairing rate of the coating under the condition of microcrack reaches 73%.
Example 5
Preparing the amphiphilic chain segment microcapsule: (1) 600g of 37% formaldehyde and 200g of urea are added to a reaction vessel, and the mixture is stirred and mixed until the urea is sufficiently dissolved in the formaldehyde. NaOH is added to adjust the pH value to 9, and the urea-formaldehyde resin prepolymer is obtained after the reaction for 3 hours at the temperature of 65 ℃. (2) 400g of acrylic acid and 40g of styrene are weighed, 3g of N, N-Dimethylaniline (DMA) and 3g of N, N-dimethyl-p-toluidine are added, stirred and mixed uniformly for later use. (3) 20g of sodium dodecyl benzene sulfonate, 5g of sodium dodecyl sulfate and 5g of Tween 60 are weighed and added into 1KG of ionized water, and the mixture is stirred and dispersed until the mixture is completely dissolved. 250g of a mixture of acrylic acid and styrene was added thereto, and 8g of a benzoyl peroxide solution was added dropwise with stirring, followed by stirring and reacting for 2 hours. Adding 80g of urea-formaldehyde resin prepolymer, stirring and dispersing, dropwise adding 12g of potassium persulfate solution, stirring and reacting for 3.5h to form stable emulsion. The reaction temperature is 70 ℃, and the stirring speed is controlled to be 200-750 r/min. And (3) adding hydrochloric acid to adjust the pH value to 3.5 to form a suspension, repeatedly filtering and washing the suspension for 3-5 times by using deionized water, and drying the suspension in a drying oven at the temperature of 50-60 ℃ for 24 hours to obtain the amphiphilic chain segment microcapsule.
Preparation of a (meth) acrylate copolymer: the product prepared in example 2 was used.
Preparation of self-repairing acrylic adhesive polymer: weighing 500g of (methyl) acrylate copolymer, 15g of amphiphilic chain segment microcapsule, 35g of silicon dioxide, 2g of talcum powder, 6g of hydroxyethyl methylacrylate, 3g of blue pigment and 2g of flatting agent, adding into a star-shaped stirring container, stirring at room temperature until the mixture is uniformly mixed, and controlling the stirring speed to be 200-600 r/min. Vacuum degassing was performed, and when the vacuum gauge was set to-1 Mpa, the vacuum was maintained for 7min, resulting in the repair of the acrylic binding polymer. The test shows that the shearing strength of the bonding polypropylene material and the ceramic surface reaches 723Mpa, the tensile strength reaches 811Mpa, the scratch resistance of the surface of the coating with the thickness of 3mm reaches 2H, and the self-repairing rate of the coating under the condition of microcracks reaches 75%.
Claims (10)
1. A self-repairing acrylic bonding polymer is characterized by comprising the following components: amphiphilic segment microcapsule, (methyl) acrylate copolymer, nano filler, acrylic hydroxyl compound and other auxiliary agents; the amounts of the components are as follows, calculated on the basis of 100 parts of the (meth) acrylate copolymer: 1.5-15 parts of amphiphilic chain segment microcapsule, 3-12 parts of nano filler, 0.8-6 parts of acrylic hydroxyl compound and 0-2 parts of other auxiliary agents.
2. The self-repairing acrylic acid bonding polymer of claim 1, characterized in that the amphiphilic segment microcapsule is prepared from urea-formaldehyde resin prepolymer, acrylic acid and styrene mixture, emulsifier and initiator; calculated by 100 parts of deionized water, the dosage of each component is as follows: 5-10 parts of urea-formaldehyde resin prepolymer, 18-32 parts of acrylic acid and styrene mixture, 0.8-3.6 parts of emulsifier, 0.9-2.1 parts of initiator and the balance of deionized water;
the emulsifier is as follows: one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, ethylene maleic anhydride copolymer, span 80, tween 60 and tween 80;
the initiator is one or more of benzoyl peroxide, ammonium persulfate, potassium persulfate and azobisisobutyronitrile.
3. The self-healing acrylic binding polymer of claim 1, characterized in that the (meth) acrylate copolymer is comprised of: the acrylic acid monomer containing methyl, the acrylic acid monomer, the vinyl silane, the solvent and the initiator; the dosage of each component is calculated by taking the solvent as 100 parts: 25-35 parts of methyl-containing acrylic monomer, 20-40 parts of acrylic monomer, 5-12 parts of vinyl silane and 0.9-3 parts of initiator;
the acrylic monomer containing methyl is one or more of methyl methacrylate, ethyl methacrylate, methacrylic acid and butyl methacrylate;
the acrylic monomer is one or a composition of more than one of acrylic acid, ethyl acrylate and butyl acrylate;
the vinyl silane is vinyl trimethoxy silane and vinyl triethoxy silane;
the solvent is one or more of toluene, xylene, ethanol, ethyl acetate and methanol;
the initiator is one or a composition of more than one of ammonium persulfate, potassium persulfate, sodium persulfate and benzoyl peroxide.
4. The self-repairing acrylic acid bonded polymer of claim 1, characterized in that the nano-filler is one or more of fumed silica, talc and mica powder, wherein the specific surface area of the fumed silica, the talc and the mica powder is more than 1000 meshes.
5. The self-healing acrylic adhesive polymer of claim 1, wherein said hydroxyl acrylic compound is one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate.
6. The self-healing acrylic binding polymer of claim 1, characterized in that the method of making the self-healing acrylic binding polymer comprises the steps of:
(1) firstly, preparing an amphiphilic segment microcapsule and a (methyl) acrylate copolymer for later use;
(2) weighing the amphiphilic chain segment microcapsule, (methyl) acrylate copolymer, nano filler, acrylic hydroxyl compound and other auxiliary agents according to the proportion, adding the mixture into a star-shaped stirring container, stirring and mixing the mixture evenly, and vacuumizing and degassing to obtain the repair acrylic adhesive polymer; the reaction temperature is room temperature, the stirring speed is 200-600 r/min, and the reaction is kept for 5-10min when the vacuum is pumped to-0.1 MPa.
7. The amphiphilic chain segment microcapsule of claim 2, wherein the urea resin prepolymer is prepared by the following steps: adding 37% of formaldehyde and urea into a reaction container, stirring and mixing to fully dissolve the urea in the formaldehyde; adding sodium hydroxide to adjust the pH value to 8-10, and reacting at the temperature of 60-85 ℃ for 1-3 h to obtain a urea-formaldehyde resin prepolymer; the mass ratio of the 37 percent of formaldehyde to the urea is 6: (1.5 to 3).
8. The amphiphilic segment microcapsule of claim 2, wherein said mixture of acrylic acid and styrene is prepared by the following process: taking acrylic acid and styrene, adding a reaction promoter, and stirring and mixing uniformly; the mass ratio of the acrylic acid to the styrene is as follows: 10: (0.5 to 1.5); the reaction accelerator comprises: one or more of N, N-Dimethylaniline (DMA), N-dimethyl-p-toluidine, N-di-2-hydroxyethylaniline, N-di (2-hydroxyethyl) p-toluidine and N, N-di (2-hydroxypropyl) p-toluidine (DHPT), and the amount of the composition is 0.8-2.1% of the total amount of acrylic acid and styrene.
9. The amphiphilic segment microcapsule according to claim 2, characterized in that the specific preparation method comprises the following steps: (1) adding deionized water and an emulsifier into a reaction container, and uniformly stirring and dispersing; adding a mixture of acrylic acid and styrene, dropwise adding 1/2 initiator under a stirring state, and stirring for reacting for 1-3 h; the reaction temperature is 55-85 ℃, and the stirring speed is 200-750 r/min;
(2) adding the urea-formaldehyde resin prepolymer, stirring and dispersing, dropwise adding 1/2 initiator, stirring and reacting for 2-4 h to form stable emulsion; the reaction temperature is 55-85 ℃, and the stirring speed is 200-750 r/min;
(3) and (3) adding hydrochloric acid to adjust the pH value to 3-4 to form a suspension, repeatedly filtering and washing the suspension for 3-5 times by using deionized water, and drying the suspension in a drying oven at the temperature of 50-60 ℃ for 24 hours to obtain the amphiphilic chain segment microcapsule.
10. The (meth) acrylate copolymer according to claim 3, characterized in that the preparation method comprises the steps of: (1) adding a solvent into a reaction vessel provided with a stirrer, a thermometer, a condenser pipe and a nitrogen inlet pipe, and heating while stirring; (2) adding a methyl-containing acrylic monomer, an acrylic monomer, vinyl silane and an initiator into a reaction vessel according to the component proportion, and stirring for reaction for 3-6 h to obtain a (methyl) acrylate copolymer; the reaction temperature is 55-85 ℃, the stirring speed is 200-650 r/min, and nitrogen is adopted for protection in the reaction process.
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| CN117143552A (en) * | 2023-11-01 | 2023-12-01 | 宁德时代新能源科技股份有限公司 | Adhesive composition, preparation method thereof, battery pole piece, secondary battery and power utilization device |
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| CN117143552A (en) * | 2023-11-01 | 2023-12-01 | 宁德时代新能源科技股份有限公司 | Adhesive composition, preparation method thereof, battery pole piece, secondary battery and power utilization device |
| CN117143552B (en) * | 2023-11-01 | 2024-03-29 | 宁德时代新能源科技股份有限公司 | Adhesive composition, preparation method thereof, battery pole piece, secondary battery and power utilization device |
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