CN111518506A - Self-repairing high-molecular adhesive for tire and preparation method thereof - Google Patents
Self-repairing high-molecular adhesive for tire and preparation method thereof Download PDFInfo
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- CN111518506A CN111518506A CN202010434661.0A CN202010434661A CN111518506A CN 111518506 A CN111518506 A CN 111518506A CN 202010434661 A CN202010434661 A CN 202010434661A CN 111518506 A CN111518506 A CN 111518506A
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- C—CHEMISTRY; METALLURGY
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/02—Polyureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7875—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/7887—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring having two nitrogen atoms in the ring
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- Chemical Kinetics & Catalysis (AREA)
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention belongs to the technical field of self-repairing materials of automobile tires, and discloses a self-repairing high-molecular adhesive for tires and a preparation method thereof. The preparation method comprises the steps of preparing polyacrylate prepolymer containing 2- (tert-butylamino) ethyl methacrylate, preparing the polyurea trimer, and carrying out mixed reaction on the polyacrylate prepolymer and the polyurea trimer to finally prepare the self-repairing adhesive for the tire. The adhesive prepared by the preparation method has higher repair efficiency and better repair performance, and is reacted under the heating condition to be tightly combined with the surface of the tire.
Description
Technical Field
The invention relates to the technical field of self-repairing materials of automobile tires, in particular to a self-repairing high-molecular adhesive for tires and a preparation method thereof.
Background
In the case of high-speed running, the automobile is very easy to have a tire burst under the condition that the tire is over-high in temperature or punctured, so that serious casualty accidents are caused, therefore, for safety consideration, new tire varieties such as run-flat tires, explosion-proof tires, bulletproof tires, puncture-proof self-repairing tires and the like are widely developed and play a certain safety role. However, these functional tires have problems of high fuel consumption, poor performance in terms of tire dynamic uniformity due to structural change of the tires, high economic cost, and the like, and some tires can be used only in some special environments such as military conditions.
The polyurea material is a polymer material which is formed by polymerization reaction of NCO containing polyisocyanate and polyamine as main compounds and has urea bonds (such as-NHCONH). Research shows that reversible urea bonds are generated when secondary amine groups and isocyanate groups react, and for small-molecule polyurea polymers (polymers with smaller molecular weight), even if the urea bonds are formed in the main chain structure of the polymers, the polymer materials with the reversible dynamic urea bonds can be formed due to small molecular chain molecular weight, small intermolecular interaction and flexible chain segment movement. The rubber is bonded by a macromolecular polyisocyanate adhesive or a polyisocyanate adhesive modified by a rubber adhesive, wherein the surface of the rubber can be swelled by an organic solvent contained in the adhesive, the polyisocyanate adhesive can permeate into the surface layer of the rubber after heating and react with active hydrogen existing in the rubber to form a covalent bond, but for the rubber macromolecular material, a urea bond prepared by a one-step reaction method is formed in a polymer main chain structure, the movement of the polymer main chain is subjected to a larger steric hindrance effect under the condition of larger molecular weight, the movement of a molecular chain is limited, the mobility of the molecular chain can be increased by heating, so that the activation energy of the reversible dynamic reaction of the urea bond is increased, the automatic repair at the broken opening of the rubber is difficult at normal temperature, and the reversible dynamic urea bond cannot be realized among material groups at normal temperature when the common polyurethane adhesive is used for bonding the rubber, a good adhesive effect cannot be produced. Therefore, it is highly desirable to develop an adhesive that can provide a tire with a high self-healing capacity and good post-healing properties at room temperature.
Disclosure of Invention
The invention provides a self-repairing high-molecular adhesive for a tire, aiming at solving the problem that the tire repairing adhesive in the prior art is difficult to automatically repair at a rubber laceration for multiple times at normal temperature.
In the prior art, the preparation of the high polymer material containing urea bonds is to react terminal polyisocyanate NCO and terminal polyamine to form the high polymer material with urea bonds-NHCONH-, and the reaction route is as follows:
the macromolecular compound obtained by the reaction is generally synthesized by a one-step synthesis method (one-pot method), wherein a urea bond in the compound prepared by the one-pot method is formed in a main chain structure of a polymer, and the reversible dynamic reaction of the urea bond can be realized only by heating, so that the compound is difficult to automatically repair at the broken opening of the rubber for many times at normal temperature. Meanwhile, for rubber macromolecular materials, if the silane coupling agent is not heated, the rubber macromolecular materials are difficult to be compatible with white carbon black in tire rubber.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a preparation method of a self-repairing high polymer adhesive for a tire, which can self-repair at normal temperature, and specifically comprises the following steps:
1) dissolving 2- (tert-butylamino) ethyl methacrylate, an acrylate monomer and an initiator in an organic solvent, heating and carrying out free radical reaction to obtain a polyacrylate prepolymer (a compound with a structure shown in a formula I) containing 2- (tert-butylamino) ethyl methacrylate;
the polyacrylate prepolymer obtained in step 1) may be dried at 80 ℃ for 12h to remove the solvent for further use.
2) Respectively dissolving a cross-linking agent, a silane coupling agent and an isocyanate monomer in an organic solvent, and uniformly mixing a cross-linking agent solution, a silane coupling agent solution and an isocyanate monomer solution for reaction to obtain a micromolecular polyurea trimer (a compound with a structure shown in a formula II), wherein the reaction route is as follows:
and (3) carrying out rotary evaporation on the polyurea tripolymer solution obtained in the step 2) until the solution is turbid, then separating out the polyurea tripolymer, carrying out suction filtration, and carrying out vacuum drying for 8h at the temperature of 60 ℃ to obtain a white polyurea tripolymer for later use.
3) And respectively dissolving the polyurea tripolymer (the compound shown in the formula I) and the polyacrylate prepolymer (the compound shown in the formula II) in an organic solvent, mixing the polyurea tripolymer and the polyacrylate prepolymer for reaction, and drying the obtained reaction solution at the temperature of 80 ℃ for 12 hours to obtain the tire self-repairing adhesive (the compound shown in the formula III).
The self-repairing adhesive of the compound shown in the formula III is solid and in a plaster shape, is coated on an inner airtight layer of a tire, forms a puncture-proof and air leakage-proof coating on the inner wall of the tire, and can be isolated from an inner liner layer by adding a film. When the tire is penetrated by an object in the driving process of an automobile, the material of the leakage-proof layer can tightly wrap the sharp object, so that the leakage-proof effect is achieved, when the sharp object is pulled out, the self-repairing adhesive is squeezed between the rubber materials at the crevasse under the internal pressure of the tire, the leakage-proof layer at the crevasse is adhered by the viscosity of the self-repairing adhesive and the rubber at the crevasse of the tire, and self-repairing can be achieved under the normal temperature condition; the product can accept repeated destruction-repair of the same repair position due to carrying reversible urea bonds, thereby meeting the requirement of repeated self-repair, and the adhesive carries siloxy which can react with silanol groups of the white carbon black under the heating condition to ensure better compatibility and better repair viscosity.
The branched chain of the molecular chain of the adhesive comprises a large number of reversible urea bonds generated by isocyanic acid radicals and amino groups, the flexibility of the branched chain is greater than that of the main chain, the activation energy of reversible dynamic reaction of the urea bonds is lower, and the urea bonds can freely move at normal temperature, so that the adhesive can self-repair at normal temperature without stimulation; specifically, under the condition that a polymer molecular chain is damaged, the molecular chain is broken, a urea bond is damaged, and the reverse reaction is generated to decompose the molecular chain into isocyanate and amino groups, the urea bond is quickly and reversibly synthesized, and the molecular chain can be quickly healed after being damaged, so that the adhesive coated on the tire wound has the self-repairing performance, the reversible reaction of the urea bond can be repeatedly performed at normal temperature, and the macromolecular compound shown in the formula III also has the function of multiple self-repairing. Moreover, the macromolecular compound can greatly improve the compatibility of the adhesive and the tire rubber with the white carbon black filler, and the silane oxygen group of the silane coupling agent and the silanol group on the surface of the white carbon black react under the heating condition to ensure that the adhesive is tightly combined with the surface of the tire, so that the repairing viscosity of the adhesive is better.
Preferably, the mass ratio of the 2- (tert-butylamino) ethyl methacrylate to the acrylate monomer to the initiator is 0.1-2.5: 10-15: 0.02-0.15; the mass ratio of the cross-linking agent to the silane coupling agent to the isocyanate monomer is 0.5-1.2: 0.2: 1-2.6; the mass ratio of the polyurea tripolymer to the polyacrylate prepolymer is 2-12.5: 35-65.
Preferably, the reaction temperature in the step 1) is 80 ℃, and the polyacrylate prepolymer is obtained after the reaction is carried out for 4 hours at the constant temperature of 80 ℃; the mixing reaction time in the step 2) is 1-4 h; the mixing reaction time in the step 3) is 4 hours, and the reaction temperature is 80 ℃.
The invention adopts heat-resistant polyacrylate as a base material, and has the advantages of wide application temperature range, light weight and excellent mechanical property. Preferably, the acrylate monomer in step 1) is selected from one or more of methyl methacrylate, ethyl acrylate, ethyl methacrylate and butyl acrylate.
The organic solvent is not particularly limited, and preferably, the organic solvent in the steps 1) and 3) is N, N dimethylformamide or tetrahydrofuran; the organic solvent in step 2) can be one or more of chloroform, dichloromethane, toluene, xylene and acetone, preferably, the organic solvent in step 2) is chloroform.
Preferably, the initiator in the step 1) is one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, cumene hydroperoxide, tert-butyl hydroperoxide, diisopropyl peroxydicarbonate or dicyclohexyl peroxydicarbonate.
Preferably, the cross-linking agent solution in the step 2) is one or more of piperazine, piperidine and imidazole, wherein piperazine contains two amino groups, and the reaction activity and structure of piperazine are superior to those of pyridine and imidazole, so that when the cross-linking agent is piperazine, the obtained high molecular compound has higher repair efficiency and better repair performance.
The silane coupling agent is isocyanatopropyl triethoxysilane; the isocyanate monomer solution is one or more of diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate and naphthalene diisocyanate.
Preferably, the tire self-repairing adhesive obtained in the step 3) can be mixed with a rubber adhesive at normal temperature, wherein the rubber adhesive is one or more of water-based polychloroprene, a carboxylated chloroprene rubber adhesive, a methyl methacrylate grafted chloroprene rubber adhesive, an MMA-CR binary grafted adhesive, a phenolic butyronitrile adhesive, an epoxy-carboxyl butyronitrile rubber adhesive and a silane modified phenolic butyronitrile adhesive.
The invention also aims to provide the self-repairing high polymer adhesive for the tire, which is prepared by the preparation method.
The preparation method provided by the invention adopts a step-by-step method to prepare the polymer adhesive containing reversible urea bonds, and test results show that the preparation method provided by the invention can enable the reversible urea bonds of the finally obtained polymer adhesive to be positioned at branched chains, the flexibility of the branched chains is greater than that of the main chains, the polymer adhesive can freely move at normal temperature, and the polymer adhesive can complete self-repair at normal temperature. According to the technical scheme, the adhesive of the compound shown in the formula III obtained by the preparation method has higher repair efficiency and better repair performance, and the adhesive is tightly combined with the surface of the tire by reaction under the heating condition.
Drawings
FIG. 1 is a nuclear magnetic resonance image of a self-repairing polymeric adhesive for a tire in example 1;
FIG. 2 is an infrared spectrum of the compound obtained in comparative example 1, example 1 and example 2 provided by the present invention;
fig. 3 is a graph showing the repair frequency and repair efficiency at normal temperature of comparative example 1, examples 1 and 2 provided by the present invention.
Detailed Description
The invention discloses a self-repairing high-molecular adhesive for a tire and a preparation method thereof, and a person skilled in the art can appropriately improve process parameters by referring to the content. It is expressly intended that all such similar substitutes and modifications which would be obvious to those skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The following detailed description of the invention refers to specific embodiments thereof for better understanding by those skilled in the art.
Comparative example 1
Dissolving ethyl acrylate, butyl acrylate, 2- (tert-butylamino) ethyl methacrylate and dimethyl azodiisobutyrate in the mass ratio of 3.5:5.5:1:0.02 in N, N-dimethylformamide and uniformly mixing; adding isocyanatopropyl triethoxysilane or toluene diisocyanate with the weight ratio of 1:5 to the total weight of the acrylate monomer for mixing and reacting; and finally, heating the mixed solution to 60 ℃ for reaction for 24 hours, and carrying out one-pot reaction to obtain the polyurea polymer.
Example 1
Respectively dissolving methyl methacrylate, ethyl acrylate, 2- (tert-butylamino) ethyl methacrylate and azobisisobutyronitrile in a mass ratio of 7.5:6:1:0.06 in a solvent N-N dimethylformamide, mixing and heating to 80 ℃, reacting at constant temperature for 4 hours to obtain a polyacrylate prepolymer, drying the prepolymer at 80 ℃ for 12 hours, and removing the solvent to obtain a prepolymer containing 2- (tert-butylamino) ethyl methacrylate;
dissolving piperazine, isocyanatopropyl triethoxysilane and isophorone diisocyanate in a mass ratio of 0.8:0.2:1.5 in chloroform respectively, uniformly mixing the piperazine solution and the isophorone diisocyanate solution, reacting for 1h to obtain a small-molecular polyurea trimer solution, performing rotary evaporation on the polyurea trimer solution until the solution is turbid, separating out the polyurea trimer, performing suction filtration, and performing vacuum drying at 60 ℃ for 8h to obtain white polyurea trimer;
respectively dissolving polyurea tripolymer and prepolymer containing 2- (tert-butylamino) ethyl methacrylate in N-N dimethylformamide according to the mass ratio of 10:43.5, uniformly mixing the polyurea tripolymer solution and the prepolymer solution, reacting at the constant temperature of 80 ℃ for 4h, drying the obtained solution at the temperature of 80 ℃ for 12h to obtain the self-repairing high-molecular adhesive for the tire, and showing the nuclear magnetic spectrum of the adhesive in figure 1, wherein figure 1 verifies the synthesis of a target product.
Example 2
Weighing methyl methacrylate, ethyl acrylate, 2- (tert-butylamino) ethyl methacrylate and azobisisobutyronitrile in a mass ratio of 7.5:6:1:0.06, dissolving in N-N dimethylformamide as a solvent, mixing and heating to 80 ℃, reacting at constant temperature for 4h to obtain an amino group-containing branched polyacrylate prepolymer, drying the prepolymer at 80 ℃ for 12h, and removing the solvent to obtain the polyacrylate prepolymer containing 2- (tert-butylamino) ethyl methacrylate.
Respectively dissolving aminopyridine, isopropyltriethoxysilane and isophorone diisocyanate in a mass ratio of 0.8:0.2:1.5 in chloroform, mixing a pyridine solution with an isophorone diisocyanate solution and reacting for 1h to obtain a polyurea trimer solution, carrying out rotary evaporation on the polyurea trimer solution at 40 ℃, then separating out the polyurea trimer, carrying out suction filtration, and drying at 60 ℃ for 8h to obtain the white polyurea trimer.
Respectively dissolving polyurea tripolymer and polyacrylate prepolymer containing 2- (tert-butylamino) ethyl methacrylate in a mass ratio of 10:43.5 in N-dimethylformamide, uniformly mixing the polyurea tripolymer solution and the prepolymer solution, reacting at the constant temperature of 80 ℃ for 4 hours, and drying the obtained solution at the temperature of 80 ℃ for 12 hours to obtain the self-repairing high polymer adhesive for the tire.
The infrared spectra of the compounds obtained in comparative example 1 and examples 1 and 2 are shown in FIG. 2 at 1640--1The peaks in between all indicate the presence of urea linkages.
Example 3
The polymer compounds obtained in comparative example 1 and examples 1 and 2 were subjected to a performance study test:
the polymer compounds obtained in comparative example 1, examples 1 and 2 were applied to the inner liner of the tire, forming a layer of puncture-proof and air leakage-proof coating on the inner wall of the tire, cutting off the dumbbell-shaped tire splines at the middle position by using a clean blade, splicing the splines together according to the original position, covering the two sides by using transparent slides, applying a certain pressure (500g weight) at the splicing position to observe the repairing condition of the cutting-splicing position of the three sample strips at normal temperature, and the mechanical property and the self-repairing property of the sample strips are measured in a tensile testing machine at room temperature according to the standard GB/T528-1998 for 0.5h, 1h, 2h and 24h, multiple cutting-repairing experiments are carried out on the self-repairing polymer to verify the repeated repairability of the self-repairing polymer, wherein the repair efficiency is equal to the tensile properties of the repaired sample divided by the tensile properties of the uncut original sample.
The mechanical properties and self-repairing properties of the sample strips and the uncut original samples after 0.5h, 1h, 2h and 24h at normal temperature are shown in the table 1.
Table 1 adhesive mechanical properties and repair efficiency test results
Table 1 is a statistical table of repair efficiency and mechanical property of the comparative example and the example at room temperature for different times, which shows that the mechanical property and the multiple self-repair test of the comparative example 1 are both stronger than those of the comparative example 1 and the comparative example, and compared with the examples 1 and 2, the repair efficiency is lower because the urea bond of the comparative example 1 is on the main chain and the chain movement capability is more limited, and the self-repair urea bond group of the adhesive polymer in the examples 1 and 2 is on the side chain of the main molecular chain, the chain movement is more flexible, the bonding of the urea bond is convenient, the repair efficiency of the examples 1 and 2 is higher, and the performance after repair is better; the amine group activity on piperazine of example 1 is greater than the amine group activity on pyridine of example 2, so the repair efficiency of example 2 is lower than that of example 1.
Fig. 3 is a graph of repair times and repair efficiency of comparative examples and examples at normal temperature, wherein the repair-cutting interval is 24 hours, the graph illustrates that examples 1 and 2 can repair most of mechanical properties after 24 hours, while the repair efficiency of comparative example 1 is basically unchanged after multiple repairs, which illustrates that urea bonds on the molecular chain main chain cannot be repaired at normal temperature due to limited movement, and the repair efficiency may be mainly due to physical adhesion caused by physical entanglement of the molecular chain on the cross section rather than re-bonding of chemical bonds.
Example 4
Weighing ethyl acrylate, butyl acrylate, 2- (tert-butylamino) ethyl methacrylate, azobisisoheptonitrile and dimethyl azobisisobutyrate in a mass ratio of 5.5:7:0.5:0.02, dissolving in tetrahydrofuran solvent, mixing, heating to 80 ℃, reacting at constant temperature for 4h to obtain amino group-containing branched polyacrylate prepolymer, drying the prepolymer at 80 ℃ for 12h, and removing the solvent to obtain the polyacrylate prepolymer containing 2- (tert-butylamino) ethyl methacrylate.
Respectively dissolving aminopyridine, isopropyltriethoxysilane and dicyclohexylmethane diisocyanate in a mass ratio of 0.95:0.2:2.5 in dichloromethane, mixing the pyridine solution with the toluene diisocyanate solution and reacting for 4 hours to obtain a polyurea trimer solution, carrying out rotary evaporation on the polyurea trimer solution at 40 ℃, then separating out the polyurea trimer, carrying out suction filtration, and drying at 60 ℃ for 8 hours to obtain the white polyurea trimer.
Respectively dissolving polyurea tripolymer and polyacrylate prepolymer containing 2- (tert-butylamino) ethyl methacrylate in a mass ratio of 4:1 in N-N dimethylformamide, uniformly mixing the polyurea tripolymer solution and the prepolymer solution, reacting at the constant temperature of 80 ℃ for 4 hours, and drying the obtained solution at the temperature of 80 ℃ for 12 hours to obtain the self-repairing high molecular adhesive for the tire.
Example 5
Weighing ethyl methacrylate, 2- (tert-butylamino) ethyl methacrylate and cumene hydroperoxide in a mass ratio of 15:2.5:0.15, dissolving in tetrahydrofuran solvent, mixing and heating to 80 ℃, reacting at constant temperature for 4h to obtain polyacrylate prepolymer containing amino branched chains, drying the prepolymer at 80 ℃ for 12h, and removing the solvent to obtain the polyacrylate prepolymer containing 2- (tert-butylamino) ethyl methacrylate.
Imidazole, isopropyltriethoxysilane and naphthalene diisocyanate in the mass ratio of 1.2:0.2:2.6 are respectively dissolved in toluene, a pyridine solution and a toluene diisocyanate solution are mixed and reacted for 2 hours to obtain a polyurea trimer solution, the polyurea trimer solution is subjected to rotary evaporation at 40 ℃, then the polyurea trimer is separated out, and after suction filtration, drying is carried out at 60 ℃ for 8 hours to obtain white polyurea trimer.
Respectively dissolving polyurea tripolymer and polyacrylate prepolymer containing 2- (tert-butylamino) ethyl methacrylate in a mass ratio of 12.5:65 in N-N dimethylformamide, uniformly mixing the polyurea tripolymer solution and the prepolymer solution, reacting at the constant temperature of 80 ℃ for 4 hours, drying the obtained solution at the temperature of 80 ℃ for 12 hours to obtain the self-repairing high polymer adhesive for the tire, and mixing the obtained self-repairing high polymer adhesive for the tire and the rubber adhesive water-based polychloroprene at the normal temperature.
Example 6
Weighing butyl acrylate, ethyl 2- (tert-butylamino) methacrylate and dicyclohexyl peroxydicarbonate in a mass ratio of 10:0.1:0.02, dissolving in tetrahydrofuran solvent, mixing and heating to 80 ℃, reacting at constant temperature for 4h to obtain polyacrylate prepolymer containing amino branched chain, drying the prepolymer at 80 ℃ for 12h, and removing the solvent to obtain the polyacrylate prepolymer containing the ethyl 2- (tert-butylamino) methacrylate.
Dissolving piperazine, isopropyltriethoxysilane and p-xylylene diisocyanate in a mass ratio of 0.5:0.2:1 in acetone respectively, mixing a pyridine solution and a toluene diisocyanate solution, reacting for 1h to obtain a polyurea trimer solution, carrying out rotary evaporation on the polyurea trimer solution at 40 ℃, then separating out the polyurea trimer, carrying out suction filtration, and drying at 60 ℃ for 8h to obtain a white polyurea trimer.
Respectively dissolving polyurea tripolymer and polyacrylate prepolymer containing 2- (tert-butylamino) ethyl methacrylate in a mass ratio of 2:35 in N-N dimethylformamide, uniformly mixing the polyurea tripolymer solution and the prepolymer solution, reacting at a constant temperature of 80 ℃ for 4 hours, drying the obtained solution at 80 ℃ for 12 hours to obtain the self-repairing high polymer adhesive for the tire, and mixing the obtained self-repairing high polymer adhesive for the tire and rubber adhesives (water-based polychloroprene and carboxylated chloroprene rubber adhesive) at normal temperature.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a self-repairing high polymer adhesive for a tire is characterized by comprising the following steps:
1) dissolving 2- (tert-butylamino) ethyl methacrylate, an acrylate monomer and an initiator in an organic solvent I, heating, and carrying out free radical reaction to obtain a polyacrylate prepolymer containing 2- (tert-butylamino) ethyl methacrylate;
2) respectively dissolving a cross-linking agent, a silane coupling agent and an isocyanate monomer in an organic solvent II, and uniformly mixing and reacting a cross-linking agent solution, a silane coupling agent solution and an isocyanate monomer solution to obtain a polyurea trimer;
3) and respectively dissolving the polyurea tripolymer and the polyacrylate prepolymer in an organic solvent I, mixing the polyurea tripolymer and the polyacrylate prepolymer solution for reaction, and drying the obtained solution to obtain the self-repairing adhesive for the tire.
2. The preparation method according to claim 1, wherein the mass ratio of the ethyl 2- (tert-butylamino) methacrylate to the acrylate monomer to the initiator is 0.1-2.5: 10-15: 0.02-0.15; the mass ratio of the cross-linking agent to the silane coupling agent to the isocyanate monomer is 0.5-1.2: 0.2: 1-2.6; the mass ratio of the polyurea tripolymer to the polyacrylate prepolymer is 2-12.5: 35-65.
3. The method according to claim 1, wherein the temperature of the radical reaction in step 1) is 80 ℃ and the isothermal reaction time is 4 hours; the mixing reaction time in the step 2) is 1-4 h; the mixing reaction time in the step 3) is 4 hours, and the reaction temperature is 80 ℃.
4. The preparation method of claim 1, wherein the acrylate monomer in step 1) is selected from one or more of methyl methacrylate, ethyl acrylate, ethyl methacrylate and butyl acrylate.
5. The method according to claim 1, wherein the first organic solvent in steps 1) and 3) is N, N dimethylformamide or tetrahydrofuran; the organic solvent II in the step 2) is one or more of chloroform, dichloromethane, toluene, xylene and acetone.
6. The preparation method of claim 1, wherein the initiator in the step 1) is one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, cumene hydroperoxide, tert-butyl hydroperoxide, diisopropyl peroxydicarbonate or dicyclohexyl peroxydicarbonate.
7. The preparation method of claim 1, wherein the cross-linking agent solution in the step 2) is one or more of piperazine, piperidine and imidazole.
8. The method according to claim 1, wherein the silane coupling agent in step 2) is isocyanatopropyltriethoxysilane; the isocyanate monomer solution is one or more of diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate and naphthalene diisocyanate.
9. The preparation method of claim 1, wherein the tire self-repair adhesive obtained in the step 3) is mixed with a rubber adhesive at normal temperature, and the rubber adhesive is one or more of water-based polychloroprene, carboxylated chloroprene rubber adhesive, methyl methacrylate grafted chloroprene rubber adhesive, MMA-CR binary grafted adhesive, phenolic nitrile adhesive, epoxy-carboxyl nitrile rubber adhesive and silane modified phenolic nitrile adhesive.
10. The self-repairing high-molecular adhesive for the tire, which is prepared by the preparation method of any one of claims 1 to 9.
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Application publication date: 20200811 |