阅读说明：本技术 一种轮胎硫化胶囊用修补胶浆及其制备和使用方法 (Repair rubber cement for tire curing bladder and preparation and use methods thereof ) 是由 赵会岩 范屏 赵海林 张凯 于 2021-12-08 设计创作，主要内容包括：本发明涉及轮胎硫化胶囊技术领域,尤其涉及一种轮胎硫化胶囊用修补胶浆及其制备和使用方法,具体包括以下步骤：步骤S100、天然凹凸棒土清洗获得洁净凹凸棒土；步骤S200、双酚A型环氧树脂和二异氰酸酯反应获得异氰酸酯改性环氧树脂；步骤S300、异氰酸酯改性环氧树脂与洁净凹凸棒土混合获得凹凸棒土/环氧树脂复合颗粒；步骤S400、卤化橡胶、凹凸棒土/环氧树脂复合颗粒、六方氮化硼、硫磺混炼后获得混炼胶；步骤S500、脂环族多元醇、脂环族多元酸和二异氰酸酯反应获得聚氨酯预聚体；步骤S600、混炼胶、乙酸乙酯和聚氨酯预聚体混合获得修补胶浆。本发明提供的修补胶浆粘合强度高、耐高温性好、韧性好、导热性好。(The invention relates to the technical field of tire curing bladders, in particular to a repair adhesive for a tire curing bladder and a preparation and use method thereof, which specifically comprise the following steps: step S100, cleaning natural attapulgite to obtain clean attapulgite; step S200, reacting bisphenol A epoxy resin with diisocyanate to obtain isocyanate modified epoxy resin; step S300, mixing isocyanate modified epoxy resin and clean attapulgite to obtain attapulgite/epoxy resin composite particles; s400, mixing halogenated rubber, attapulgite/epoxy resin composite particles, hexagonal boron nitride and sulfur to obtain a rubber compound; step S500, reacting alicyclic polyol, alicyclic polyacid and diisocyanate to obtain a polyurethane prepolymer; and step S600, mixing the rubber compound, ethyl acetate and the polyurethane prepolymer to obtain the repair rubber cement. The repair mucilage provided by the invention has the advantages of high bonding strength, good high temperature resistance, good toughness and good heat conductivity.)

1. The preparation method of the repair mucilage for the tire curing bladder is characterized by comprising the following steps of:

s100, dispersing natural attapulgite in deionized water, stirring for 5-10 minutes under the assistance of 40-50 KHz ultrasonic by using an ultrasonic disperser, and performing vacuum drying to obtain clean attapulgite;

step S200, heating bisphenol A epoxy resin to 150-160 ℃, slowly adding diisocyanate and 2, 4, 6-tris (dimethylaminomethyl) phenol under a stirring state, and reacting for 5-6 hours to obtain isocyanate modified epoxy resin;

step S300, mixing and stirring isocyanate modified epoxy resin and ethyl acetate uniformly at room temperature, adding the clean attapulgite obtained in the step S100, stirring for 30-60 minutes under the assistance of 40 KHz-50 KHz ultrasound by using an ultrasonic disperser, carrying out reduced pressure distillation to obtain attapulgite/epoxy resin composite particles, and condensing and recovering the distilled ethyl acetate;

step S400, mixing halogenated rubber, attapulgite/epoxy resin composite particles, castor oil, zinc oxide, stearic acid, hexagonal boron nitride, sulfur and magnesium oxide to obtain a rubber compound;

step S500, mixing and stirring alicyclic polyol, alicyclic polyacid and a catalyst uniformly, stirring and reacting at 140-200 ℃ for 4-5 hours, cooling to 70-80 ℃, slowly adding diisocyanate under a stirring state, and continuously stirring and reacting for 5-6 hours to obtain a polyurethane prepolymer with 13-15 wt% of-NCO content;

and S600, soaking the mixed rubber obtained in the step S400 in ethyl acetate, adding the polyurethane prepolymer obtained in the step S500 and 2, 4, 6-tris (dimethylaminomethyl) phenol after soaking and swelling, and uniformly mixing and stirring to obtain the repair adhesive cement.

2. The method of producing a repair cement for a tire curing bladder according to claim 1,

in the step S200, the bisphenol A type epoxy resin is at least one of bisphenol A type epoxy resin E44, bisphenol A type epoxy resin E51 and bisphenol A type epoxy resin E55;

in step S200, the diisocyanate is at least one of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, and methylcyclohexane diisocyanate.

3. The method of claim 1, wherein the halogenated rubber in step S400 is at least one of neoprene, chlorinated natural rubber, chlorinated butyl rubber, and brominated butyl rubber.

4. The method of producing a repair cement for a tire curing bladder according to claim 1,

in the step S500, the alicyclic polybasic acid is at least one of tetrahydrophthalic acid, hexahydroisophthalic acid, 1, 2-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid and 1, 4-cyclohexanedicarboxylic acid;

in step S500, the alicyclic polyol is at least one of cyclohexanedimethanol and cyclohexanediol;

in the step S500, the catalyst is at least one of dibutyltin dilaurate, stannous octoate, dibutyltin bis (dodecyl sulfide) and dibutyltin diacetate;

in step S500, the diisocyanate is at least one of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, and methylcyclohexane diisocyanate.

5. The method of producing a repair cement for a tire curing bladder according to claim 1,

in step S200, the mass ratio of bisphenol A epoxy resin, diisocyanate and 2, 4, 6-tris (dimethylaminomethyl) phenol is (140-150): (50-60): (1-3);

in the step S300, the mass ratio of the isocyanate modified epoxy resin to the ethyl acetate to the clean attapulgite is (30-40): 100: (60-70);

in step S400, the mass ratio of the halogenated rubber, the attapulgite/epoxy resin composite particles, the castor oil, the zinc oxide, the stearic acid, the hexagonal boron nitride, the sulfur and the magnesium oxide is 100: (40-60): (3-4): (3-6): (1-3): (2-5): (1-3): (4-6);

in step S500, the mass ratio of the alicyclic polyol, the alicyclic polyacid, the catalyst and the diisocyanate is (120-140): 100: (0.5-1): (180-200);

in step S600, ethyl acetate: mixing rubber: a polyurethane prepolymer: 2, 4, 6-tris (dimethylaminomethyl) phenol = 100: 20: 5: 0.03.

6. the method for preparing a repair cement for a tire curing bladder according to claim 1, wherein the pre-activating the clean attapulgite in step S100 comprises the following steps:

step S110, soaking the clean attapulgite in a dilute acid solution after sieving the attapulgite by a sieve of 300-500 meshes, stirring the mixture for 1-2 hours under the assistance of 40-50 KHz ultrasonic by an ultrasonic disperser, washing the mixture to be neutral by deionized water, and drying the mixture in vacuum at 100-120 ℃ to obtain acid-modified attapulgite;

s120, putting the acid modified attapulgite obtained in the step S110 into an ion beam irradiation device for ion beam bombardment, wherein the ion beam energy range is 5-1000 keV, and the dosage range is 20-100000 keV, so as to obtain pre-activated clean attapulgite;

the dilute acid solution is a dilute hydrochloric acid solution or a dilute nitric acid solution with the concentration of 0.5-1 wt%.

7. The method of claim 1, wherein the step S400 of preparing the rubber compound specifically comprises the steps of:

step S410, adding halogenated rubber, castor oil, zinc oxide and stearic acid into an internal mixer, mixing for 40 seconds, adding attapulgite/epoxy resin composite particles and hexagonal boron nitride, and continuously mixing for 240 seconds to obtain a master batch;

and step S420, adding the master batch, sulfur and magnesium oxide into the open mill, performing triangular bag at least five times, and discharging rubber to obtain the rubber compound.

8. The method of producing a repair cement for a tire curing bladder according to claim 7,

in the step S410, banburying temperature is 100-110 ℃;

in step S420, the open milling temperature is 60-80 ℃.

9. A repair cement for a tire curing bladder, characterized by being produced by the method for producing a repair cement for a tire curing bladder according to any one of claims 1 to 8.

10. The use method of the repair cement for the tire curing bladder as claimed in claim 9, wherein the repair cement is applied to the surfaces of the locations to be repaired of the repair rubber sheet and the curing bladder, and left at room temperature, and the repair rubber sheet and the curing bladder are adhered together after the solvent is volatilized, and then cured and adhered at 150-160 ℃.

Technical Field

The invention relates to the technical field of tire curing bladders, in particular to a repair rubber cement for a tire curing bladder and a preparation and use method thereof.

Background

The vulcanization capsule plays roles of inflation expansion shaping, transmission of superheated water pressure, guarantee of the fact that the rubber material is filled in the mold cavity to achieve the required contour, transmission of heat required by tire vulcanization and the like in the tire vulcanization process.

The curing bladder is indispensable in tire production, the consumption of the curing bladder is also an important part of the tire manufacturing cost, the damage of the curing bladder can cause the tire to generate gaps, toe fillets and rubber shortage, and the appearance quality defects such as delamination and the like occur in severe cases, so that the vulcanized tire is defective, and therefore, the curing bladder must be replaced in time when being damaged. The damage of the curing bladder is generally divided into aging, soft hole, mechanical damage, block falling, impact explosion and the like, and the curing bladder can be repaired to improve the use times of the curing bladder and reduce the production cost of the tire.

Disclosure of Invention

In order to solve the technical problems, the invention provides a preparation method of a repair cement for a tire curing bladder, which comprises the following steps:

s100, dispersing natural attapulgite in deionized water, stirring for 5-10 minutes under the assistance of 40-50 KHz ultrasonic by using an ultrasonic disperser, and performing vacuum drying to obtain clean attapulgite;

step S200, heating bisphenol A epoxy resin to 150-160 ℃, slowly adding diisocyanate and 2, 4, 6-tris (dimethylaminomethyl) phenol under a stirring state, and reacting for 5-6 hours to obtain isocyanate modified epoxy resin;

step S300, mixing and stirring isocyanate modified epoxy resin and ethyl acetate uniformly at room temperature, adding the clean attapulgite obtained in the step S100, stirring for 30-60 minutes under the assistance of 40 KHz-50 KHz ultrasound by using an ultrasonic disperser, carrying out reduced pressure distillation to obtain attapulgite/epoxy resin composite particles, and condensing and recovering the distilled ethyl acetate;

step S400, mixing halogenated rubber, attapulgite/epoxy resin composite particles, castor oil, zinc oxide, stearic acid, hexagonal boron nitride, sulfur and magnesium oxide to obtain a rubber compound;

step S500, mixing and stirring alicyclic polyol, alicyclic polyacid and a catalyst uniformly, stirring and reacting at 140-200 ℃ for 4-5 hours, cooling to 70-80 ℃, slowly adding diisocyanate under a stirring state, and continuously stirring and reacting for 5-6 hours to obtain a polyurethane prepolymer with 13-15 wt% of-NCO content;

and S600, soaking the mixed rubber obtained in the step S400 in ethyl acetate, adding the polyurethane prepolymer obtained in the step S500 and 2, 4, 6-tris (dimethylaminomethyl) phenol after soaking and swelling, and uniformly mixing and stirring to obtain the repair adhesive cement.

In the technical scheme, the attapulgite and the isocyanate modified epoxy resin are mixed and stirred, so that the isocyanate modified epoxy resin is loaded on the surface and in the pores of the attapulgite, and then is used as a filler to be mixed with the halogenated rubber. The attapulgite is used as a carrier of the isocyanate modified epoxy resin, so that on one hand, the attapulgite can play a role in slowly releasing the isocyanate modified epoxy resin, prolong the reaction time of the isocyanate modified epoxy resin and a polyurethane prepolymer, and increase the operation time of brushing the repair mucilage, on the other hand, the attapulgite can replace carbon black to be used as a reinforcing filler of halogenated rubber, and the production cost is reduced. During vulcanization, the cross-linked elastic polymer formed by the halogenated rubber interpenetrates with the cross-linked resin formed by the reaction of the isocyanate modified epoxy resin and the polyurethane prepolymer to form an interpenetrating polymer network structure, so that the bonding strength of the repair mortar is improved.

The bisphenol A epoxy resin and diisocyanate are adopted to react at the temperature of 150-160 ℃, the diisocyanate has a toughening effect on the epoxy resin, and simultaneously the diisocyanate can react with the bisphenol A epoxy resin to generate isocyanate modified epoxy resin with an oxazolidone structure, and the oxazolidone structure can improve the heat resistance of the repair adhesive cement.

The hexagonal boron nitride is added during the mixing of the halogenated rubber, so that the thermal conductivity of the repair mortar can be improved.

The alicyclic polyol and the alicyclic polyacid react to generate high-temperature-resistant polyester polyol, and the polyurethane prepolymer generated by the reaction of the high-temperature-resistant polyester polyol and the diisocyanate has excellent high-temperature resistance.

The diisocyanate reacts the epoxy resin and the polyurethane prepolymer at the subsequent vulcanization temperature (150-160 ℃), so that the crosslinked resin with the oxazolidone structure can be further obtained, and the heat resistance of the repair adhesive cement is improved.

Preferably, the first and second liquid crystal materials are,

in the step S200, the bisphenol A type epoxy resin is at least one of bisphenol A type epoxy resin E44, bisphenol A type epoxy resin E51 and bisphenol A type epoxy resin E55;

in step S200, the diisocyanate is at least one of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, and methylcyclohexane diisocyanate.

Preferably, the halogenated rubber in step S410 is at least one of neoprene, chlorinated natural rubber, chlorinated butyl rubber and brominated butyl rubber.

Preferably, the first and second liquid crystal materials are,

in the step S500, the alicyclic polybasic acid is at least one of tetrahydrophthalic acid, hexahydroisophthalic acid, 1, 2-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid and 1, 4-cyclohexanedicarboxylic acid;

in step S500, the alicyclic polyol is at least one of cyclohexanedimethanol and cyclohexanediol;

in the step S500, the catalyst is at least one of dibutyltin dilaurate, stannous octoate, dibutyltin bis (dodecyl sulfide) and dibutyltin diacetate;

in step S500, the diisocyanate is at least one of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, and methylcyclohexane diisocyanate.

Preferably, the first and second liquid crystal materials are,

in step S200, the mass ratio of bisphenol A epoxy resin, diisocyanate and 2, 4, 6-tris (dimethylaminomethyl) phenol is (140-150): (50-60): (1-3);

in the step S300, the mass ratio of the isocyanate modified epoxy resin to the ethyl acetate to the clean attapulgite is (30-40): 100: (60-70);

in step S400, the mass ratio of the halogenated rubber, the attapulgite/epoxy resin composite particles, the castor oil, the zinc oxide, the stearic acid, the hexagonal boron nitride, the sulfur and the magnesium oxide is 100: (40-60): (3-4): (3-6): (1-3): (2-5): (1-3): (4-6);

in step S500, the mass ratio of the alicyclic polyol, the alicyclic polyacid, the catalyst and the diisocyanate is (120-140): 100: (0.5-1): (180-200);

in step S600, ethyl acetate: mixing rubber: a polyurethane prepolymer: 2, 4, 6-tris (dimethylaminomethyl) phenol = 100: 20: 5: 0.03.

in an embodiment of the present invention, the pre-activating the clean attapulgite in the step S100 specifically includes the following steps:

step S110, soaking the clean attapulgite in a dilute acid solution after sieving the attapulgite by a sieve of 300-500 meshes, stirring the mixture for 1-2 hours under the assistance of 40-50 KHz ultrasonic by an ultrasonic disperser, washing the mixture to be neutral by deionized water, and drying the mixture in vacuum at 100-120 ℃ to obtain acid-modified attapulgite;

s120, putting the acid modified attapulgite obtained in the step S110 into an ion beam irradiation device for ion beam bombardment, wherein the ion beam energy range is 5-1000 keV, and the dosage range is 20-100000 keV, so as to obtain pre-activated clean attapulgite;

the dilute acid solution is a dilute hydrochloric acid solution or a dilute nitric acid solution with the concentration of 0.5-1 wt%.

In the technical scheme, the number of the pore channels of the attapulgite can be increased by soaking the attapulgite in the dilute acid solution, and the volume of the pore channels is increased. The attapulgite is soaked in dilute acid solution, tetrahedrons and octahedral structures in crystal lattices are partially dissolved, and undissolved octahedral structures play a supporting role, so that the number of pore passages of the attapulgite is increased, and the specific surface area is increased. Meanwhile, impurities distributed in the attapulgite pore channels can be removed through dilute hydrochloric acid soaking treatment, the pore channels are dredged, the cation exchangeability is improved, and potassium ions, sodium ions, calcium ions, magnesium ions and the like in the interlayer part of the attapulgite can be replaced by hydrogen ions with smaller radius, so that the volume of the pore channels is increased, and the loading capacity of the isocyanate modified epoxy resin is improved.

The high-energy density ion beam bombardment can disperse the original attapulgite aggregation state structure in beam distribution into single rod crystals, and the rod crystals are mutually linked to form a three-dimensional porous nano network under the local heat effect of the ion beam, so that the dispersity of the attapulgite and the load capacity of the isocyanate modified epoxy resin are greatly improved.

In one embodiment of the present invention, the preparation of the rubber compound in step S400 specifically includes the following steps:

step S410, adding halogenated rubber, castor oil, zinc oxide and stearic acid into an internal mixer, mixing for 40 seconds, adding attapulgite/epoxy resin composite particles and hexagonal boron nitride, and continuously mixing for 240 seconds to obtain a master batch;

and step S420, adding the master batch, sulfur and magnesium oxide into the open mill, performing triangular bag at least five times, and discharging rubber to obtain the rubber compound.

In the technical scheme, the homogeneity of the rubber compound can be improved through sectional mixing.

Preferably, the first and second liquid crystal materials are,

in the step S410, banburying temperature is 100-110 ℃;

in step S420, the open milling temperature is 60-80 ℃.

The invention provides a repair rubber cement for a tire curing bladder, which is prepared by adopting the preparation method of the repair rubber cement for the tire curing bladder.

The invention provides a use method of a repair adhesive cement for a tire curing bladder, which comprises the steps of coating the repair adhesive cement on the surfaces of the positions to be repaired of a repair rubber sheet and a curing bladder, standing at room temperature, adhering the repair rubber sheet and the curing bladder together after a solvent is volatilized, and vulcanizing and adhering at 150-160 ℃.

Compared with the prior art, the invention has the following beneficial technical effects:

1. the attapulgite is loaded with the isocyanate modified epoxy resin, so that the slow release effect on the isocyanate modified epoxy resin can be realized, the reaction time of the isocyanate modified epoxy resin and the polyurethane prepolymer is prolonged, and the operation time of coating the repair mucilage is prolonged;

2. the attapulgite can replace carbon black to be used as a reinforcing filler of halogenated rubber, so that the production cost is reduced;

3. during vulcanization, the cross-linked elastic polymer formed by the halogenated rubber interpenetrates with the cross-linked resin formed by the reaction of the isocyanate modified epoxy resin and the polyurethane prepolymer to form an interpenetrating polymer network structure, so that the bonding strength of the repair mortar is improved;

4. the isocyanate modified epoxy resin is obtained by modifying and toughening the bisphenol A epoxy resin through diisocyanate, and the diisocyanate reacts with the bisphenol A epoxy resin to generate an oxazolidone structure, so that the heat resistance of the repair adhesive cement can be improved; the isocyanate modified epoxy resin and the polyurethane prepolymer react at the subsequent vulcanization temperature to further generate the cross-linked resin with the oxazolidone structure, so that the heat resistance of the repair adhesive cement is improved;

5. the hexagonal boron nitride is added during the mixing of the halogenated rubber, so that the thermal conductivity of the repair mortar can be improved;

6. the alicyclic polyol and the alicyclic polyacid react to generate high-temperature-resistant polyester polyol, and the polyurethane prepolymer generated by the reaction of the high-temperature-resistant polyester polyol and diisocyanate has excellent high-temperature resistance;

7. the attapulgite is pre-activated by dilute acid solution impregnation and ion beam bombardment, so that the number and the volume of the pore channels of the attapulgite are increased, and the dispersion effect of the attapulgite in chlorinated rubber, the loading capacity of isocyanate modified epoxy resin and the slow release effect are improved;

in conclusion, the repair adhesive cement provided by the invention has the advantages of high bonding strength, high operation tolerance, good high temperature resistance, good toughness and good heat conductivity.

Detailed Description

In order that the above objects, features and advantages of the present invention can be more clearly understood, the present invention will be described in further detail with reference to specific embodiments. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.

Example 1

The embodiment provides a preparation method of a repair cement for a tire curing bladder, which comprises the following steps:

s100, dispersing natural attapulgite in deionized water, stirring for 5-10 minutes under the assistance of 40-50 KHz ultrasonic by using an ultrasonic disperser, and performing vacuum drying to obtain clean attapulgite;

s200, heating bisphenol A type epoxy resin E44 to 150-160 ℃, slowly adding hexamethylene diisocyanate and 2, 4, 6-tris (dimethylaminomethyl) phenol under a stirring state, and reacting for 5-6 hours to obtain isocyanate modified epoxy resin; the mass ratio of bisphenol A epoxy resin E44, hexamethylene diisocyanate and 2, 4, 6-tris (dimethylaminomethyl) phenol is 140: 60: 1;

step S300, mixing and stirring isocyanate modified epoxy resin and ethyl acetate uniformly at room temperature, adding the clean attapulgite obtained in the step S100, stirring for 30-60 minutes under the assistance of 40 KHz-50 KHz ultrasound by using an ultrasonic disperser, carrying out reduced pressure distillation to obtain attapulgite/epoxy resin composite particles, and condensing and recovering the distilled ethyl acetate; the mass ratio of the isocyanate modified epoxy resin to the ethyl acetate to the clean attapulgite is 30: 100: 70;

step S400, mixing chloroprene rubber, attapulgite/epoxy resin composite particles, castor oil, zinc oxide, stearic acid, hexagonal boron nitride, sulfur and magnesium oxide to obtain a rubber compound; the mass ratio of the chloroprene rubber, the attapulgite/epoxy resin composite particles, the castor oil, the zinc oxide, the stearic acid, the hexagonal boron nitride, the sulfur and the magnesium oxide is 100: 40: 3: 3: 1: 5: 3: 6;

the preparation method of the rubber compound specifically comprises the following steps:

step S410, adding chloroprene rubber, castor oil, zinc oxide and stearic acid into an internal mixer, mixing for 40 seconds, adding attapulgite/epoxy resin composite particles and hexagonal boron nitride, and continuously mixing for 240 seconds to obtain master batch;

step S420, adding the master batch, sulfur and magnesium oxide into an open mill, performing triangular bag at least five times, and discharging rubber to obtain a rubber compound;

step S500, uniformly mixing and stirring cyclohexane dimethanol, tetrahydrophthalic acid and dibutyltin dilaurate, carrying out stirring reaction at the temperature of 140-200 ℃ for 4-5 hours, cooling to 70-80 ℃, slowly adding hexamethylene diisocyanate under a stirring state, and continuously stirring for reaction for 5-6 hours to obtain a polyurethane prepolymer with-NCO content of 13-15 wt%; the mass ratio of cyclohexane dimethanol, tetrahydrophthalic acid, dibutyltin dilaurate to hexamethylene diisocyanate is 120: 100: 0.5: 200 of a carrier;

step S600, dipping the mixed rubber obtained in the step S400 in ethyl acetate, adding the polyurethane prepolymer obtained in the step S500 and 2, 4, 6-tris (dimethylaminomethyl) phenol after soaking and swelling, and uniformly mixing and stirring to obtain repair adhesive cement; ethyl acetate: mixing rubber: a polyurethane prepolymer: 2, 4, 6-tris (dimethylaminomethyl) phenol = 100: 20: 5: 0.03.

example 2

The embodiment provides a preparation method of a repair cement for a tire curing bladder, which is used for pre-activating attapulgite in the preparation process and comprises the following steps:

s100, dispersing natural attapulgite in deionized water, stirring for 5-10 minutes under the assistance of 40-50 KHz ultrasonic by using an ultrasonic disperser, and performing vacuum drying to obtain clean attapulgite;

the method for pre-activating the clean attapulgite specifically comprises the following steps:

step S110, after the clean attapulgite is sieved by a sieve of 300-500 meshes, soaking the clean attapulgite in a dilute hydrochloric acid solution with the concentration of 0.5-1 wt%, stirring the mixture for 1-2 hours by an ultrasonic disperser under the assistance of 40 KHz-50 KHz of ultrasound, washing the mixture to be neutral by deionized water, and performing vacuum drying at 100-120 ℃ to obtain acid-modified attapulgite;

s120, putting the acid modified attapulgite obtained in the step S110 into an ion beam irradiation device for ion beam bombardment, wherein the ion beam energy range is 5-1000 keV, and the dosage range is 20-100000 keV, so as to obtain pre-activated clean attapulgite;

s200, heating bisphenol A type epoxy resin E44 to 150-160 ℃, slowly adding hexamethylene diisocyanate and 2, 4, 6-tris (dimethylaminomethyl) phenol under a stirring state, and reacting for 5-6 hours to obtain isocyanate modified epoxy resin; the mass ratio of bisphenol A epoxy resin E44, hexamethylene diisocyanate and 2, 4, 6-tris (dimethylaminomethyl) phenol is 140: 60: 1;

step S300, mixing and stirring isocyanate modified epoxy resin and ethyl acetate uniformly at room temperature, adding the clean attapulgite obtained in the step S100, stirring for 30-60 minutes under the assistance of 40 KHz-50 KHz ultrasound by using an ultrasonic disperser, carrying out reduced pressure distillation to obtain attapulgite/epoxy resin composite particles, and condensing and recovering the distilled ethyl acetate; the mass ratio of the isocyanate modified epoxy resin to the ethyl acetate to the clean attapulgite is 30: 100: 70;

step S400, mixing chloroprene rubber, attapulgite/epoxy resin composite particles, castor oil, zinc oxide, stearic acid, hexagonal boron nitride, sulfur and magnesium oxide to obtain a rubber compound; the mass ratio of the chloroprene rubber, the attapulgite/epoxy resin composite particles, the castor oil, the zinc oxide, the stearic acid, the hexagonal boron nitride, the sulfur and the magnesium oxide is 100: 40: 3: 3: 1: 5: 3: 6;

the preparation method of the rubber compound specifically comprises the following steps:

step S410, adding chloroprene rubber, castor oil, zinc oxide and stearic acid into an internal mixer, mixing for 40 seconds, adding attapulgite/epoxy resin composite particles and hexagonal boron nitride, and continuously mixing for 240 seconds to obtain master batch;

step S420, adding the master batch, sulfur and magnesium oxide into an open mill, performing triangular bag at least five times, and discharging rubber to obtain a rubber compound;

step S500, uniformly mixing and stirring cyclohexane dimethanol, tetrahydrophthalic acid and dibutyltin dilaurate, carrying out stirring reaction at the temperature of 140-200 ℃ for 4-5 hours, cooling to 70-80 ℃, slowly adding hexamethylene diisocyanate under a stirring state, and continuously stirring for reaction for 5-6 hours to obtain a polyurethane prepolymer with-NCO content of 13-15 wt%; the mass ratio of cyclohexane dimethanol, tetrahydrophthalic acid, dibutyltin dilaurate to hexamethylene diisocyanate is 120: 100: 0.5: 200 of a carrier;

step S600, dipping the mixed rubber obtained in the step S400 in ethyl acetate, adding the polyurethane prepolymer obtained in the step S500 and 2, 4, 6-tris (dimethylaminomethyl) phenol after soaking and swelling, and uniformly mixing and stirring to obtain repair adhesive cement; ethyl acetate: mixing rubber: a polyurethane prepolymer: 2, 4, 6-tris (dimethylaminomethyl) phenol = 100: 20: 5: 0.03.

example 3

The embodiment provides a preparation method of a repair cement for a tire curing bladder, which comprises the following steps:

s100, dispersing natural attapulgite in deionized water, stirring for 5-10 minutes under the assistance of 40-50 KHz ultrasonic by using an ultrasonic disperser, and performing vacuum drying to obtain clean attapulgite;

the method for pre-activating the clean attapulgite specifically comprises the following steps:

step S110, after the clean attapulgite is sieved by a sieve of 300-500 meshes, soaking the clean attapulgite in a dilute hydrochloric acid solution with the concentration of 0.5-1 wt%, stirring the mixture for 1-2 hours by an ultrasonic disperser under the assistance of 40 KHz-50 KHz of ultrasound, washing the mixture to be neutral by deionized water, and performing vacuum drying at 100-120 ℃ to obtain acid-modified attapulgite;

s120, putting the acid modified attapulgite obtained in the step S110 into an ion beam irradiation device for ion beam bombardment, wherein the ion beam energy range is 5-1000 keV, and the dosage range is 20-100000 keV, so as to obtain pre-activated clean attapulgite;

step S120, putting the acid modified attapulgite obtained in the step S110 into an ion beam irradiation device for ion beam bombardment, wherein the ion beam energy range is 5-1000 keV, and the dosage range is 20-100000 keV, so as to obtain pre-activated attapulgite;

s200, heating bisphenol A type epoxy resin E51 to 150-160 ℃, slowly adding isophorone diisocyanate and 2, 4, 6-tris (dimethylaminomethyl) phenol under a stirring state, and reacting for 5-6 hours to obtain isocyanate modified epoxy resin; the mass ratio of bisphenol A type epoxy resin E51, isophorone diisocyanate and 2, 4, 6-tris (dimethylaminomethyl) phenol is 150: 50: 3;

step S300, mixing and stirring isocyanate modified epoxy resin and ethyl acetate uniformly at room temperature, adding the pre-activated clean attapulgite obtained in the step S120, stirring for 30-60 minutes under the assistance of 40 KHz-50 KHz ultrasound by using an ultrasonic disperser, carrying out reduced pressure distillation to obtain attapulgite/epoxy resin composite particles, and condensing and recovering the distilled ethyl acetate; the mass ratio of the isocyanate modified epoxy resin to the ethyl acetate to the clean attapulgite is 40: 100: 60, adding a solvent to the mixture;

s400, mixing chlorinated butyl rubber, attapulgite/epoxy resin composite particles, castor oil, zinc oxide, stearic acid, hexagonal boron nitride, sulfur and magnesium oxide to obtain a rubber compound; the mass ratio of the chlorinated butyl rubber, the attapulgite/epoxy resin composite particles, the castor oil, the zinc oxide, the stearic acid, the hexagonal boron nitride, the sulfur and the magnesium oxide is 100: 60: 4: 6: 3: 2: 2: 4;

the preparation method of the rubber compound specifically comprises the following steps:

step S410, adding butyl chloride rubber, castor oil, zinc oxide and stearic acid into an internal mixer, mixing for 40 seconds, adding attapulgite/epoxy resin composite particles and hexagonal boron nitride, and continuously mixing for 240 seconds to obtain a master batch;

step S420, adding the master batch, sulfur and magnesium oxide into an open mill, performing triangular bag at least five times, and discharging rubber to obtain a rubber compound;

step S500, uniformly mixing and stirring cyclohexanediol, hexahydro-isophthalic acid and stannous octoate, stirring and reacting at 140-200 ℃ for 4-5 hours, cooling to 70-80 ℃, slowly adding isophorone diisocyanate under a stirring state, and continuously stirring and reacting for 5-6 hours to obtain a polyurethane prepolymer with 13-15 wt% of-NCO content; the mass ratio of the cyclohexanediol to the hexahydroisophthalic acid to the stannous octoate to the isophorone diisocyanate is 140: 100: 1: 180 of the total weight of the composition;

step S600, dipping the mixed rubber obtained in the step S400 in ethyl acetate, adding the polyurethane prepolymer obtained in the step S500 and 2, 4, 6-tris (dimethylaminomethyl) phenol after soaking and swelling, and uniformly mixing and stirring to obtain repair adhesive cement; ethyl acetate: mixing rubber: a polyurethane prepolymer: 2, 4, 6-tris (dimethylaminomethyl) phenol = 100: 20: 5: 0.03.

example 4

The embodiment provides a preparation method of a repair cement for a tire curing bladder, which comprises the following steps:

s100, dispersing natural attapulgite in deionized water, stirring for 5-10 minutes under the assistance of 40-50 KHz ultrasonic by using an ultrasonic disperser, and performing vacuum drying to obtain clean attapulgite;

the method for pre-activating the clean attapulgite specifically comprises the following steps:

step S110, after the clean attapulgite is sieved by a sieve of 300-500 meshes, soaking the clean attapulgite in a dilute hydrochloric acid solution with the concentration of 0.5-1 wt%, stirring the mixture for 1-2 hours by an ultrasonic disperser under the assistance of 40 KHz-50 KHz of ultrasound, washing the mixture to be neutral by deionized water, and performing vacuum drying at 100-120 ℃ to obtain acid-modified attapulgite;

s120, putting the acid modified attapulgite obtained in the step S110 into an ion beam irradiation device for ion beam bombardment, wherein the ion beam energy range is 5-1000 keV, and the dosage range is 20-100000 keV, so as to obtain pre-activated clean attapulgite;

s200, heating bisphenol A type epoxy resin E55 to 150-160 ℃, slowly adding methylcyclohexane diisocyanate and 2, 4, 6-tris (dimethylaminomethyl) phenol under a stirring state, and reacting for 5-6 hours to obtain isocyanate modified epoxy resin; the mass ratio of bisphenol A epoxy resin E55, methylcyclohexane diisocyanate and 2, 4, 6-tris (dimethylaminomethyl) phenol is 150: 50: 2;

step S300, mixing and stirring isocyanate modified epoxy resin and ethyl acetate uniformly at room temperature, adding the pre-activated clean attapulgite obtained in the step S120, stirring for 30-60 minutes under the assistance of 40 KHz-50 KHz ultrasound by using an ultrasonic disperser, carrying out reduced pressure distillation to obtain attapulgite/epoxy resin composite particles, and condensing and recovering the distilled ethyl acetate; the mass ratio of the isocyanate modified epoxy resin to the ethyl acetate to the clean attapulgite is 35: 100: 65;

s400, mixing chlorinated butyl rubber, brominated butyl rubber, attapulgite/epoxy resin composite particles, castor oil, zinc oxide, stearic acid, hexagonal boron nitride, sulfur and magnesium oxide to obtain a rubber compound; the mass ratio of chlorinated butyl rubber, brominated butyl rubber, attapulgite/epoxy resin composite particles, castor oil, zinc oxide, stearic acid, hexagonal boron nitride, sulfur and magnesium oxide is 80: 20: 50: 4: 4: 2: 4: 1: 4;

the preparation method of the rubber compound specifically comprises the following steps:

step S410, adding chlorinated butyl rubber, brominated butyl rubber, castor oil, zinc oxide and stearic acid into an internal mixer, mixing for 40 seconds, adding attapulgite/epoxy resin composite particles and hexagonal boron nitride, and continuously mixing for 240 seconds to obtain a master batch;

step S420, adding the master batch, sulfur and magnesium oxide into an open mill, performing triangular bag at least five times, and discharging rubber to obtain a rubber compound;

step S500, uniformly mixing and stirring cyclohexanediol, 1, 4-cyclohexanedicarboxylic acid and dibutyltin diacetate, stirring and reacting at the temperature of 140-200 ℃ for 4-5 hours, cooling to 70-80 ℃, slowly adding methylcyclohexane diisocyanate under the stirring state, and continuously stirring and reacting for 5-6 hours to obtain a polyurethane prepolymer with 13-15 wt% of-NCO content; the mass ratio of the cyclohexanediol to the 1, 4-cyclohexanedicarboxylic acid to the dibutyltin diacetate to the methylcyclohexane diisocyanate is 130: 100: 1: 190;

step S600, dipping the mixed rubber obtained in the step S400 in ethyl acetate, adding the polyurethane prepolymer obtained in the step S500 and 2, 4, 6-tris (dimethylaminomethyl) phenol after soaking and swelling, and uniformly mixing and stirring to obtain repair adhesive cement; ethyl acetate: mixing rubber: a polyurethane prepolymer: 2, 4, 6-tris (dimethylaminomethyl) phenol = 100: 20: 5: 0.03.

and (3) performance detection:

1. tear Strength test

The repair cements of examples 1-4 were vulcanized into sheet samples at 150-160 ℃ and tested for tear strength according to standard GB/T529-2008. A sample of the sheet was prepared as a specimen having a length x, a width x and a thickness x of 150mmx20mmx3mm, and a slit having a length of 10mm was cut at a width of 10mm of the specimen in the longitudinal direction by a cutter. The two sides of the cut of the sample were clamped to the clamps of a CSS-44100 electronic universal tester at 25 ℃ respectively, and the tear strength was measured.

2. Tensile Strength and elongation at Break test

The repair cements of examples 1-4 were vulcanized at 150-160 ℃ to give sheet samples, which were tested for tensile strength and elongation at break according to standard GB/T1701-2001. A sheet sample was cut into a dumbbell-shaped specimen having a thickness of 3mm with a standard specimen cutter, and the specimen was clamped at 25 ℃ by a chuck of a CSS-44100 electronic universal testing machine to measure the tensile strength and elongation at break.

3.100% -300% stress at definite elongation

The repair cement in the embodiment 1-4 is vulcanized into a thin sheet sample at 150-160 ℃, and a 100-300% stress at definite elongation is tested according to the standard GB/528-2009. A sheet sample is cut into a dumbbell-shaped sample with the thickness of 2mm by a standard sample cutter, the sample is clamped on a clamp of a CSS-44100 electronic universal testing machine at the temperature of 25 ℃, and the 100-300% stress at definite elongation is measured.

4. Testing of repair effectiveness

The repairing adhesive paste in the embodiment 1-4 is coated on the surfaces of the positions to be repaired of the repairing adhesive sheet and the vulcanized rubber bag, the repairing adhesive sheet and the vulcanized rubber bag are placed at room temperature, the repairing adhesive sheet and the vulcanized rubber bag are adhered together after the solvent is volatilized, the vulcanization adhesion is carried out at the temperature of 150-160 ℃, and the using times of the repaired vulcanized rubber bag are recorded.

The test results are shown in table 1:

table 1 examples 1-4 performance test results

	Example 1	Example 2	Example 3	Example 4
					Tear Strength (N. M)	40	42	46	45
Tensile Strength (MPa)	10	11	13	12
					Elongation at Break (%)	710	713	725	721
100% stress at definite elongation (MPa)	1.4	1.4	1.6	1.5
					Stress at definite elongation of 200% (MPa)	3.1	3.2	3.5	3.4
300% stress at definite elongation (MPa)	5.2	5.2	5.6	5.5
					Hardness (Shao Er A)	51	51	53	52
Number of times of use after repair	60	61	67	66

As can be seen from Table 1, the repair cement for the tire curing bladder has good physical and mechanical properties, can meet the use environment of the curing bladder, can be continuously used for more than 60 times after being repaired, and effectively reduces the production cost.

The present invention is not limited to the above-described embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention are intended to be equivalent substitutions and should be included in the scope of the present invention.