Adhesive for heat vulcanized rubber surface with high reaction activity at low temperature and preparation method thereof

Abstract

The invention relates to the technical field of adhesives, in particular to a high-reactivity adhesive for a heat-vulcanized rubber surface at a low temperature and a preparation method of the adhesive. The adhesive is prepared from the following raw materials in percentage by mass: 1-15% of a film-forming agent, 5-20% of a rubber base material, 3-15% of a modified latent curing agent, 5-15% of phenolic resin and the balance of a solvent. According to the invention, p-aminobenzene sulfonyl guanidine is preferably selected to modify p-dinitrosobenzene, active nitrogen atoms of p-dinitrosobenzene are captured at a depolymerization temperature of p-dinitrosobenzene, and existence of a polymerization state is avoided, so that the curing and bonding functions can be fully exerted under a low-temperature reaction condition, and low-temperature limit vulcanization is realized. Meanwhile, the thermosetting phenolic resin with high free phenol content is used in a matched manner, so that an interface penetration type cross-linking reaction is realized, the bonding strength of the adhesive is improved, and the bonding stability of a low-temperature reaction part in the center of a shock insulation support product is ensured.

Description

Technical Field

[0001] The invention relates to the technical field of adhesives, and in particular to an adhesive for hot-vulcanized rubber surfaces with high reactivity at low temperatures and a preparation method thereof. Background Art

[0002] Building seismic isolation bearings are one of the most important products in seismic isolation technology. Their main raw materials include rubber, steel, hot-vulcanized adhesives, coatings, lead ingots, etc. Among them, hot-vulcanized adhesives are used to achieve vulcanization bonding between multiple layers of rubber and multiple layers of steel plates in seismic isolation bearings to ensure that seismic isolation bearing products have high damping characteristics and maintain bonding effects within a 60-year service life.

[0003] The seismic isolation bearing is a thick rubber-metal composite product with a multi-layer composite structure. Its maximum length can reach about 1.5m and its maximum height can reach about 1m. The vulcanization bonding method in the production process of the seismic isolation bearing is generally to transfer heat through the upper and lower heating templates of the vulcanizer to achieve hot vulcanization bonding. In actual operation, the heating temperature of the upper and lower templates of the vulcanizer is too high, which will cause the rubber at both ends of the bearing to over-vulcanize and deteriorate the mechanical properties, so a lower heating template temperature is generally used. However, the seismic isolation bearing often has a large thickness, and the thermal conductivity of the rubber is poor, which leads to a significant decrease in temperature when it is transferred to the middle layer during the vulcanization process. The actual middle layer temperature of the bearing is as low as about 90-100°C. Under such low temperature conditions, the reaction activity of conventional hot vulcanization adhesives is insufficient, and it is difficult to achieve a good bonding effect with rubber, resulting in the seismic isolation bearing products often having bonding failure problems in the middle layer, which has potential safety hazards.

[0004] Chinese patent CN109790435B discloses a heat-vulcanizable adhesive and an adhesive strip made from it, which includes a meltable polybutadiene-polyurethane, ground sulfur and optionally at least one vulcanization accelerator, at least one filler, at least one epoxy resin, at least one tackifier resin, asphalt, at least one softener and other auxiliary and additive materials. The adhesive can maintain adhesion and shear strength, but its heat vulcanization temperature is 130°C to 230°C, which cannot meet the use requirements of low-temperature vulcanization. Chinese patent CN115058221B discloses a highly flexible heat-vulcanized adhesive specially used for bonding deformable substrates, and the curing agent is selected as at least one of aromatic amine compounds, ester compounds, and aliphatic tetraamines, so that the bonding performance of the cured heat-vulcanized adhesive is improved. However, the vulcanization temperature of the adhesive is 165°C, which also cannot meet the use requirements of low-temperature vulcanization.

[0005] Under such circumstances, there is an urgent need to provide an adhesive that can be vulcanized under low temperature conditions, has high curing activity and strong adhesion to meet the use requirements of seismic isolation bearing products. Summary of the invention

[0006] In order to solve the above-mentioned technical problems, improve the bonding effect of the middle layer of the seismic isolation bearing products, and enhance the mechanical properties of the seismic isolation bearing products, the present invention provides a hot-vulcanized adhesive with high reactivity at extremely low vulcanization temperatures. The core uses a modified latent curing agent, combined with a specific amount of thermosetting phenolic resin and other functional components, to achieve the technical effect of the adhesive having high bonding reaction activity at a vulcanization temperature as low as 90-100°C. The obtained adhesive can ensure stable and firm bonding of the middle layer of the seismic isolation bearing. Compared with ordinary hot-vulcanized adhesives, the performance is significantly improved, and it has great technical advantages.

[0007] The first aspect of the present invention provides a heat-vulcanized adhesive for rubber surfaces with high reactivity at low temperature. The raw materials for preparing the adhesive include, by mass percentage:

[0008] Film former 1-15%;

[0009] Rubber base material 5-20%;

[0010] Modified latent curing agent 3-15%;

[0011] Phenolic resin 5-15%;

[0012] Make up the balance with solvent.

[0013] In some preferred embodiments, the raw materials for preparing the binder include, by mass percentage:

[0014] Film former 2-7%;

[0015] Rubber base material 5-10%;

[0016] Modified latent curing agent 3-9%;

[0017] Phenolic resin 5-10%;

[0018] Make up the balance with solvent.

[0019] In some preferred embodiments, the film-forming agent is a halogenated rubber, which is prepared by halogenating natural rubber, isoprene rubber, butadiene rubber and other rubbers with halogen; the halogen is chlorine or bromine.

[0020] In order to ensure that the heat-vulcanized adhesive forms a uniform film interface at the bonding interface with certain adhesion and hardness, it is more preferred that the halogenated rubber is chlorinated natural rubber.

[0021] In some preferred embodiments, the rubber base material includes chlorosulfonated polyethylene rubber.

[0022] Preferably, the Mooney viscosity of the chlorosulfonated polyethylene rubber is 45-75 ML (1+4) 100°C; more preferably, it is 50-70 ML (1+4) 100°C.

[0023] Preferably, the sulfur content of the chlorosulfonated polyethylene rubber is 0.7-1.5%; more preferably 0.9-1.3%.

[0024] In some preferred embodiments, the adhesive further comprises an accelerator, and the added amount of the accelerator is 2-20 wt %.

[0025] Preferably, the promoter includes a first promoter and a second promoter; the first promoter includes a metal oxide, and the second promoter includes a bismaleimide compound.

[0026] Preferably, the metal oxide includes zinc oxide or magnesium oxide. The metal oxidant can also serve as an acid absorber to promote curing, increase bonding strength, and enhance the overall performance of the adhesive.

[0027] More preferably, the first accelerator is nano-calcium carbonate-supported active zinc oxide; further preferably, the zinc oxide content in the nano-calcium carbonate-supported active zinc oxide is greater than 90%.

[0028] Preferably, the bismaleimide compounds include diphenylmethane bismaleimide, 1,2-phenylene-bismaleimide, N,N'-m-phenylene bismaleimide, 4,4'-bismaleimide diphenyl ether, 4,4'-bismaleimide diphenylmethane, 4,4'-bismaleimide-bis(3-methylphenyl)methane, 4,4'-bismaleimide-bis(3-ethylphenyl)methane , 4,4'-bismaleimide-bis(3-methyl-5-ethyl-phenyl)methane, N,N'-(2,2-bis-(4-phenoxyphenyl)propane)dimaleimide, N,N'-2,4-toluenedimaleimide, N,N'-2,6-toluenedimaleimide, 1,10-bis(maleimide)decane; more preferably N,N'-m-phenylene bismaleimide.

[0029] In some preferred embodiments, the addition amount of the first accelerator is 1-10 wt %, more preferably 2-5 wt %.

[0030] In some preferred embodiments, the amount of the second accelerator added is 1-10 wt %, more preferably 2-5 wt %.

[0031] In some preferred embodiments, the modified latent curing agent is an aromatic nitroso compound modified by a guanidine compound.

[0032] More preferably, the aromatic nitroso compound is p-dinitrosobenzene, and the guanidine compound is p-aminobenzenesulfonylguanidine.

[0033] The present invention selects the curing agent p-nitrosobenzene. Under room temperature conditions, the industrial product of p-nitrosobenzene exists in the form of polymerized macromolecules connected by N=N double bonds, and is not an independently existing small molecule monomer. In the actual vulcanization bonding process, the polymerized macromolecules need to first undergo a polymerized depolymerization process at >110°C, and only after depolymerization into p-nitrosobenzene monomer small molecules can they fully exert the vulcanization bonding function. The present invention uses guanidine compounds to modify the aromatic nitroso compound p-nitrosobenzene, and utilizes multiple active nitrogen atoms on the aminobenzenesulfonylguanidine molecule to temporarily capture the nitrogen atoms of p-nitrosobenzene that are depolymerized into monomers at high temperature, preventing them from forming polymerized p-nitrosobenzene polymerized macromolecules again, so that they are stably present in the adhesive system, and no additional depolymerization is required when used. In this way, when used for bonding of seismic isolation brackets, they can have high reactivity at a lower vulcanization temperature, thereby improving the bonding effect of the middle layer of the seismic isolation bearing product.

[0034] In some preferred embodiments, the preparation steps of the modified latent curing agent include:

[0035] Mix p-nitrosobenzene and xylene solvent, and disperse them evenly at 70-80° C. to obtain material 1;

[0036] Heat material 1 to 105-115°C and stabilize for 10-20 minutes to obtain material 2;

[0037] The material 2 is heated to 120-130° C., p-aminobenzenesulfonylguanidine is added, and the reaction is carried out by heat preservation for 40-80 minutes to obtain a modified latent curing agent.

[0038] Preferably, the molar ratio of p-dinitrosobenzene to p-aminobenzenesulfonylguanidine is (2-4):1; more preferably 3:1.

[0039] Preferably, the xylene solvent is a mixed xylene solution, and the mixed xylene solution is ethylbenzene, p-xylene, m-xylene and o-xylene compounded in a mass ratio of 15.91:18.92:39.98:24.98.

[0040] Preferably, the p-aminobenzenesulfonylguanidine is added at a uniform speed within 30 minutes.

[0041] In some preferred embodiments, the phenolic resin is a thermosetting phenolic resin.

[0042] The phenolic resin is prepared by reacting a phenolic compound and an aldehyde compound. The phenolic compound can be exemplified by phenol, cresol, diphenol, triphenol, nonylphenol, cardanol, octylphenol, bisphenol A, dimethyl phenol, o-cresol, etc., and the aldehyde compound can be exemplified by formaldehyde, acetaldehyde, furfural, etc.

[0043] In some preferred embodiments, the phenolic compound is o-cresol, and the aldehyde compound is formaldehyde, that is, the phenolic resin is an o-cresol-formaldehyde type thermosetting phenolic resin.

[0044] Preferably, the degree of polymerization of the o-cresol-formaldehyde type thermosetting phenolic resin is 4-12, more preferably 5-10.

[0045] Preferably, the hydroxymethyl content of the o-cresol-formaldehyde type thermosetting phenolic resin is 10-20%, more preferably 12-18%.

[0046] Preferably, the free phenol content of the o-cresol-formaldehyde type thermosetting phenolic resin is 10-25%, more preferably 15-20%.

[0047] The preferred o-cresol-formaldehyde type thermosetting phenolic resin of the present invention has a specific polymerization degree, and the characteristic that the thermosetting resin can self-crosslink without a curing agent is utilized to form a stable network structure in the formulation system, thereby improving the cohesive strength of the adhesive. Further controlling the methylol content of the o-cresol-formaldehyde type thermosetting phenolic resin can give the material stable chemical characteristics, help ensure that the phenolic resin fully plays a role during use, and the final adhesive has good storage stability and a long effective period. Simultaneously controlling the o-cresol-formaldehyde type thermosetting phenolic resin to contain a certain amount of free o-cresol, the free o-cresol small molecules penetrate into the rubber polymer molecular layer during the vulcanization bonding process, and the macromolecular phenolic resin undergoes a curing crosslinking reaction to achieve a penetration reaction. The free o-cresol of the small molecule penetrates into the rubber layer molecular chain part and the rubber layer polymer entanglement, realizes the connection of the microscopic interface, and further improves the bonding strength of the adhesive.

[0048] In some preferred embodiments, the preparation steps of the o-cresol-formaldehyde type thermosetting phenolic resin include: first mixing phenol and a catalyst, raising the reaction temperature to 45-55° C., adding a formaldehyde aqueous solution dropwise, raising the temperature to 75-85° C. after the addition is completed, reacting for 1-3 hours, removing water in the system by reduced pressure distillation, and then mixing the material with a mixed xylene solvent to a solid content of 70-85%, thereby obtaining a finished o-cresol-formaldehyde type thermosetting phenolic resin.

[0049] The catalyst may be hydrochloric acid, oxalic acid, sulfuric acid, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, barium hydroxide, ammonia, magnesium oxide, zinc acetate, etc., preferably sodium hydroxide.

[0050] Preferably, the added amount of the catalyst is 2.5% of the mass of phenol.

[0051] Preferably, the formaldehyde aqueous solution is added dropwise within 20-40 minutes.

[0052] In some preferred embodiments, the adhesive further comprises a pigment or filler, and the added amount of the pigment or filler is 1-10 wt %, more preferably 2-6 wt %.

[0053] Preferably, the pigment and filler include carbon black, which can be listed as a combination of one or more of N234, N326, N330, and N762. In the present invention, N234 is preferred.

[0054] In some preferred embodiments, the solvent includes one or a combination of xylene, toluene, ethylbenzene, benzene, methyl isobutyl ketone, cyclohexane, pentane, isopropanol, and ether, and xylene is preferred in the present invention.

[0055] The second aspect of the present invention provides a method for preparing the hot-vulcanized adhesive for rubber surfaces with high reactivity at low temperature as described above, the preparation steps comprising:

[0056] S1. The raw materials other than the phenolic resin are mixed, ground and dispersed to obtain a first base material;

[0057] S2. Add phenolic resin to the first base material and disperse it at high speed to obtain a finished adhesive product.

[0058] In some preferred embodiments, the grinding and dispersing conditions in step S1 are: rotation speed 2000-3000 rpm, temperature 25-50° C., and dispersing time 10-50 min; more preferably, rotation speed 2200-2500 rpm, temperature 35-45° C., and dispersing time 15-30 min.

[0059] In some preferred embodiments, the conditions for high-speed dispersion in step S2 are: rotation speed 800-2000 rpm, dispersion time 20-120 min; more preferably, rotation speed 800-1200 rpm, dispersion time 30-60 min.

[0060] The present invention does not impose any particular limitation on the dispersing equipment in the preparation step, as long as the dispersing purpose can be achieved; for example, a horizontal grinder or a basket grinder can be used for grinding and dispersing, and a high-speed disperser can be used for high-speed dispersion.

[0061] The third aspect of the present invention provides a method for using the above-mentioned adhesive for hot-vulcanized rubber surfaces with high reactivity at low temperature, wherein the vulcanization temperature of the adhesive is 90-100° C. and the vulcanization time is 3-6 hours.

[0062] Beneficial effects:

[0063] The present invention provides a hot-vulcanized adhesive for rubber surfaces with high reactivity at low temperature and a preparation method thereof, which has the following advantages:

[0064] (1) The present invention preferably uses a modified latent curing agent, especially p-aminobenzenesulfonylguanidine to modify p-nitrosobenzene, which captures its active nitrogen atoms at the depolymerization temperature of p-nitrosobenzene to prevent it from forming a polymerized state again after cooling; during vulcanization bonding, p-nitrosobenzene is released at a lower temperature, so that it can fully exert its curing and bonding function under low-temperature reaction conditions, thereby achieving low-temperature extreme vulcanization.

[0065] (2) On the basis of using a modified latent curing agent, a thermosetting phenolic resin containing a high free phenol content is used at the same time. The free o-cresol small molecules penetrate into the rubber polymer molecular layer to achieve an interfacial penetrating cross-linking reaction, thereby improving the bonding strength of the adhesive and ensuring the bonding stability of the low-temperature reaction area in the center of the seismic isolation bearing product.

[0066] (3) The present invention selects two accelerators for compounding, and preferably the first accelerator includes a metal oxide, and the second accelerator includes a bismaleimide compound, which improves the comprehensive performance of the adhesive. The obtained adhesive can be vulcanized at 90-100°C, and the bonding strength reaches more than 8MPa, the proportion of bonding failure area is low, and the performance of the adhesive is excellent.

[0067] (4) The raw materials of the present invention are easily available and the process is simple, which can greatly improve the production efficiency and meet the use requirements of seismic isolation bearing products.

[0068] (5) The present invention provides a method for improving the bonding effect under extremely low temperature vulcanization conditions, which promotes the technological progress of heat-vulcanized adhesives. The obtained heat-vulcanized adhesive has broad application prospects. DETAILED DESCRIPTION

[0069] Note: Unless otherwise specified, the raw materials used in the present invention are commercially available.

[0070] Examples 1-4

[0071] Embodiment 1-4 provides a heat-vulcanized rubber surface adhesive with high reactivity at low temperature and a preparation method thereof. The formula composition of the adhesive is shown in Table 1 below.

[0072] Table 1 Adhesive formulations of Examples 1-4

[0073]

[0074] Note: The values ​​in Table 1 are the added amounts, in g.

[0075] The chlorinated natural rubber is sourced from Ningbo Haoxin Yulong New Materials Co., Ltd., and the product model is CR400.

[0076] The chlorosulfonated polyethylene rubber is from Jiangxi Hongrun Chemical Co., Ltd., and the product model is CSM-30. The Mooney viscosity of the chlorosulfonated polyethylene rubber is 69ML(1+4)100°C.

[0077] The sulfur content of the chlorosulfonated polyethylene rubber is 1.23%.

[0078] The nano-scale calcium carbonate-supported active zinc oxide is from Inoue Lime Industry Co., Ltd., and the product model is META-Z 102. The zinc oxide content of the nano-scale calcium carbonate-supported active zinc oxide is 90.4%.

[0079] The mixed xylene is ethylbenzene, p-xylene, m-xylene and o-xylene in a mass ratio of 15.91:18.92:39.98:24.98.

[0080] The preparation steps of p-aminobenzenesulfonylguanidine modified p-dinitrosobenzene include:

[0081] Step 1: Add 400g of solvent and 136g of p-dinitrosobenzene into a 1000mL flask, heat to 75°C and disperse evenly to obtain material 1; keep the speed at 300r during the process;

[0082] Step 2: Heat material 1 to 110°C, stabilize for 15 minutes after the temperature reaches 110°C, and obtain material 2; keep the speed at 300r during the process;

[0083] Step 3: Heat the material 2 to 125°C, add 71g of p-aminobenzenesulfonylguanidine at a uniform rate within 30 minutes, and keep warm for 60 minutes after the addition is completed to obtain a modified latent curing agent; keep the rotation speed at 500r during the process.

[0084] In the first step, the stirring speed is set to 300 rpm, and a spherical condenser is installed to perform condensation reflux during the reaction process.

[0085] The o-cresol-formaldehyde type thermosetting phenolic resin F1 has a polymerization degree of 8-10, a hydroxymethyl content of 15%, and a free phenol content of 5%.

[0086] The o-cresol-formaldehyde type thermosetting phenolic resin F2 has a polymerization degree of 8-10, a hydroxymethyl content of 15%, and a free phenol content of 15%.

[0087] The o-cresol-formaldehyde type thermosetting phenolic resins F1 and F2 are both homemade, and the preparation method is as follows.

[0088] Preparation of o-cresol-formaldehyde type thermosetting phenolic resin F1:

[0089] (1) A four-necked flask is placed in an electric heating mantle to build a synthesis device, and a polytetrafluoroethylene stirring paddle, a spherical condenser and a thermometer are installed in the four-necked flask;

[0090] (2) 200 g of phenol and 5 g of catalyst (sodium hydroxide) were added to a four-necked flask, the reaction temperature was raised to 50° C., and after the temperature stabilized, 282 g of formaldehyde aqueous solution was added dropwise at a constant dropping rate (30±5 min to complete the dropping); the concentration of formaldehyde in the formaldehyde aqueous solution was 38.5 wt %;

[0091] (3) After the formaldehyde aqueous solution was added dropwise, the temperature was raised to 80°C and reacted for 2 hours;

[0092] (4) After the reaction is completed, the water in the system is removed by distillation under reduced pressure, and then the material is mixed with mixed xylene until the solid content is 80 wt %, and the o-cresol-formaldehyde type thermosetting phenolic resin F1 finished product is obtained by collection.

[0093] The preparation steps of the o-cresol-formaldehyde type thermosetting phenolic resin F2 are the same as those of the o-cresol-formaldehyde type thermosetting phenolic resin F1, except that the amount of the added formaldehyde aqueous solution is 249 g.

[0094] The preparation steps of the hot-vulcanized adhesive for rubber surfaces with high reactivity at low temperature include:

[0095] S1. The raw materials other than the phenolic resin are mixed, ground and dispersed to obtain a first base material;

[0096] S2. Add phenolic resin to the first base material and disperse it at high speed to obtain a finished adhesive product.

[0097] The grinding and dispersing conditions in step S1 are: using a horizontal grinder, a rotation speed of 2500 rpm, a temperature of 40° C., and a dispersing time of 20 min.

[0098] The conditions for high-speed dispersion in step S2 are: using a high-speed disperser, a rotation speed of 1000 rpm, and a dispersion time of 30 minutes.

[0099] Performance Testing

[0100] The bonding strength and bonding failure area of ​​Examples 1-4 were measured, and adhesives Polyton 821 (from Polyton) and Chemlok 6108 (from Chemlok) were taken as comparative samples and subjected to the same test; the test results are shown in Table 2.

[0101] Test method:

[0102] 1) Refer to ASTM D429-03 "Test Method for Adhesion of Rubber to Rigid Substrates" Method A, using a pair of 1250mm2 A circular iron test substrate is coated with Polyton 815 primer adhesive and dried, and then two groups of comparative samples and the above-mentioned examples 1-4 samples are respectively coated on the primer hot vulcanized adhesive, and the dry film thickness of the comparative samples and the example samples is controlled to be in the range of 15-20 μm. After sufficient drying, a compression vulcanizer is used to treat it at 95°C and 10MPa for 5 hours to complete the vulcanization bonding and obtain the test piece. The test rubber needs to use natural rubber with a special formula for seismic isolation (sourced from Zhen'an Technology Co., Ltd.) with a thickness of 3 mm.

[0103] 2) After the test piece is vulcanized and bonded, cool it at room temperature for less than 2 hours to eliminate the rubber thermal stress. Use a mechanical tensile tester to evenly pull apart the pair of test pieces that have completed vulcanization bonding at a rate of 25 mm / min, read the proportion of the bonding failure area in the entire bonding area and the bonding strength, and record the test results in Table 2.

[0104] Table 2 Performance test results

[0105] adhesive Bond failure area ratio Adhesion strength (MPa) Example 1 19％ 6.87 Example 2 9％ 8.06 Example 3 8％ 8.19 Example 4 6％ 8.64 Polyton 821 20％ 6.72 Chemlok 6108 19％ 6.94

[0106] It can be seen from the extreme low temperature vulcanization bonding test results of the embodiment and the comparative example in Table 2 that the adhesive prepared by the present invention using a specific modified latent curing agent in combination with a thermosetting phenolic resin significantly promotes the cross-linking reaction of the curing agent at the bonding interface under extreme low temperature vulcanization bonding conditions, and the bonding failure area ratio of the obtained adhesive is significantly reduced, and the bonding strength is significantly improved, which can meet the use requirements of application scenarios such as seismic isolation bearings. However, when p-dinitrosobenzene is not modified, the bonding strength of the obtained adhesive after low temperature vulcanization is limited, and the bonding failure area ratio is extremely high, and it cannot be used normally.

Claims

1. A hot-vulcanized adhesive for rubber surfaces with high reactivity at low temperatures, characterized in that: In terms of mass percentage, the raw materials for preparing the binder include: Film former 1-15%; Rubber base material 5-20%; Modified latent curing agent 3-15%; Phenolic resin 5-15%; Make up the balance with solvent.

2. The hot-vulcanized adhesive for rubber surfaces with high reactivity at low temperature according to claim 1, characterized in that: In terms of mass percentage, the raw materials for preparing the binder include: Film former 2-7%; Rubber base material 5-10%; Modified latent curing agent 3-9%; Phenolic resin 5-10%; Make up the balance with solvent.

3. The hot-vulcanized adhesive for rubber surfaces with high reactivity at low temperature according to claim 1, characterized in that: The modified latent curing agent is an aromatic nitroso compound modified by a guanidine compound.

4. The hot-vulcanized adhesive for rubber surfaces with high reactivity at low temperature according to claim 3, characterized in that: The aromatic nitroso compound is p-dinitrosobenzene, and the guanidine compound is p-aminobenzenesulfonylguanidine.

5. The hot-vulcanized adhesive for rubber surfaces with high reactivity at low temperature according to claim 4, characterized in that: The preparation steps of the modified latent curing agent include: Mix p-nitrosobenzene and xylene solvent, and disperse them evenly at 70-80° C. to obtain material 1; Heat material 1 to 105-115°C and stabilize for 10-20 minutes to obtain material 2; The material 2 is heated to 120-130°C, p-aminobenzenesulfonylguanidine is added, and the reaction is kept at this temperature for 40-80 minutes to obtain a modified latent curing agent; Preferably, the molar ratio of p-dinitrosobenzene to p-aminobenzenesulfonylguanidine is (2-4):

1.

6. The hot-vulcanized adhesive for rubber surfaces with high reactivity at low temperature according to claim 1, characterized in that: The phenolic resin is an o-cresol-formaldehyde type thermosetting phenolic resin.

7. The hot-vulcanized adhesive for rubber surfaces with high reactivity at low temperature according to claim 6, characterized in that: The degree of polymerization of the o-cresol-formaldehyde type thermosetting phenolic resin is 4-12; The methylol content of the o-cresol-formaldehyde type thermosetting phenolic resin is 10-20%; The free phenol content of the o-cresol-formaldehyde type thermosetting phenolic resin is 10-25%.

8. The hot-vulcanized adhesive for rubber surfaces with high reactivity at low temperature according to claim 1, characterized in that: The adhesive further comprises a promoter, and the promoter is added in an amount of 2 to 20 wt %; The accelerator includes a first accelerator and a second accelerator; The first promoter includes a metal oxide, and the second promoter includes a bismaleimide compound.

9. A method for preparing a heat-vulcanized adhesive for rubber surfaces with high reactivity at low temperature according to any one of claims 1 to 8, characterized in that: The preparation steps include: S1. The raw materials other than the phenolic resin are mixed, ground and dispersed to obtain a first base material; S2. Add phenolic resin to the first base material and disperse it at high speed to obtain a finished adhesive product.

10. A method for using the hot-vulcanized adhesive for rubber surfaces with high reactivity at low temperature according to any one of claims 1 to 8, characterized in that: The vulcanization temperature of the adhesive is 90-100° C., and the vulcanization time is 3-6 hours.

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