Puncture-resistant hole-plugging sealing composite material as well as preparation method and application thereof

Abstract

According to the anti-puncture hole-plugging sealing composite material and the preparation method and application thereof, epoxidized modified butyl rubber is adopted as a main body material, so that the heat resistance and the cross-linking curing bonding strength of conventional butyl rubber can be improved; xylene modified alkylphenol phenolic resin belongs to alkylphenols, contains a large number of phenolic hydroxyl groups and tertiary carbon atoms and has a good tackifying effect on rubber, and after the xylene modified alkylphenol phenolic resin is compounded with the rubber, an obtained composite base material has the sealing performance of butyl rubber, the bonding strength of epoxy group curing and the initial bonding performance of the alkylphenol phenolic resin at the same time. And blending with a plasticizer, a filler, a curing agent, rubber filling oil, color master batch and the like according to a certain proportion to prepare the easily-processed and molded hole-blocking sealing composite material. And meanwhile, hole blocking and sealing performance and piercing and stone impact resistance are achieved.

Description

Technical Field

[0001] The present invention belongs to the field of materials, and particularly relates to a puncture-resistant hole-blocking and sealing composite material, a preparation method thereof, and an application thereof. Background Art

[0002] Automobiles have higher requirements for the body to wade through water and float on water. Therefore, there are strict requirements for plugging holes and sealing various through holes, liquid leakage holes, through holes, positioning holes, and inspection holes on the entire vehicle body. At the same time, some holes on the vehicle body chassis also require the hole-blocking material to have puncture resistance and stone impact resistance.

[0003] To solve the requirements of plugging holes and sealing under the high requirements of wading through water, floating on water, puncture resistance, and stone impact resistance of the vehicle body chassis, the existing technologies generally adopt means such as using polymer materials such as rubber, adhesives, and thermoplastic elastomers to paste and plug holes. Polymer materials have characteristics such as resistance to high and low temperatures, high sealing and bonding, elasticity, and high toughness, and can meet the requirements of puncture resistance, stone impact resistance, and hole-blocking and sealing for some vehicle body chassis.

[0004] In the prior art, the patent with the publication number CN 116355555 A published on June 30, 2023, discloses an adhesive, a rubber layer, and a waterproof and leak-proof tape. The composite waterproof and leak-proof tape material using butyl rubber as the rubber restraint layer and resin material as the adhesive layer has high bonding strength, but its heat resistance is only 80°C. There is a risk of separation between the adhesive layer and the restraint layer in this double-layer structure, and long-term use at high temperatures may lead to bonding failure.

[0005] The patent with the publication number CN 116891659 A published on October 17, 2023, discloses a high flame-retardant vehicle bottom stone impact-resistant coating and a preparation method thereof. Applying the PVC paste resin coating to the vehicle body chassis has good puncture and stone impact resistance, but since it is a paste-like liquid material, it cannot be used to plug holes.

[0006] Therefore, how to obtain a material with hole-blocking and sealing properties and puncture and stone impact resistance is an urgent problem to be solved. Summary of the Invention

[0007] The present invention provides a puncture-resistant hole-blocking and sealing composite material and a preparation method thereof. Using epoxidized modified butyl rubber as the main material can improve the heat resistance and crosslinking and curing bonding strength of conventional butyl rubber; while xylene-modified alkylphenol phenolic resin belongs to alkylphenols and contains a large number of phenolic hydroxyl groups and tertiary carbon atoms, which has a good tackifying effect on rubber. After being compounded with rubber, the obtained composite substrate has the sealing property of butyl rubber, the bonding strength cured by epoxy groups, and the initial adhesiveness of alkylphenol phenolic resin.

[0008] Another object of the present invention is to provide an application of a puncture-resistant hole-blocking sealing composite material for hole-blocking sealing in automobiles. The material of the present invention has the characteristics of high bonding strength, good hole-blocking sealing performance, resistance to high and low temperatures, high puncture resistance, environmental protection and low VOC, meeting the requirements for plugging holes in the vehicle body.

[0009] The specific technical solution of the present invention is as follows:

[0010] A puncture-resistant hole-blocking sealing composite material, comprising the following raw materials in parts by mass:

[0011] Rubber-resin composite substrate: 30 - 35 parts

[0012] Plasticizer: 15 - 20 parts

[0013] Filler: 20 - 25 parts

[0014] Curing agent: 5 - 10 parts

[0015] Rubber filling oil: 15 - 20 parts

[0016] Color masterbatch: 5 - 10 parts.

[0017] The rubber-resin composite substrate is composed of epoxidized modified butyl rubber and xylene-modified alkylphenol phenolic resin.

[0018] The mass ratio of epoxidized modified butyl rubber to xylene-modified alkylphenol phenolic resin is: 5:1;

[0019] The preparation method of the rubber-resin composite substrate is: heating the epoxidized modified butyl rubber to a molten state, adding the xylene-modified alkylphenol phenolic resin, kneading evenly, extruding and cooling to obtain.

[0020] The preparation method of the epoxidized modified butyl rubber is:

[0021] Adding petroleum ether to butyl rubber, heating with stirring, adding formic acid and stirring, then adding sulfuric acid and p-toluenesulfonic acid, and finally dropping hydrogen peroxide solution. After the reaction, neutralize the reaction solution with an alkali solution, wash with water until neutral, filter and dry to obtain epoxidized modified butyl rubber.

[0022] In the preparation method of the epoxidized modified butyl rubber: the mass ratio of the butyl rubber to petroleum ether is 1:5; the volume ratio of petroleum ether, formic acid, sulfuric acid, p-toluenesulfonic acid and hydrogen peroxide solution is: 60:5:1:5:4; the butyl rubber is one or a mixture of two kinds of butyl rubbers selected from general butyl rubber or halogenated butyl rubber; the butyl rubber is preferably Sinopec 1751 butyl rubber or Lanxess RB301 butyl rubber; the halogenated butyl rubber is selected from Lanxess CB1240 chlorinated butyl rubber or Exxon 1066 chlorinated butyl rubber; the mixing mass ratio of the butyl rubber and the halogenated butyl rubber is 1:1; the concentration of the formic acid is 60% by mass; the sulfuric acid is concentrated sulfuric acid with a mass fraction of 98%; the p-toluenesulfonic acid is an aqueous solution with a mass fraction of 65%; the hydrogen peroxide solution is 20% by mass; the alkali solution is a 20% by mass sodium hydroxide solution; the temperature increase means increasing the temperature to 60-70 °C; the reaction means reacting for 5 hours.

[0023] The preparation method of the xylene-modified alkylphenol phenolic resin is as follows:

[0024] 1) After heating and melting the flask containing the alkylphenol in an oil bath, add the solvent and dilute hydrochloric acid catalyst, stir and raise the temperature, then add the formaldehyde solution, and gradually dropwise add xylene during stirring for reflux reaction. After the reaction ends, add the alkali solution to neutralize the reaction solution, let it stand, and separate the aqueous phase to obtain the reaction condensation liquid intermediate.

[0025] 2) Subject the reaction condensation liquid intermediate to vacuum distillation, cool and dry it to obtain the xylene-modified alkylphenol phenolic resin.

[0026] In step 1), the alkylphenol is selected from one of 4-n-octylphenol and 4-tert-octylphenol; the dosage ratio of the alkylphenol to the solvent is 0.5 g / mL; the volume ratio of the solvent, dilute hydrochloric acid catalyst and xylene is: 20:1:2; the dosage of the formaldehyde solution is: the molar ratio of formaldehyde to alkylphenol is 1:1; the solvent is tetrahydrofuran, the dilute hydrochloric acid catalyst is a dilute hydrochloric acid solution with a mass fraction of 37%; the formaldehyde solution is a 37% by mass aqueous formaldehyde solution; the stirring and temperature increase means stirring and raising the temperature to 120-125 °C; the reflux reaction means reflux reaction at 125-130 °C for 3-4 h; the alkali solution is a sodium hydroxide solution with a mass fraction of 20%.

[0027] In step 2), it means introducing a nitrogen protection gas, raising the temperature to 125-130 °C in an oil bath, and reducing the pressure to a vacuum degree of -0.1 MPa with a vacuum pump to distill out the tetrahydrofuran solvent until no solvent is distilled out and the reaction ends.

[0028] The plasticizer is a non-toxic and environmentally friendly plasticizer of tributyl citrate.

[0029] The filler described above is an inorganic filler, preferably one of calcium silicate hydrate or silica powder.

[0030] The curing agent is one of dicyandiamide, preferably DICY-5 (DICY particle size 5μm) or DICY-10 (DICY particle size 10μm).

[0031] The rubber filling oil is one or a combination mixture of polyisobutylene, aromatic oil, and paraffin oil.

[0032] The color masterbatch is rubber carbon black, preferably one of N762, N772, and N774 carbon black.

[0033] A preparation method of a puncture-resistant and hole-blocking sealing composite material provided by the present invention is as follows: Put the rubber-resin composite substrate, plasticizer, filler, curing agent, rubber filling oil, and color masterbatch in a kneader in the formulated amounts, and knead and mix evenly to obtain the puncture-resistant and hole-blocking sealing composite material.

[0034] An application of the puncture-resistant and hole-blocking sealing composite material provided by the present invention is used for puncture-resistant and hole-blocking sealing of automobiles.

[0035] Using epoxidized modified butyl rubber as the main material can improve the heat resistance and crosslinking and curing adhesion strength of conventional butyl rubber; while xylene-modified alkylphenol phenolic resin belongs to alkylphenols and contains a large number of phenolic hydroxyl groups and tertiary carbon atoms, which has a good tackifying effect on rubber. After being compounded with rubber, the obtained composite substrate has the sealing performance of butyl rubber, the adhesion strength cured by epoxy groups, and the initial adhesion of alkylphenol phenolic resin. Further blend with plasticizer, filler, curing agent, rubber filling oil, color masterbatch, etc. in a certain proportion to prepare an easily processed and formed hole-blocking sealing composite material. Among them, the epoxidized modified butyl rubber has good heat resistance characteristics and curing adhesion strength, does not shrink and deteriorate at 200°C for 3 hours, and does not crack at -40°C; the xylene-modified alkylphenol phenolic resin as a tackifying resin greatly improves the adhesion of butyl rubber itself, and the 180° peel strength reaches more than 15 N / cm; at the same time, the hole-blocking sealing depth of this composite material is 500 mm, the diameter is 70 mm water column, and it does not leak water after testing for 15 days; the puncture and stone impact resistance reaches more than 300 N. It has both hole-blocking sealing and puncture and stone impact resistance. Description of the Drawings

[0036] Figure 1 It is a physical picture of the hole-blocking sealing material product;

[0037] Figure 2 It is a preparation route diagram of the rubber-resin composite substrate;

[0038] Figure 3 It is an effect picture of the puncture resistance test. Detailed Embodiments

[0039] To make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of them. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.

[0040] The test materials, reagents, etc. used in the following embodiments can be obtained from commercial channels without special instructions.

[0041] For those not specifying specific techniques or conditions in the embodiments, they can all be carried out according to the techniques or conditions described in the literature in the field or according to the product specifications.

[0042] The formic acid used in the present invention has a concentration of 60% by mass; the sulfuric acid is concentrated sulfuric acid with a mass fraction of 98%; the p-toluenesulfonic acid is an aqueous solution with a mass fraction of 65%; the hydrogen peroxide solution has a mass fraction of 20%; and the lye is a sodium hydroxide solution with a mass fraction of 20%.

[0043] An anti-puncture hole-blocking sealing composite material provided by the present invention comprises the following raw materials in parts by mass:

[0044] Rubber-resin composite substrate: 30-35 parts

[0045] Plasticizer: 15-20 parts

[0046] Filler: 20-25 parts

[0047] Curing agent: 5-10 parts

[0048] Rubber filling oil: 15-20 parts

[0049] Color masterbatch: 5-10 parts.

[0050] The preparation method of the anti-puncture hole-blocking sealing composite material is as follows:

[0051] Step 1: In a three-necked flask equipped with magnetic stirring and a thermometer, add shredded and powdered butyl rubber, add a certain amount of petroleum ether, heat up to 60-70 °C while stirring, add formic acid and stir, then add p-toluenesulfonic acid solution, dropwise add sulfuric acid, and finally dropwise add a certain amount of hydrogen peroxide solution. After reacting for 5 hours, neutralize the reaction solution with sodium hydroxide and wash it with water until neutral, then filter and dry to obtain formic acid-epoxidized modified butyl rubber S0.

[0052] Step 2: Add alkylphenol into a three-necked flask equipped with a magnetic stirrer, a thermometer, a dropping funnel, and a condenser. Place it in an oil bath and heat to maintain a temperature of 60 - 70 °C to melt the alkylphenol. Add a certain amount of tetrahydrofuran solvent and dilute hydrochloric acid solution, raise the temperature and stir to control the temperature at 120 - 125 °C, then add a certain amount of formaldehyde solution, and finally slowly drop a certain amount of xylene solution into the three-necked flask. After the dropping is completed, control the temperature between 125 - 130 °C and maintain reflux for 3 - 4 hours. After the reaction is completed, neutralize the reaction solution by dropping sodium hydroxide, and wash and filter with water until neutral to obtain the reaction condensation liquid intermediate S1.

[0053] Step 3: Add the condensation liquid intermediate S1 obtained from the reaction into a three-necked flask equipped with a magnetic stirrer, a thermometer, and a vacuum distillation device. Introduce nitrogen as a protective gas, heat in an oil bath to 125 - 130 °C, and distill out the tetrahydrofuran solvent under reduced pressure until no more solvent is distilled out and the reaction ends. Stop the reaction and pour the resin in the three-necked flask into a ceramic container while it is still hot to cool. After crushing, obtain the dark brown product xylene-modified alkylphenol phenolic resin S2.

[0054] Step 4: Heat the epoxidized modified butyl rubber S0 in a kneader to 155 - 165 °C to make it in a molten state, add a certain amount of xylene-modified alkylphenol phenolic resin S2, knead evenly, extrude and cool to obtain the modified rubber-resin composite substrate.

[0055] Step 5: Put the rubber-resin composite substrate, plasticizer, filler, curing agent, rubber filling oil, and color masterbatch into a mixer in accordance with a certain proportion and process in sequence, control the mixing temperature in the mixer at 60 - 70 °C, mix evenly by mixing to obtain a puncture-resistant stone impact and hole-blocking sealing composite material.

[0056] The following are several specific implementation processes of the present invention.

[0057] Example 1

[0058] A preparation method of a puncture-resistant hole-blocking sealing composite material, comprising the following steps:

[0059] Step 1: In a 500 mL three-necked flask equipped with a magnetic stirrer and a thermometer, add 40 grams of crushed butyl rubber RB301, add 300 mL (200 grams) of petroleum ether, heat to 60 - 70 °C while stirring, add 25 mL of formic acid solution and stir, then add 25 mL of p-toluenesulfonic acid solution, and finally dropwise add 5 mL of sulfuric acid as a catalyst and stir. Finally, dropwise add 20 mL of hydrogen peroxide solution, continuously stir and react for 5 hours, neutralize the reaction solution with sodium hydroxide solution, wash with water until neutral, filter and dry to obtain the epoxidized modified butyl rubber S0.

[0060] Step 2: Add 100 g of 4-n-octylphenol to a 500 mL three-necked flask equipped with a magnetic stirrer, a thermometer, a dropping funnel, and a condenser, place the mixture in an oil bath and heat to maintain a temperature of 60-70 ° C to melt the 4-n-octylphenol, add 200 mL of tetrahydrofuran solvent and 10 mL of dilute hydrochloric acid solution, heat and stir to control the temperature at 120-125 ° C, then add formaldehyde solution in an amount of 1:1 in a molar ratio of 4-n-octylphenol to formaldehyde, and finally dropwise add 20 mL of xylene solution to the three-necked flask. After the addition is completed, control the temperature between 125-130 ° C, keep reflux for 4 hours, and after the reaction is completed, neutralize the reaction solution by dropping sodium hydroxide solution, and wash and filter with water until neutral to obtain a reaction condensation liquid intermediate S1.

[0061] Step 3: Add the condensation liquid intermediate S1 obtained by the reaction into a three-necked flask equipped with a magnetic stirrer, a thermometer, and a vacuum distillation apparatus, introduce nitrogen protective gas, heat the oil bath to 125-130° C., use a vacuum pump to reduce the pressure to a vacuum degree of -0.1 MPa to distill out the tetrahydrofuran solvent, until the reaction is completed and no solvent is evaporated, stop the reaction, pour the resin in the three-necked flask into a ceramic container while hot, cool it, and crush it to obtain a dark brown product, xylene-modified alkylphenol novolac resin S2.

[0062] Step 4: Heat 1000 g of epoxidized butyl rubber S0 to 155-165° C. in a kneader to make it molten, add 200 g of xylene-modified alkylphenol novolac resin S2, knead evenly, extrude and cool, and obtain an epoxidized rubber-resin composite substrate.

[0063] Step 5: Add the rubber-resin composite substrate, tributyl citrate, hydrated calcium silicate, dicyandiamide DICY-5, polyisobutylene PB6130, and carbon black N774 in a ratio of 35:15:20:5:20:5 into an internal mixer in sequence, control the internal mixing temperature at 60-70°C, mix evenly, and obtain a puncture-resistant stone-impact pore-blocking sealing composite material.

[0064] Example 2

[0065] A method for preparing a puncture-resistant pore-blocking sealing composite material comprises the following steps:

[0066] Step 1: In a 500mL three-necked flask equipped with a magnetic stirrer and a thermometer, 40 grams of crushed butyl rubber RB301 and chlorinated butyl rubber CB1240 were added in a mass ratio of 1:1, and 300mL (200 grams) of petroleum ether were added. The temperature was raised to 60-70°C while stirring. After adding 25mL of formic acid and stirring, 25mL of p-toluenesulfonic acid solution was added, and then 5mL of sulfuric acid was added dropwise as a catalyst and stirred. Finally, 20mL of hydrogen peroxide solution was added dropwise. After the reaction was continued for 5 hours, the reaction solution was neutralized with sodium hydroxide, washed with water until neutral, and filtered and dried to obtain epoxidized modified butyl rubber S0.

[0067] Step 2: Add 100 g of 4-n-octylphenol to a 500 mL three-necked flask equipped with a magnetic stirrer, a thermometer, a dropping funnel, and a condenser, place the mixture in an oil bath and heat to maintain a temperature of 60-70 ° C to melt the 4-n-octylphenol, add 200 mL of tetrahydrofuran solvent and 10 mL of dilute hydrochloric acid solution, heat and stir to control the temperature at 120-125 ° C, then add formaldehyde solution in an amount of 1:1 in a molar ratio of 4-n-octylphenol to formaldehyde, and finally drop 20 mL of xylene solution into the three-necked flask. After the addition is completed, control the temperature between 125-130 ° C, keep reflux for 4 hours, and after the reaction is completed, add sodium hydroxide to neutralize the reaction solution, wash with water and filter to neutrality to obtain a reaction condensation liquid intermediate S1.

[0068] Step 3: Add the condensation liquid intermediate S1 obtained by the reaction into a three-necked flask equipped with a magnetic stirrer, a thermometer, and a vacuum distillation device, introduce nitrogen protective gas, heat the oil bath to 125-130° C., and vacuum distill out the tetrahydrofuran solvent until the reaction is completed and no solvent is evaporated. Stop the reaction and pour the resin in the three-necked flask into a ceramic container while it is hot to cool. After crushing, a dark brown product, xylene-modified alkylphenol novolac resin S2, is obtained.

[0069] Step 4: Heat 1000 g of epoxidized butyl rubber S0 to 155-165° C. in a kneader to make it molten, add 200 g of xylene-modified alkylphenol novolac resin S2, knead evenly, extrude and cool, and obtain an epoxidized rubber-resin composite substrate.

[0070] Step 5: Add the rubber-resin composite substrate, tributyl citrate, hydrated calcium silicate, dicyandiamide DICY-5, polyisobutylene PB6130, and carbon black N774 in a ratio of 35:15:20:5:20:5 into an internal mixer in sequence, control the internal mixing temperature at 60-70°C, mix evenly, and obtain an anti-puncture stone impact pore-blocking sealing composite material.

[0071] Example 3

[0072] A method for preparing a puncture-resistant pore-blocking sealing composite material comprises the following steps:

[0073] Step 1: In a 500mL three-necked flask equipped with a magnetic stirrer and a thermometer, add 40g of crushed butyl rubber RB301, add 300mL (200g) of petroleum ether, heat to 60-70°C while stirring, add 25mL of formic acid solution and stir, then add 25mL of p-toluenesulfonic acid solution, then add 5mL of sulfuric acid dropwise as a catalyst and stir, finally add 20mL of hydrogen peroxide solution dropwise, continue the reaction for 5 hours, neutralize the reaction solution with sodium hydroxide solution, wash with water until neutral, filter and dry to obtain epoxidized modified butyl rubber S0.

[0074] Step 2: Add 100 g of 4-tert-octylphenol to a 500 mL three-necked flask equipped with a magnetic stirrer, a thermometer, a dropping funnel, and a condenser, place the mixture in an oil bath and heat to maintain a temperature of 60-70° C. to melt the 4-tert-octylphenol, add 200 mL of tetrahydrofuran solvent and 10 mL of dilute hydrochloric acid solution, heat and stir to control the temperature at 120-125° C., then add formaldehyde solution in an amount of 1:1 at a molar ratio of 4-tert-octylphenol to formaldehyde, and finally dropwise add 20 mL of xylene solution to the three-necked flask. After the addition is completed, control the temperature between 125-130° C. and keep reflux for 4 hours. After the reaction is completed, add sodium hydroxide to neutralize the reaction solution, wash with water and filter until neutral to obtain a reaction condensation liquid intermediate S1.

[0075] Step 3: Add the condensation liquid intermediate S1 obtained by the reaction into a three-necked flask equipped with a magnetic stirrer, a thermometer, and a vacuum distillation device, introduce nitrogen protective gas, heat the oil bath to 125-130° C., and vacuum distill out the tetrahydrofuran solvent until the reaction is completed and no solvent is evaporated. Stop the reaction and pour the resin in the three-necked flask into a ceramic container while it is hot to cool. After crushing, a dark brown product, xylene-modified alkylphenol novolac resin S2, is obtained.

[0076] Step 4: Heat 1000 g of epoxidized butyl rubber S0 to 155-165° C. in a kneader to make it molten, add 200 g of xylene-modified alkylphenol novolac resin S2, knead evenly, extrude and cool, and obtain an epoxidized rubber-resin composite substrate.

[0077] Step 5: Add the rubber-resin composite substrate, tributyl citrate, hydrated calcium silicate, dicyandiamide DICY-5, aromatic oil, and carbon black N774 in a ratio of 35:15:20:5:20:5 into an internal mixer in sequence, control the internal mixing temperature at 60-70°C, mix evenly, and obtain an anti-puncture stone impact pore-blocking sealing composite material.

[0078] Example 4

[0079] A preparation method of a puncture-resistant hole-blocking sealing composite material, comprising the following steps:

[0080] Step 1: In a 500 mL three-necked flask equipped with magnetic stirring and a thermometer, add 40 grams of crushed butyl rubber RB301, add 300 mL (200 grams) of petroleum ether, heat to 60 - 70 °C while stirring, add 25 mL of formic acid and stir, then add 25 mL of p-toluenesulfonic acid solution, and finally dropwise add 5 mL of sulfuric acid as a catalyst and stir. Finally, dropwise add 20 mL of hydrogen peroxide solution and continuously react for 5 hours. Then, neutralize the reaction solution with sodium hydroxide solution and wash it with water until neutral, and filter and dry to obtain epoxidized modified butyl rubber S0.

[0081] Step 2: In a 500 mL three-necked flask equipped with magnetic stirring, a thermometer, a dropping funnel, and a condenser, add 100 grams of 4-tert-octylphenol, place it in an oil bath and heat to keep the temperature at 60 - 70 °C to melt the 4-tert-octylphenol. Add 200 mL of tetrahydrofuran solvent and 10 mL of dilute hydrochloric acid solution, raise the temperature and stir to control the temperature at 120 - 125 °C. Then, add formaldehyde solution according to the molar ratio of 4-tert-octylphenol to formaldehyde of 1:1, and finally dropwise add 20 mL of xylene solution into the three-necked flask. After the addition is completed, control the temperature between 125 - 130 °C and keep refluxing for 4 hours. After the reaction ends, neutralize the reaction solution by dropwise adding sodium hydroxide and wash and filter it with water until neutral to obtain the reaction condensation liquid intermediate S1.

[0082] Step 3: Add the reaction condensation liquid intermediate S1 obtained to a three-necked flask equipped with magnetic stirring, a thermometer, and a vacuum distillation device, introduce nitrogen as a protective gas, heat in an oil bath to 125 - 130 °C, and vacuum distill out the tetrahydrofuran solvent until no solvent is distilled out at the end of the reaction. Stop the reaction and pour the resin in the three-necked flask into a ceramic container while it is hot to cool. After crushing, obtain a dark brown product, xylene-modified alkylphenol phenolic resin S2.

[0083] Step 4: Heat 1000 g of epoxidized modified butyl rubber S0 in a kneader to 155 - 165 °C to make it in a molten state, add 200 g of xylene-modified alkylphenol phenolic resin S2, knead evenly, extrude and cool to obtain an epoxidized modified rubber-resin composite substrate.

[0084] Step 5: Put the rubber-resin composite substrate, tributyl citrate, silica powder, dicyandiamide DICY-5, aromatic oil, and carbon black N774 into a mixer in the ratio of 35:15:20:5:20:5 in sequence, control the mixing temperature at 60 - 70 °C, and mix evenly by mixing to obtain a puncture-resistant and stone-impact hole-blocking sealing composite material.

[0085] Comparative Example 1

[0086] A preparation method of a puncture-resistant hole-blocking sealing composite material, comprising the following steps:

[0087] Step 1: In a 500 mL three-necked flask equipped with magnetic stirring and a thermometer, add 40 g of crushed butyl rubber RB301, add 300 mL (200 g) of petroleum ether, heat to 60 - 70 °C while stirring, add 25 mL of formic acid and stir, then add 25 mL of p-toluenesulfonic acid solution, and then dropwise add 5 mL of sulfuric acid as a catalyst and stir. Finally, dropwise add 20 mL of hydrogen peroxide solution and continuously stir and react for 5 hours. Then, neutralize the reaction solution with sodium hydroxide solution and wash and filter with water until neutral, and filter and dry to obtain epoxidized modified butyl rubber S0.

[0088] Step 2: Add epoxidized modified butyl rubber, tributyl citrate, calcium silicate hydrate, dicyandiamide DICY-5, polyisobutylene PB6130, and carbon black N774 into a mixer in a ratio of 35:15:20:5:20:5 in sequence, control the mixing temperature at 60 - 70 °C, and mix and knead evenly to obtain a puncture-resistant stone-impact hole-blocking sealing composite material.

[0089] Comparative Example 2

[0090] A preparation method of a puncture-resistant hole-blocking sealing composite material, comprising the following steps:

[0091] Step 1: In a 500 mL three-necked flask equipped with magnetic stirring and a thermometer, add 40 g of crushed butyl rubber RB301, add 300 mL (200 g) of petroleum ether, heat to 60 - 70 °C while stirring, add 25 mL of formic acid and stir, then add 25 mL of p-toluenesulfonic acid solution, and then dropwise add 5 mL of sulfuric acid as a catalyst and stir. Finally, dropwise add 20 mL of hydrogen peroxide solution and continuously stir and react for 5 hours. Then, neutralize the reaction solution with sodium hydroxide solution and wash and filter with water until neutral, and filter and dry to obtain epoxidized modified butyl rubber S0.

[0092] Step 2: Add 100 g of 4-n-octylphenol into a 500 mL three-necked flask equipped with magnetic stirring, a thermometer, a dropping funnel, and a condenser, place it in an oil bath and heat to keep the temperature at 60 - 70 °C to melt 4-n-octylphenol. Add 200 mL of tetrahydrofuran solvent and 10 mL of dilute hydrochloric acid solution, heat and stir to control the temperature at 120 - 125 °C, then add formaldehyde solution according to the molar ratio of 4-n-octylphenol to formaldehyde of 1:1, and finally dropwise add 20 mL of xylene solution into the three-necked flask. After the addition is completed, control the temperature between 125 - 130 °C and keep refluxing for 4 hours. After the reaction is completed, neutralize the reaction solution by dropwise adding sodium hydroxide solution and wash and filter with water until neutral to obtain a reaction condensation liquid intermediate S1.

[0093] Step 3: Add the obtained condensation liquid intermediate S1 into a three-necked flask equipped with a magnetic stirrer, a thermometer, and a vacuum distillation device. Introduce nitrogen as a protective gas, heat it up to 125 - 130 °C in an oil bath, and distill out the tetrahydrofuran solvent under reduced pressure until no more solvent is distilled out at the end of the reaction. Stop the reaction and pour the resin in the three-necked flask into a ceramic container while it is still hot for cooling. After crushing, a dark brown product, xylene-modified alkylphenol phenolic resin S2, is obtained.

[0094] Step 4: Heat 500 g of the epoxidized modified butyl rubber S0 in a kneader to 155 - 165 °C until it is in a molten state. Add 500 g of the xylene-modified alkylphenol phenolic resin S2, knead evenly, extrude and cool to obtain an epoxidized modified rubber-resin composite substrate.

[0095] Step 5: Put the rubber-resin composite substrate, tributyl citrate, calcium silicate hydrate, dicyandiamide DICY-5, polyisobutylene PB6130, and carbon black N774 into a mixer in the ratio of 35:15:20:5:20:5 in sequence. Control the mixing temperature in the mixer at 60 - 70 °C, mix evenly by kneading to obtain a puncture-resistant stone impact and hole-blocking sealing composite material.

[0096] Comparative Example 3

[0097] A preparation method of a puncture-resistant hole-blocking sealing composite material includes the following steps:

[0098] Step 1: In a 500 mL three-necked flask equipped with a magnetic stirrer and a thermometer, add 40 g of crushed butyl rubber RB301 and 300 mL (200 g) of petroleum ether. Heat it up to 60 - 70 °C while stirring, add 25 mL of formic acid and stir, then add 25 mL of p-toluenesulfonic acid solution, and finally dropwise add 5 mL of sulfuric acid as a catalyst for stirring. Finally, dropwise add 20 mL of hydrogen peroxide solution and continuously stir and react for 5 hours. Neutralize the reaction solution with sodium hydroxide solution and wash it with water until it is neutral. Filter and dry to obtain epoxidized modified butyl rubber S0.

[0099] Step 2: Add 100 g of 4-n-octylphenol to a 500 mL three-necked flask equipped with a magnetic stirrer, a thermometer, a dropping funnel, and a condenser, place the mixture in an oil bath and heat to maintain a temperature of 60-70 ° C to melt the 4-n-octylphenol, add 200 mL of tetrahydrofuran solvent and 10 mL of dilute hydrochloric acid solution, heat and stir to control the temperature at 120-125 ° C, then add formaldehyde solution in an amount of 1:1 in a molar ratio of 4-n-octylphenol to formaldehyde, and finally dropwise add 20 mL of xylene solution to the three-necked flask. After the addition is completed, control the temperature between 125-130 ° C, keep reflux for 4 hours, and after the reaction is completed, neutralize the reaction solution by dropping sodium hydroxide solution, and wash and filter with water until neutral to obtain a reaction condensation liquid intermediate S1.

[0100] Step 3: Add the condensation liquid intermediate S1 obtained by the reaction into a three-necked flask equipped with a magnetic stirrer, a thermometer, and a vacuum distillation device, introduce nitrogen protective gas, heat the oil bath to 125-130° C., and vacuum distill out the tetrahydrofuran solvent until the reaction is completed and no solvent is evaporated. Stop the reaction and pour the resin in the three-necked flask into a ceramic container while it is hot to cool. After crushing, a dark brown product, xylene-modified alkylphenol novolac resin S2, is obtained.

[0101] Step 4: Heat 1000 g of epoxidized butyl rubber S0 to 155-165° C. in a kneader to make it molten, add 200 g of xylene-modified alkylphenol novolac resin S2, knead evenly, extrude and cool, and obtain an epoxidized rubber-resin composite substrate.

[0102] Step 5: Add the rubber-resin composite substrate, tributyl citrate, hydrated calcium silicate, dicyandiamide DICY-5, polyisobutylene PB6130, and carbon black N774 in a ratio of 20:15:35:5:20:5 into an internal mixer in sequence, control the internal mixing temperature at 60-70°C, mix evenly, and obtain a puncture-resistant stone-impact pore-blocking sealing composite material.

[0103] For the anti-puncture stone impact plugging hole sealing composite materials prepared according to the above Examples 1-4 and Comparative Examples 1-3, tablets are pressed and attached with aluminum foil according to the specified size requirements of certain tests, cut into test samples, and different key properties are tested as shown in Table 1 below. Among them: For the heat resistance test, samples with a size of 200×100 mm are respectively vertically and inverted pasted on a steel plate and baked at 200 °C for 3 h for testing; for the low temperature resistance test, samples with a size of 200×100 mm are respectively vertically and inverted pasted on a steel plate and placed at -40 °C for 3 h for testing; for the initial adhesion test, samples with a size of 150×25 mm are pasted on a steel plate for 180° peel test; for the water tightness test, a container with a diameter of 70 mm and a depth of 500 mm is filled with water, a hole with a diameter of 15 mm is opened at the bottom, and a sample with a diameter of 30 mm is pasted for plugging hole sealing to test the water tightness; for the anti-puncture force test, a 50 mm direct sample is attached with 0.08 mm aluminum foil, baked at 170 °C for 20 minutes and then cooled, and a 10 mm needle is used for piercing test; for the weather resistance water tightness test, samples with a diameter of 30 mm are pasted on a water sealing device, placed in a high and low temperature test cabinet, baked at 170 °C for 20 minutes, and then subjected to a 168 h cyclic weather resistance test at 80 °C×8 h, 23 °C×4 h, -40 °C×8 h, 23 °C×4 h. After completion, it is filled with water for water tightness test; the odor level test is carried out according to the odor emission level of VDA270 interior trim parts; the VOC test is carried out according to the limit of volatile organic compounds in adhesives GB / T GB 33372-2020.

[0104] Table 1 Key properties of anti-puncture stone impact plugging hole sealing composite materials

[0105]

[0106] It can be seen from Example 1 and Example 2 in the table that the anti-puncture stone impact plugging hole sealing composite material prepared by epoxidizing and modifying the two-component butyl rubber has better initial adhesion and similar anti-puncture force; it can be seen from Example 3 that the 4-tert-octylphenol modified phenolic resin has better adhesion and higher anti-puncture force. It can be seen from Example 4 that the material prepared with aromatic rubber filling oil has significantly lower initial adhesion and anti-puncture force than others. It can be seen from Comparative Example 1 that only the epoxidized butyl rubber is used. Although the prepared plugging hole sealing material has a large anti-puncture force, its adhesiveness is low and it is difficult to seal and prevent water leakage. It can be seen from Comparative Example 2 that when the epoxidized butyl rubber and xylene-modified alkylphenol phenolic resin are in a ratio of 1:1, the rubber content is low, the anti-puncture force of the material is reduced, and the water pressure bearing sealing performance declines, resulting in water leakage. Comparative Example 3 shows that when the mass fraction of the rubber-resin composite substrate is reduced from 35 to 20, the anti-puncture force drops significantly and the weather resistance decreases.

[0107] Based on the above embodiments, it can be concluded that the prepared anti-puncture and stone impact plugging hole sealing material has high high and low temperature resistance characteristics, can maintain no water leakage for 15 days in waterproof sealing, has better weather resistance sealing performance and anti-puncture performance, and fully meets the requirements of the vehicle body for plugging hole sealing and anti-puncture stone impact.

[0108] The description of the above embodiments is for the convenience of those of ordinary skill in the art to understand and use the invention. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative efforts. Therefore, the present invention is not limited to the above embodiments, and the improvements and modifications made by those skilled in the art without departing from the scope of the present invention according to the disclosure of the present invention should be within the protection scope of the present invention.

Claims

1. A puncture-resistant pore-blocking sealing composite material, characterized in that: The puncture-resistant pore-blocking and sealing composite material comprises the following raw materials in parts by weight: Rubber-resin composite substrate: 30-35 parts Plasticizer: 15-20 parts Filling: 20-25 parts Curing agent: 5-10 parts Rubber filling oil: 15-20 parts Masterbatch: 5-10 parts; The rubber-resin composite substrate is composited by epoxidized modified butyl rubber and xylene modified alkylphenol phenolic resin.

2. The puncture-resistant pore-blocking sealing composite material according to claim 1, characterized in that: The mass ratio of the epoxidized modified butyl rubber to the xylene modified alkylphenol novolac resin is 5:

1.

3. The puncture-resistant pore-blocking sealing composite material according to claim 1 or 2, characterized in that: The preparation method of the rubber-resin composite substrate is as follows: heating the epoxidized modified butyl rubber to a molten state, adding xylene modified alkylphenol novolac resin, kneading them evenly, extruding and cooling them, and obtaining the composite substrate.

4. The puncture-resistant pore-blocking sealing composite material according to any one of claims 1 to 3, characterized in that: The preparation method of the epoxidized modified butyl rubber is: Petroleum ether is added to butyl rubber, and the temperature is raised while stirring. Formic acid is added and stirred, and then sulfuric acid and p-toluenesulfonic acid are added. Finally, a hydrogen peroxide solution is added dropwise. After the reaction, the reaction solution is neutralized with an alkali solution, washed with water until neutral, filtered and dried to obtain epoxidized modified butyl rubber.

5. The puncture-resistant pore-blocking sealing composite material according to claim 4, characterized in that: The mass ratio of the butyl rubber to petroleum ether is 1:5; the volume ratio of the petroleum ether, formic acid, sulfuric acid, p-toluenesulfonic acid and hydrogen peroxide solution is 60:5:1:5:4; the heating refers to heating to 60-70°C; the reaction refers to reacting for 5 hours.

6. The puncture-resistant pore-blocking sealing composite material according to any one of claims 1 to 4, characterized in that: The preparation method of the xylene modified alkylphenol novolac resin is as follows: 1) After the alkylphenol is heated and melted, a solvent and a dilute hydrochloric acid catalyst are added, and after stirring and heating, a formaldehyde solution is added, and during the stirring process, xylene is added dropwise for reflux reaction. After the reaction is completed, an alkali solution is added to neutralize the reaction solution, and the solution is allowed to stand and the aqueous phase is separated to obtain a reaction condensation liquid intermediate. 2) distilling the reaction condensation liquid intermediate under reduced pressure, cooling and drying, and obtaining a xylene-modified alkylphenol novolac resin.

7. The puncture-resistant pore-blocking and sealing composite material according to claim 6, characterized in that: In step 1), the amount ratio of the alkylphenol to tetrahydrofuran is 0.5 g / mL, the volume ratio of the tetrahydrofuran, the dilute hydrochloric acid catalyst, and the xylene solution is 20:1:2; and the alkylphenol is one of 4-n-octylphenol and 4-tert-octylphenol.

8. The puncture-resistant pore-blocking and sealing composite material according to claim 6 or 7, characterized in that: The molar ratio of the alkylphenol to the formaldehyde in the formaldehyde solution is 1:1; the temperature control to maintain the reflux reaction means that the temperature is between 125-130° C. and the reflux is maintained for 3-4 hours.

9. A method for preparing the puncture-resistant pore-blocking and sealing composite material according to any one of claims 1 to 8, characterized in that: The preparation method comprises the following steps: putting the rubber-resin composite substrate, plasticizer, filler, curing agent, rubber filling oil and masterbatch in the prescribed mass proportion into an internal mixer, mixing them uniformly to obtain the puncture-resistant pore-blocking sealing composite material.

10. An application of the puncture-resistant pore-blocking sealing composite material according to any one of claims 1 to 8, characterized in that: Used for automobile anti-puncture hole sealing.

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