Epoxy-furan modified polybutadiene, modified butyl hot melt adhesive and preparation method thereof

Abstract

The invention discloses epoxy-furan modified polybutadiene, a modified butyl hot melt adhesive and a preparation method of the epoxy-furan modified polybutadiene and the modified butyl hot melt adhesive. The epoxy-furan modified polybutadiene is obtained by reacting epoxidized polybutadiene and furyl carboxylic acid under the action of a polymerization inhibitor and a phase transfer catalyst. Epoxy-furan modified polybutadiene is introduced into raw materials such as polyisobutene, and bismaleimide is used as a dynamic cross-linking agent, so that the epoxy-furan modified butyl hot melt adhesive is prepared. The butyl hot melt adhesive has good cohesiveness with glass and has an excellent self-repairing function.

Description

Technical Field

[0001] This invention relates to the field of sealant technology, specifically to butyl hot melt adhesive, and particularly to an epoxy-furan modified polybutadiene, a modified butyl hot melt adhesive, and a method for preparing the same. Background Technology

[0002] Butyl rubber's regular molecular structure endows it with excellent airtightness and very low water vapor permeability, making it widely used in the airtight layer of tire inner tubes, the first seal of insulated glass, building waterproof membranes, and special waterproof tapes. Butyl hot melt adhesive, a single-component, solvent-free, non-fogging, and non-vulcanizing thermoplastic material based on butyl rubber and polyisobutylene, can be used as the first sealant for the inner layer of insulated glass. However, traditional butyl hot melt adhesives have poor adhesion to glass and cannot provide good bonding, easily leading to delamination after a certain period. To improve the adhesion of butyl hot melt adhesives to insulating glass, researchers have introduced silane-modified polyolefins or silane-modified polyisobutylenes, using a moisture-curing reaction of siloxane groups to enhance the adhesion between the butyl hot melt adhesive and glass (e.g., CN 113897159 A, CN 112795337 A, CN 112795338 A, and CN 118360012 A). However, the moisture-curing reaction is irreversible. After moisture curing, the irreversible Si-O-Si covalent bonds in the crosslinking network of the silane-modified butyl hot melt adhesive significantly reduce the thermoplasticity of the material.

[0003] In addition, during the application of sealant, improper or incorrect construction operations may easily cause damage, defects or bubbles in the sealant, leading to a decrease in the mechanical properties of butyl hot melt sealant. In severe cases, it may even cause sealing performance failure, accelerate the leakage of inert gas, and greatly reduce the service life of insulated glass. Summary of the Invention

[0004] Therefore, the purpose of this invention is to provide a butyl hot melt adhesive that has good adhesion to glass and self-healing function.

[0005] To achieve the above objectives, the present invention includes the following technical solutions.

[0006] In a first aspect, the present invention provides an epoxy-furan modified polybutadiene with the following structural formula:

[0007]

[0008] Where, l = 0.18~0.22, m = 0.17~0.22, x+y = 0.5~0.7;

[0009] n is 2500~3500, preferably 2900~3100;

[0010] a can be 1, 2, or 3.

[0011] The epoxy-furan modified polybutadiene of the present invention is obtained by reacting epoxidized polybutadiene and furanylcarboxylic acid under the action of a polymerization inhibitor and a phase transfer catalyst.

[0012] The structural formula of the epoxidized polybutadiene is:

[0013]

[0014] l=0.18~0.22, m=0.17~0.22, r=0.5~0.7;

[0015] n is between 2500 and 3500;

[0016] The structural formula of the furanylcarboxylic acid is: , where a is 1, 2 or 3.

[0017] Secondly, the present invention provides a method for preparing the epoxy-furan modified polybutadiene, comprising the following steps: reacting the mixture of the epoxy polybutadiene, furanylcarboxylic acid, polymerization inhibitor and phase transfer catalyst at a temperature of 100°C to 140°C for 3 to 8 hours to obtain the epoxy-furan modified polybutadiene.

[0018] Thirdly, the present invention provides the application of the epoxy-furan modified polybutadiene in the preparation of butyl hot melt adhesive.

[0019] Fourthly, the present invention provides a butyl hot melt adhesive, the raw materials of which include the epoxy-furan modified polybutadiene, wherein the epoxy-furan modified polybutadiene accounts for 3% to 12% of the weight of the butyl hot melt adhesive, preferably 4% to 8%, and more preferably 5% to 7%.

[0020] For example, the butyl hot melt adhesive is prepared from raw materials comprising the following components, by weight:

[0021] 1-7 parts of butyl rubber

[0022] 30-70 parts of polyisobutylene

[0023] 4-10 parts of epoxy-furan modified polybutadiene

[0024] 3-15 parts of tackifying resin

[0025] 15-40 parts of inorganic filler

[0026] 1-8 parts of absorbent

[0027] 8-30 parts of reinforcing agent

[0028] Dynamic crosslinking agent 0.5~4 parts

[0029] Antioxidant 0.5 to 2 parts

[0030] Light stabilizer 0.5-2 parts;

[0031] The dynamic crosslinking agent is one or more of 1,2-bis(maleimide) ethane, N,N'-m-phenylenebismaleimide, and N,N'-(4,4'-methylenediphenyl)bismaleimide.

[0032] Fifthly, the present invention provides a method for preparing the butyl hot melt adhesive, comprising the following steps:

[0033] At a temperature of 110℃~160℃, the butyl rubber, polyisobutylene, epoxy-furan modified polybutadiene, tackifying resin, inorganic filler, water absorbent, reinforcing agent, dynamic crosslinking agent, antioxidant and light stabilizer are added sequentially to a kneader and mixed under vacuum for 30 minutes to 130 minutes to obtain the butyl hot melt adhesive.

[0034] This invention involves reacting furanylcarboxylic acid with epoxidized polybutadiene to prepare an epoxy-furan modified polybutadiene. This modified polybutadiene is then introduced into raw materials such as polyisobutylene, and combined with bismaleimide as a dynamic crosslinking agent to prepare an epoxy-furan modified butyl hot melt adhesive. By introducing epoxy groups and furan groups into the butyl hot melt adhesive, and using bismaleimide as a dynamic crosslinking agent, dynamic covalent bonds of furan and maleimide can be formed, increasing the crosslinking density of the material and thus improving hardness, water resistance, and shear strength. Furthermore, the epoxy groups undergo acid-base attack ring-opening reactions to generate hydroxyl groups, which can form hydrogen bonds with hydroxyl groups on the glass surface, improving the adhesion between the adhesive and the glass. Moreover, when the butyl hot melt adhesive is subjected to tensile damage, the crosslinking bonds can be dissociated and restored through high-temperature-to-room-temperature heat treatment, thereby restoring the mechanical properties of the butyl hot melt adhesive and giving it a self-healing function.

[0035] Therefore, the butyl hot melt adhesive of the present invention exhibits high hardness, water resistance, shear strength, and good processability through the synergistic effect of its components. Furthermore, the butyl hot melt adhesive of the present invention demonstrates good adhesion to glass and excellent self-healing properties. The butyl hot melt adhesive of the present invention is suitable for use as an inner sealant in insulating glass units, which helps to extend the service life of insulating glass. Attached Figure Description

[0036] Figure 1 The 1H NMR spectrum of the epoxy-furan modified polybutadiene (a=1, x=0.22) prepared in Example 1 is shown, with CD3OD as the solvent.

[0037] Figure 2 The 1H NMR spectrum of the epoxy-furan modified polybutadiene (a=2, x=0.20) prepared in Example 5 is shown in CD3OD solvent.

[0038] Figure 3 This is a schematic diagram of the dynamic crosslinking network of the butyl hot melt adhesive of the present invention. Detailed Implementation

[0039] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments are merely illustrative of the present invention and should not be construed as limiting the invention.

[0040] Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to limit the invention.

[0041] The terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion. For example, a process, method, apparatus, product, or device that includes a series of steps is not limited to the steps or modules listed, but may optionally include steps not listed, or may optionally include other steps inherent to such process, method, product, or device.

[0042] In this invention, "multiple" refers to two or more. "And / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A alone, A and B simultaneously, or B alone. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0043] Some embodiments of the present invention relate to an epoxy-furan modified polybutadiene, the structural formula of which is:

[0044]

[0045] Where, l = 0.18~0.22, m = 0.17~0.22, x+y = 0.5~0.7;

[0046] n is 2500~3500, preferably 2900~3100;

[0047] a can be 1, 2, or 3.

[0048] In some of these embodiments, x+y=0.55~0.65, preferably 0.58~0.62, and most preferably 0.60.

[0049] In some of these implementations, l = 0.21, m = 0.19, and x + y = 0.6.

[0050] In some embodiments, x is 0.05 to 0.5, preferably 0.09 to 0.4, more preferably 0.15 to 0.35, and even more preferably 0.2 to 0.25.

[0051] The epoxy-furan modified polybutadiene of the present invention is obtained by reacting epoxidized polybutadiene and furanylcarboxylic acid under the action of a polymerization inhibitor and a phase transfer catalyst.

[0052] The structural formula of the epoxidized polybutadiene is: Where, l = 0.18~0.22, m = 0.17~0.22, r = 0.5~0.7, and n is 3000~3500;

[0053] The structural formula of the furanylcarboxylic acid is: , where a is 1, 2 or 3.

[0054] In some embodiments, r = 0.55~0.65, preferably 0.58~0.62, and most preferably 0.60.

[0055] In some of these implementations, l=0.21, m=0.19, and r=0.6.

[0056] In some implementations, n is 2900~3100.

[0057] In some embodiments, the phase transfer catalyst is tetrabutylammonium bromide.

[0058] In some embodiments, the polymerization inhibitor is hydroquinone.

[0059] In some embodiments, the molar ratio of the epoxy group in the epoxidized polybutadiene to the furanylcarboxylic acid is 1 to 4:1, preferably 1 to 3.5:1, more preferably 1.0 to 2.0:1, and even more preferably 1.2 to 1.5:1.

[0060] In some embodiments, the molar ratio of the epoxy groups in the epoxidized polybutadiene to the phase transfer catalyst is 1:0.001~0.03, preferably 1:0.003~0.008.

[0061] In some embodiments, the molar ratio of the epoxy groups in the epoxidized polybutadiene to the polymerization inhibitor is 1:0.001~0.03, preferably 1:0.005~0.01.

[0062] Some embodiments of the present invention relate to a method for preparing the epoxy-furan modified polybutadiene, comprising the following steps: reacting a mixture of the epoxy polybutadiene, furanylcarboxylic acid, polymerization inhibitor and phase transfer catalyst at a temperature of 100°C to 140°C for 3 to 8 hours to obtain the epoxy-furan modified polybutadiene.

[0063] In some embodiments, the reaction is carried out at a temperature of 115°C to 125°C for a duration of 4 to 6 hours.

[0064] In some embodiments, the reaction is carried out under the protection of an inert gas.

[0065] Some embodiments of the present invention relate to the application of the epoxy-furan modified polybutadiene in the preparation of butyl hot melt adhesives.

[0066] Some embodiments of the present invention relate to a butyl hot melt adhesive, the raw materials of which include the epoxy-furan modified polybutadiene described in the present invention.

[0067] In some embodiments, the epoxy-furan modified polybutadiene is preferably 3% to 12% by weight in the butyl hot melt adhesive, preferably 4% to 8%, and more preferably 5% to 7%.

[0068] In some embodiments, the butyl hot melt adhesive is prepared from raw materials comprising the following components, in parts by weight:

[0069] 1-7 parts of butyl rubber

[0070] 30-70 parts of polyisobutylene

[0071] 4-10 parts of epoxy-furan modified polybutadiene

[0072] 3-15 parts of tackifying resin

[0073] 15-40 parts of inorganic filler

[0074] 1-8 parts of absorbent

[0075] 8-30 parts of reinforcing agent

[0076] Dynamic crosslinking agent 0.5~4 parts

[0077] Antioxidant 0.5 to 2 parts

[0078] Light stabilizer 0.5-2 parts;

[0079] The dynamic crosslinking agent is one or more of 1,2-bis(maleimide) ethane, N,N'-m-phenylenebismaleimide, and N,N'-(4,4'-methylenediphenyl)bismaleimide.

[0080] In some embodiments, the butyl hot melt adhesive is prepared from raw materials comprising the following components, in parts by weight:

[0081] Butyl rubber 1.5 to 3 parts

[0082] 35-45 parts of polyisobutylene

[0083] 5-7 parts of epoxy-furan modified polybutadiene

[0084] 4-6 parts of tackifying resin

[0085] 20-30 parts of inorganic filler

[0086] 4-6 parts absorbent

[0087] 8-12 parts of reinforcing agent

[0088] Dynamic crosslinking agent 1.5~3 parts

[0089] Antioxidant 0.5 to 2 parts

[0090] Light stabilizer 0.5 to 2 parts.

[0091] In some embodiments, the raw butyl rubber has a Mooney viscosity of 27-56, preferably 48-53.

[0092] In some embodiments, the viscosity-average molecular weight of the polyisobutylene is 100,000 to 200,000, preferably 100,000 to 150,000.

[0093] In some embodiments, the tackifying resin is selected from one or more combinations of C5 petroleum resin, C9 petroleum resin, terpene resin, styrene-grafted terpene resin, polyterpene resin, and natural resin and rosin resin.

[0094] In some embodiments, the absorbent is selected from one or more combinations of calcium oxide, molecular sieve, calcium sulfate, anhydrous calcium chloride, anhydrous magnesium sulfate, and activated alumina.

[0095] In some embodiments, the reinforcing agent is selected from carbon black and / or silica.

[0096] In some embodiments, the inorganic filler is selected from one or more combinations of mica powder, silica powder, kaolin, calcium carbonate, talc, kaolin, clay, and diatomaceous earth.

[0097] In some embodiments, the antioxidant is selected from one or more combinations of pentaerythritol tetrakis[2-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-methylphenol, tris[2,4-di-tert-butylphenyl]phosphite, 2-methyl-4,6-dinonylphenol, 2,6-di-tert-butyl-α-methoxy-p-cresol, 2,4,6-tri-tert-butylphenol, and 2,2,4-trimethyl-1,2-dihydroquinoline polymer.

[0098] In some embodiments, the light stabilizer is selected from one or more combinations of hindered amine light stabilizers and hindered phenolic light stabilizers, preferably 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole.

[0099] Some embodiments of the present invention relate to a method for preparing the butyl hot melt adhesive, comprising the following steps:

[0100] At a temperature of 110℃~160℃, the butyl rubber, polyisobutylene, epoxy-furan modified polybutadiene, tackifying resin, inorganic filler, water absorbent, reinforcing agent, dynamic crosslinking agent, antioxidant and light stabilizer are added sequentially to a kneader and mixed under vacuum for 30 minutes to 130 minutes to obtain the butyl hot melt adhesive.

[0101] In some embodiments, the method for preparing the butyl hot melt adhesive includes the following steps:

[0102] At a temperature of 130℃~150℃, the butyl rubber, polyisobutylene, epoxy-furan modified polybutadiene, tackifying resin, inorganic filler, water absorbent, reinforcing agent, dynamic crosslinking agent, antioxidant and light stabilizer are added sequentially to a kneader and mixed under vacuum for 60 minutes to 100 minutes to obtain the butyl hot melt adhesive.

[0103] The present invention will be further described in detail below with reference to specific embodiments.

[0104] In the following embodiments, unless otherwise specified, "parts" refers to parts by weight.

[0105] In the following examples, the structural formula of epoxidized polybutadiene is:

[0106]

[0107] In the following examples, the structural formula of furanylcarboxylic acid is: , a=1,2,3.

[0108] In the following examples, the reaction formula for preparing epoxy-furan modified polybutadiene is as follows:

[0109]

[0110]

[0111] Where x+y=0.60, a=1,2,3.

[0112] Example 1

[0113] Preparation of epoxy-furan modified polybutadiene: 10 g of epoxy polybutadiene (epoxy value 2.5 mmol / g, n=3000, Tianyuan Aerospace Materials EHTPB3023), 18.1 mmol of 2-furanacetic acid, 0.2 mmol of hydroquinone, and 0.14 mmol of tetrabutylammonium bromide were added to a round-bottom flask equipped with a reflux condenser and a magnetic stirrer. The reaction was carried out at 120 °C for 5 hours under a nitrogen atmosphere. Then, ethyl acetate was added to extract the product. The mixture was washed three times with saturated NaCl solution and dried with anhydrous MgSO4. Finally, ethyl acetate was removed by distillation at 50 °C, and column chromatography was performed using silica gel column and a mixed solvent of dichloromethane / methanol = (10 / 1). After removing the solvent by rotary evaporation, epoxy-furan modified polybutadiene (a=1, x=0.22) was obtained.

[0114] The calculation method for x is as follows: Figure 1 As shown, taking the known proportion of double-bonded hydrogens (at position a) as a reference, and based on the number and proportion of double-bonded hydrogens at position a (2×0.21+3×0.19=0.99), the integral of the double-bonded hydrogens at position a is set to 0.99. The integral of one hydrogen in the furan double bond (at position b) is 0.22, thus we know that x is 0.22. Then, we use the hydrogens at positions d and e to verify. The integral of d+e is 1.49. Using the number and proportion of hydrogens at the corresponding positions, we calculate 4×0.21+1×0.19+2×0.22=1.47, which is basically consistent with the integral.

[0115] Preparation of epoxy-furan modified butyl hot melt adhesive: At 140℃, butyl rubber, medium molecular weight polyisobutylene, epoxy-furan modified polybutadiene, tackifying resin, inorganic filler, water absorbent, reinforcing agent, dynamic crosslinking agent, antioxidant and light stabilizer were added to a kneader in sequence as shown in Table 1, and the mixture was blended under vacuum for 80 minutes to obtain epoxy-furan modified butyl hot melt adhesive.

[0116] Table 1

[0117]

[0118] Example 2

[0119] Preparation of epoxy-furan modified polybutadiene: 10 g of epoxy polybutadiene (epoxy value 2.5 mmol / g, n=3000, Tianyuan Aerospace Materials EHTPB3023), 7.5 mmol of 2-furanacetic acid, 0.2 mmol of hydroquinone, and 0.14 mmol of tetrabutylammonium bromide were added to a round-bottom flask equipped with a reflux condenser and a magnetic stirrer. The reaction was carried out at 120 °C for 5 hours under a nitrogen atmosphere. Then, ethyl acetate was added to extract the product. The mixture was washed three times with saturated NaCl solution and dried with anhydrous MgSO4. Finally, ethyl acetate was removed by distillation at 50 °C, and column chromatography was performed using a silica gel column and a mixed solvent of dichloromethane / methanol = (10 / 1). After removing the solvent by rotary evaporation, epoxy-furan modified polybutadiene (a=1, x was approximately 0.09 as determined by the method in Example 1) was obtained.

[0120] Preparation of epoxy-furan modified butyl hot melt adhesive: At 140℃, butyl rubber, medium molecular weight polyisobutylene, epoxy-furan modified polybutadiene, tackifying resin, inorganic filler, water absorbent, reinforcing agent, dynamic crosslinking agent, antioxidant and light stabilizer were added to a kneader in sequence as shown in Table 2, and the mixture was blended under vacuum for 80 minutes to obtain epoxy-furan modified butyl hot melt adhesive.

[0121] Table 2

[0122]

[0123] Example 3

[0124] Preparation of epoxy-furan modified polybutadiene: 10 g of epoxy polybutadiene (epoxy value 2.5 mmol / g, n=3000, Tianyuan Aerospace Materials EHTPB3023), 23.75 mmol of 2-furanacetic acid, 0.2 mmol of hydroquinone, and 0.14 mmol of tetrabutylammonium bromide were added to a round-bottom flask equipped with a reflux condenser and a magnetic stirrer. The reaction was carried out at 120 °C for 5 hours under a nitrogen atmosphere. Then, ethyl acetate was added to extract the product. The mixture was washed three times with saturated NaCl solution and dried with anhydrous MgSO4. Finally, ethyl acetate was removed by distillation at 50 °C, and column chromatography was performed using a silica gel column and a mixed solvent of dichloromethane / methanol = (10 / 1). After removing the solvent by rotary evaporation, epoxy-furan modified polybutadiene (a=1, x was approximately 0.31 as determined by the method in Example 1) was obtained.

[0125] Preparation of epoxy-furan modified butyl hot melt adhesive: At 140℃, butyl rubber, medium molecular weight polyisobutylene, epoxy-furan modified polybutadiene, tackifying resin, inorganic filler, water absorbent, reinforcing agent, dynamic crosslinking agent, antioxidant and light stabilizer were added to a kneader in sequence as shown in Table 3, and the mixture was blended under vacuum for 80 minutes to obtain epoxy-furan modified butyl hot melt adhesive.

[0126] Table 3

[0127]

[0128] Example 4

[0129] Preparation of epoxy-furan modified polybutadiene: 10 g of epoxy polybutadiene (epoxy value 2.5 mmol / g, n=3000, Tianyuan Aerospace Materials EHTPB3023), 7.5 mmol of 3-(2-furan)propionic acid, 0.2 mmol of hydroquinone, and 0.14 mmol of tetrabutylammonium bromide were added to a round-bottom flask equipped with a reflux condenser and a magnetic stirrer. The reaction was carried out at 120 °C for 5 hours under a nitrogen atmosphere. Then, ethyl acetate was added to extract the product. The mixture was washed three times with saturated NaCl solution and dried with anhydrous MgSO4. Finally, ethyl acetate was removed by distillation at 50 °C, and column chromatography was performed using silica gel column and a mixed solvent of dichloromethane / methanol = (10 / 1). After removing the solvent by rotary evaporation, epoxy-furan modified polybutadiene (a=2, x=0.09) was obtained.

[0130] Preparation of epoxy-furan modified butyl hot melt adhesive: At 140℃, butyl rubber, medium molecular weight polyisobutylene, epoxy-furan modified polybutadiene, tackifying resin, inorganic filler, water absorbent, reinforcing agent, dynamic crosslinking agent, antioxidant and light stabilizer were added to a kneader in sequence as shown in Table 4, and the mixture was blended under vacuum for 80 minutes to obtain epoxy-furan modified butyl hot melt adhesive.

[0131] Table 4

[0132]

[0133] Example 5

[0134] Preparation of epoxy-furan modified polybutadiene: 10 g of epoxy polybutadiene (epoxy value 2.5 mmol / g, n=3000, Tianyuan Aerospace Materials EHTPB3023), 16.25 mmol of 3-(2-furan)propionic acid, 0.2 mmol of hydroquinone, and 0.14 mmol of tetrabutylammonium bromide were added to a round-bottom flask equipped with a reflux condenser and a magnetic stirrer. The reaction was carried out at 120 °C for 5 hours under a nitrogen atmosphere. Then, ethyl acetate was added to extract the product. The mixture was washed three times with saturated NaCl solution and dried with anhydrous MgSO4. Finally, ethyl acetate was removed by distillation at 50 °C, and column chromatography was performed using a silica gel column and a mixed solvent of dichloromethane / methanol = (10 / 1). After removing the solvent by rotary evaporation, epoxy-furan modified polybutadiene (a=2, x=0.20 as determined by the method in Example 1) was obtained.

[0135] Preparation of epoxy-furan modified butyl hot melt adhesive: At 140℃, butyl rubber, medium molecular weight polyisobutylene, epoxy-furan modified polybutadiene, tackifying resin, inorganic filler, water absorbent, reinforcing agent, dynamic crosslinking agent, antioxidant and light stabilizer were added to a kneader in sequence as shown in Table 5, and the mixture was blended under vacuum for 80 minutes to obtain epoxy-furan modified butyl hot melt adhesive.

[0136] Table 5

[0137]

[0138] Comparative Example 1

[0139] The difference from Example 2 is that no dynamic crosslinking agent is added.

[0140] Preparation of epoxy-furan modified polybutadiene: 10 g of epoxy polybutadiene (epoxy value 2.5 mmol / g, n=3000, Tianyuan Aerospace Materials EHTPB3023), 7.5 mmol of 2-furanacetic acid, 0.2 mmol of hydroquinone, and 0.14 mmol of tetrabutylammonium bromide were added to a round-bottom flask equipped with a reflux condenser and a magnetic stirrer. The reaction was carried out at 120 °C for 5 hours under a nitrogen atmosphere. Then, ethyl acetate was added to extract the product. The mixture was washed three times with saturated NaCl solution and dried with anhydrous MgSO4. Finally, ethyl acetate was removed by distillation at 50 °C, and column chromatography was performed using silica gel column and a mixed solvent of dichloromethane / methanol = (10 / 1). After removing the solvent by rotary evaporation, epoxy-furan modified polybutadiene (a=1, x=0.09) was obtained.

[0141] Preparation of epoxy-furan modified butyl hot melt adhesive: At 140℃, butyl rubber, medium molecular weight polyisobutylene, epoxy-furan modified polybutadiene, tackifying resin, inorganic filler, water absorbent, reinforcing agent, antioxidant and light stabilizer were added to a kneader in sequence as shown in Table 6. The mixture was then blended under vacuum for 80 minutes to obtain epoxy-furan modified butyl hot melt adhesive.

[0142] Table 6

[0143]

[0144] Comparative Example 2

[0145] The difference from Example 2 is that the epoxidized polybutadiene is not modified by furan grafting.

[0146] Preparation of epoxy-modified butyl hot melt adhesive: At 140℃, butyl rubber, medium molecular weight polyisobutylene, epoxy-modified polybutadiene, tackifying resin, inorganic filler, water absorbent, reinforcing agent, dynamic crosslinking agent, antioxidant and light stabilizer were added to a kneader in sequence as shown in Table 7, and the mixture was blended under vacuum for 80 minutes to obtain epoxy-modified butyl hot melt adhesive.

[0147] Table 7

[0148]

[0149] Comparative Example 3

[0150] The difference from Example 2 is that no dynamic crosslinking agent is added, and the epoxy-modified polybutadiene is not modified with furan.

[0151] Preparation of epoxy-modified butyl hot melt adhesive: At 140℃, butyl rubber, medium molecular weight polyisobutylene, epoxy-modified polybutadiene, tackifying resin, inorganic filler, water absorbent, reinforcing agent, antioxidant and light stabilizer were added to a kneader in sequence as shown in Table 8, and the mixture was blended under vacuum for 80 minutes to obtain epoxy-modified butyl hot melt adhesive.

[0152] Table 8

[0153]

[0154] Comparative Example 4

[0155] The difference between this comparative example and Example 2 is that it uses silane-modified polybutadiene (Evonik, ST-E).

[0156] Preparation of modified butyl hot melt adhesive: At 140℃, butyl rubber, medium molecular weight polyisobutylene, silane-modified polybutadiene, tackifying resin, inorganic filler, water absorbent, reinforcing agent, dynamic crosslinking agent, antioxidant and light stabilizer were added to a kneader in sequence as shown in Table 9, and the mixture was blended under vacuum for 80 minutes to obtain modified butyl hot melt adhesive.

[0157] Table 9

[0158]

[0159] The butyl hot melt adhesives prepared in Examples 1-5 and Comparative Examples 1-4 were subjected to the performance tests shown in Table 10. The performance test methods for the samples in Table 10 are as follows:

[0160] 1. Melt Flow Index: The volumetric flow rate at 130℃ and 10kg load is tested according to GB / T 3682.1-2018.

[0161] 2. 25℃ Penetration: Take a whole piece of clay with a height of not less than 30 mm and a length and width of not less than 50 mm, place it in the container provided with the equipment or other suitable container, and conduct the test according to the provisions of GB / T 4509-2010. Use three needles to test different positions of the clay, and take the integer of the average of the three results as the test result.

[0162] 3. 38℃, 90%RH water vapor transmission rate: The test shall be conducted in accordance with the provisions of GB / T 26253-2010. Place the putty on the release paper, heat it to a suitable temperature, and then press it into a sheet with a thickness of (1±0.1) mm, a length of not less than 120 mm, and a width of not less than 120 mm. Take a circular test piece with a diameter of not less than 100 mm for testing.

[0163] 4. Shear strength of glass-aluminum: The shear strength shall be tested according to the relevant provisions of JC / T 914-2014;

[0164] 5. Repair test: The adhesive cross-section of the sample that has completed the shear strength test is reassembled, heat-treated at 130℃ for 30 minutes, and then placed at room temperature for 1 day before the shear strength test is repeated.

[0165] The results are shown in Table 10.

[0166] Furan-maleimide can dissociate at 130°C. The butyl hot melt adhesives in Examples 1-4 exhibit high melt flow rates, indicating good processability. At room temperature, the cross-linked structure is restored (e.g., ...). Figure 3 Butyl rubber exhibits high shear strength, good adhesion (exhibiting shear failure in the form of cohesive failure), low penetration, and low water vapor permeability. After the broken rubber sections are rejoined and subjected to high-temperature heat treatment, the mechanical properties of butyl hot melt adhesive can be restored, demonstrating excellent self-healing properties.

[0167] The data from Examples 1-3 also show that as the x value (i.e., the grafting rate of furan) increases, the penetration of butyl hot melt adhesive decreases, the water vapor transmission rate decreases, and the shear strength increases. However, a larger x value is not always better. When the x value is too large, it will affect the mechanical properties and density of butyl hot melt adhesive, resulting in a decrease in its water resistance and shear strength. When x is 0.22, the butyl hot melt adhesive has the best overall performance.

[0168] Comparative Examples 1-3, lacking dynamic crosslinking agents and / or without furan graft modification of epoxidized polybutadiene, resulted in butyl hot melt adhesives that failed to form a crosslinked network, exhibiting low shear strength, high penetration, and high water vapor permeability. Even after reassembling the fractured adhesive surfaces and subjecting them to high-temperature heat treatment, the mechanical properties of the butyl hot melt adhesives could not be restored. Specifically, Comparative Examples 2-3, lacking modification, showed poor adhesion between the butyl hot melt adhesives and glass, exhibiting interfacial damage. In Comparative Example 4, due to the irreversible nature of the Si-O-Si crosslinking, the mechanical properties of the butyl hot melt adhesive could not be restored even after reassembling the fractured adhesive surfaces and subjecting them to high-temperature heat treatment.

[0169] Table 10 Summary of the properties of butyl hot melt adhesives in Examples 1-5 and Comparative Examples 1-4

[0170]

[0171] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0172] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. An epoxy-furan modified polybutadiene, characterized in that, Its structural formula is: Wherein, l = 0.18~0.22, m = 0.17~0.22, x+y = 0.5~0.7, and x+y is preferably 0.58~0.62; n is 2500~3500, preferably 2900~3100; a can be 1, 2, or 3.

2. The epoxy-furan modified polybutadiene according to claim 1, characterized in that, x is 0.05~0.5, preferably 0.09~0.4, preferably 0.15~0.35, and preferably 0.2~0.

25.

3. An epoxy-furan modified polybutadiene, characterized in that, It is obtained by reacting epoxidized polybutadiene and furanylcarboxylic acid in the presence of a polymerization inhibitor and a phase transfer catalyst; The structural formula of the epoxidized polybutadiene is: l = 0.18~0.22, m = 0.17~0.22, r = 0.5~0.7, with r preferably being 0.58~0.62; n is between 2500 and 3500; The structural formula of the furanylcarboxylic acid is: , where a is 1, 2 or 3.

4. The epoxy-furan modified polybutadiene according to claim 3, characterized in that, n is between 2900 and 3100; And / or, the phase transfer catalyst is tetrabutylammonium bromide; And / or, the polymerization inhibitor is hydroquinone; The molar ratio of the epoxy group to furanyl carboxylic acid in the epoxidized polybutadiene is 1~4:1, preferably 1~3.5:1, more preferably 1.0~2.0:1, and even more preferably 1.2~1.5:1; And / or, the molar ratio of the epoxy groups in the epoxidized polybutadiene to the phase transfer catalyst is 1:0.001~0.03, preferably 1:0.003~0.008; And / or, the molar ratio of the epoxy groups in the epoxidized polybutadiene to the polymerization inhibitor is 1:0.001~0.03, preferably 1:0.005~0.

01.

5. A method for preparing epoxy-furan modified polybutadiene according to any one of claims 2-4, characterized in that, The process includes the following steps: reacting the mixture of epoxidized polybutadiene, furanylcarboxylic acid, polymerization inhibitor and phase transfer catalyst at a temperature of 100℃~140℃ for 3 hours~8 hours to obtain the epoxidized-furan modified polybutadiene. Preferably, the reaction temperature is 115℃~125℃ and the time is 4 hours~6 hours; Preferably, the reaction is carried out under the protection of an inert gas.

6. The use of the epoxy-furan modified polybutadiene according to any one of claims 1-4 in the preparation of butyl hot melt adhesive.

7. A butyl hot melt adhesive, characterized in that, The raw materials used in its preparation include the epoxy-furan modified polybutadiene as described in any one of claims 1-4, wherein the epoxy-furan modified polybutadiene is preferably 3% to 12% by weight in the butyl hot melt adhesive, preferably 4% to 8%, and more preferably 5% to 7%.

8. The butyl hot melt adhesive according to claim 7, characterized in that, It is prepared from raw materials comprising the following components, in parts by weight: 1-7 parts of butyl rubber 30-70 parts of polyisobutylene 4-10 parts of epoxy-furan modified polybutadiene 3-15 parts of tackifying resin 15-40 parts of inorganic filler 1-8 parts of absorbent 8-30 parts of reinforcing agent Dynamic crosslinking agent 0.5~4 parts Antioxidant 0.5 to 2 parts Light stabilizer 0.5-2 parts; The dynamic crosslinking agent is one or more of 1,2-bis(maleimide) ethane, N,N'-m-phenylenebismaleimide and N,N'-(4,4'-methylenediphenyl)bismaleimide; Preferably, the butyl hot melt adhesive is prepared from raw materials comprising the following components, in parts by weight: Butyl rubber 1.5 to 3 parts 35-45 parts of polyisobutylene 5-7 parts of epoxy-furan modified polybutadiene 4-6 parts of tackifying resin 20-30 parts of inorganic filler 4-6 parts absorbent 8-12 parts of reinforcing agent Dynamic crosslinking agent 1.5~3 parts Antioxidant 0.5 to 2 parts Light stabilizer 0.5 to 2 parts.

9. The butyl hot melt adhesive according to claim 8, characterized in that, The raw butyl rubber Mooney viscosity ML 1+8 The value is 27~56, preferably 48~53; And / or, the viscosity-average molecular weight of the polyisobutylene is 100,000 to 200,000, preferably 100,000 to 150,000; And / or, the tackifying resin is selected from one or more combinations of C5 petroleum resin, C9 petroleum resin, terpene resin, styrene-grafted terpene resin, polyterpene resin, natural resin, and rosin resin; And / or, the water absorbent is selected from one or more combinations of calcium oxide, molecular sieve, calcium sulfate, anhydrous calcium chloride, anhydrous magnesium sulfate and activated alumina; And / or, the reinforcing agent is selected from carbon black and / or silica; And / or, the inorganic filler is selected from one or more combinations of mica powder, silica powder, kaolin, calcium carbonate, talc powder, kaolin, clay and diatomaceous earth; And / or, the antioxidant is selected from one or more combinations of the following: pentaerythritol tetrakis[2-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-methylphenol, tris[2,4-di-tert-butylphenyl] phosphite, 2-methyl-4,6-dinonylphenol, 2,6-di-tert-butyl-α-methoxy-p-cresol, 2,4,6-tri-tert-butylphenol, and 2,2,4-trimethyl-1,2-dihydroquinoline polymer; And / or, the light stabilizer is selected from one or more combinations of hindered amine light stabilizers and hindered phenolic light stabilizers, preferably 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole.

10. A method for preparing the butyl hot melt adhesive according to claim 8 or 9, characterized in that, Includes the following steps: At a temperature of 110℃~160℃, the butyl rubber, polyisobutylene, epoxy-furan modified polybutadiene, tackifying resin, inorganic filler, water absorbent, reinforcing agent, dynamic crosslinking agent, antioxidant and light stabilizer are added sequentially to a kneader and mixed under vacuum for 30 minutes to 130 minutes to obtain the butyl hot melt adhesive.

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