Self-repairing butyl hot melt adhesive for hollow glass and preparation method thereof

Abstract

The present application relates to a kind of self-repairing type butyl hot melt adhesive for hollow glass and its preparation method.The butyl hot melt adhesive is prepared from raw materials comprising the following components: modified butyl rubber, polyisobutylene, crosslinking agent, tackifying resin, plasticizer, water absorbent, inorganic filler, reinforcing agent, antioxidant;The modified butyl rubber is obtained by halogenated butyl rubber sequentially and hydroxy acid compound, hydrogen-containing silane reaction;The structural formula of the hydroxy acid compound is HO (CH2) m CH=CHCOOH;The structural formula of the hydrogen-containing silane is HSi (R1) (OR2) 2;The crosslinking agent is amine compound with di-functionality or above.This butyl hot melt adhesive has excellent bonding performance with glass and silicone glue, and also has good self-repairing performance.

Description

Technical Field

[0001] This invention belongs to the field of sealant technology, specifically relating to a self-healing butyl hot melt adhesive for insulating glass and its preparation method. 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, special waterproof tapes, and photovoltaic modules. 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 a first-layer sealant for the inner layer of insulated glass, for example, in conjunction with polysulfide sealant or silicone sealant to achieve long-term structural bonding. However, traditional butyl hot melt adhesives have poor adhesion to glass or silicone sealant and cannot provide effective fixing and bonding.

[0003] Furthermore, improper application or errors during sealant use can easily lead to damage, defects, or bubbles in the sealant, causing a decline in the mechanical properties of the butyl hot melt sealant. In severe cases, this can even result in sealing failure, accelerating inert gas leakage and significantly reducing the lifespan of the insulated glass unit. As the first layer of sealing, if damage or bubbles within the sealant are not detected before applying the second layer of silicone sealant, the first layer is difficult to repair, greatly reducing the pass rate of the insulated glass product and increasing its cost. Summary of the Invention

[0004] Based on this, the purpose of the present invention is to provide a self-healing butyl hot melt adhesive for insulating glass, which improves the bonding performance of butyl hot melt adhesive with glass and silicone sealant while giving butyl hot melt adhesive good self-healing properties.

[0005] The technical solutions for achieving the above objectives include the following.

[0006] A first aspect of the present invention is to provide a self-healing butyl hot melt adhesive for insulating glass, wherein the butyl hot melt adhesive is prepared from raw materials comprising the following components, by weight:

[0007]

[0008] The modified butyl rubber is obtained by reacting halogenated butyl rubber with hydroxyl olefin compounds and hydrogen-containing silanes in sequence.

[0009] The structural formula of the hydroxyolefin compound is HO(CH2). m CH=CHCOOH, where m is selected from: 2, 3, 4, 5, 6, 7, 8;

[0010] The structural formula of the hydrogen-containing silane is HSi(R1)(OR2)2, wherein R1 is selected from: C1-C6 alkoxy, C1-C6 alkyl, and R2 is selected from: C1-C6 alkyl.

[0011] The crosslinking agent is an amine compound with difunctionality or higher.

[0012] In some embodiments, the self-healing butyl hot melt adhesive for insulating glass is prepared from raw materials comprising the following components, by weight:

[0013]

[0014] In some embodiments, the self-healing butyl hot melt adhesive for insulating glass is prepared from raw materials comprising the following components, by weight:

[0015]

[0016] In some embodiments, the halogenated butyl rubber is brominated butyl rubber and / or chlorinated butyl rubber.

[0017] In some embodiments, the raw Mooney viscosity ML of the halogenated butyl rubber is... 1+8 The value is 27-50, preferably 30-40.

[0018] In some embodiments, the halogenated butyl rubber contains 1 to 2.2% halogen groups by mass.

[0019] In some embodiments, R1 is selected from: -OCH3, -OCH2CH3, -CH3, -CH2CH3, and R2 is -CH3 or -CH2CH3.

[0020] In some embodiments, the molar ratio of halogen groups, hydroxyl olefin compounds and hydrogen-containing silanes in the halogenated butyl rubber is 1:0.8-3:0.8-3, preferably 1:0.9-1.1:0.9-1.1.

[0021] In some embodiments, the method for preparing the modified butyl rubber includes the following steps:

[0022] (1) The halobutyl rubber and hydroxyolefin compounds are reacted in an organic solvent under the action of an inorganic base to obtain an intermediate product;

[0023] (2) The intermediate product and the hydrogen-containing silane are reacted in an organic solvent under the action of a platinum catalyst to obtain the modified butyl rubber.

[0024] In some of these embodiments, the organic solvent in step (1) is tetrahydrofuran.

[0025] In some embodiments, the inorganic base in step (1) is potassium carbonate.

[0026] In some embodiments, the molar ratio of the halogen groups of the halogenated butyl rubber to potassium carbonate is 1:1 to 2.

[0027] In some embodiments, the temperature of the reaction in step (1) is 15°C to 35°C, and the reaction time is 10 hours to 20 hours.

[0028] In some embodiments, the platinum catalyst in step (2) is chloroplatinic acid or a cassiterite catalyst.

[0029] In some embodiments, the mass ratio of the hydrogen-containing silane to the platinum catalyst is 1:0.02% to 0.08%.

[0030] In some embodiments, the organic solvent in step (2) is toluene.

[0031] In some embodiments, the reaction in step (2) includes reacting at a temperature of 60°C to 90°C for 2 to 8 hours, and then raising the temperature to 70°C to 100°C to continue the reaction for 3 to 9 hours.

[0032] In some embodiments, the reaction in step (2) includes reacting at a temperature of 65°C to 75°C for 3 to 6 hours, and then raising the temperature to 90°C to 100°C to continue the reaction for 5 to 7 hours.

[0033] In some embodiments, the method for preparing the modified butyl rubber includes the following steps:

[0034] The halogenated butyl rubber is dissolved in tetrahydrofuran, and then the hydroxyl olefin compound and inorganic base are added to the solution. The mixture is stirred at 15°C to 35°C for 10 to 20 hours. After removing the solid, the tetrahydrofuran is removed. The resulting intermediate product is dissolved in toluene, and the hydrogen-containing silane and platinum catalyst are added. The temperature is raised to 60°C to 90°C, and the reaction is carried out for 2 to 8 hours. Then the temperature is raised to 70°C to 100°C, and the reaction is continued for 3 to 9 hours. Finally, the temperature in the reactor is raised to 110°C to 130°C, and the solvent is removed by vacuum to obtain the modified butyl rubber.

[0035] In some embodiments, the crosslinking agent is selected from at least one of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, N,N'-dimethyl-1,6-diaminohexane, and N,N'-dimethyl-1,8-octanediamine.

[0036] In some embodiments, the polyisobutylene is composed of low molecular weight polyisobutylene and high molecular weight polyisobutylene; the low molecular weight polyisobutylene has a viscosity-average molecular weight of 30,000 to 100,000; and the high molecular weight polyisobutylene has a viscosity-average molecular weight of 100,000 to 2,000,000.

[0037] In some embodiments, the low molecular weight polyisobutylene has a viscosity-average molecular weight of 50,000 to 80,000; and the high molecular weight polyisobutylene has a viscosity-average molecular weight of 150,000 to 250,000.

[0038] In some embodiments, the low molecular weight polyisobutylene has a viscosity-average molecular weight of 60,000 to 70,000; and the high molecular weight polyisobutylene has a viscosity-average molecular weight of 150,000 to 200,000.

[0039] In some embodiments, the polyisobutylene is composed of low molecular weight polyisobutylene and high molecular weight polyisobutylene in a mass ratio of 1-3:1.

[0040] In some embodiments, the plasticizer is one or more of polybutene, phthalate, di-n-octyl adipate and diisooctyl adipate.

[0041] 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, natural resin and rosin resin.

[0042] 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.

[0043] 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.

[0044] In some embodiments, the reinforcing agent is selected from one or a combination of two of carbon black and fumed silica.

[0045] In some embodiments, the antioxidant is selected from one or more combinations of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl 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.

[0046] A second aspect of the present invention is to provide a method for preparing a self-healing butyl hot melt adhesive for insulating glass, comprising the following steps:

[0047] At 110℃~160℃, the modified butyl rubber, polyisobutylene, tackifying resin and antioxidant are added sequentially to a kneader and mixed under vacuum for 20 minutes to 130 minutes; then the inorganic filler, reinforcing agent, water absorbent and crosslinking agent are added sequentially and mixed under vacuum for 60 minutes to 180 minutes to obtain the self-healing butyl hot melt adhesive for insulating glass.

[0048] In some embodiments, the method for preparing the self-healing butyl hot melt adhesive for insulating glass includes the following steps:

[0049] At 140℃~170℃, the modified butyl rubber, polyisobutylene, plasticizer, tackifying resin and antioxidant are added sequentially to a kneader and mixed under vacuum for 20 minutes to 60 minutes; then the inorganic filler, reinforcing agent, water absorbent and crosslinking agent are added sequentially and mixed under vacuum for 100 minutes to 150 minutes to obtain the self-healing butyl hot melt adhesive for insulating glass.

[0050] The present invention has the following beneficial effects:

[0051] This invention modifies halogenated butyl rubber with hydroxyl acrylic compounds and hydrogen-containing silanes to obtain modified butyl rubber with siloxane and carboxyl groups. This modified butyl rubber, along with polyisobutylene, multifunctional amine crosslinking agents, and other components, is formulated into a reactive butyl hot melt adhesive with self-healing properties. In this butyl hot melt adhesive system, the siloxane groups serve two purposes: firstly, they facilitate the formation of a first chemical crosslinking network through a de-alcoholization reaction after application; secondly, they improve the adhesion of the butyl hot melt adhesive to glass and silicone sealants. The carboxyl groups interact with the multifunctional amine crosslinking agent through acid-base electrostatic interactions to form a second physical crosslinking network, enhancing the mechanical properties of the material while also imparting excellent self-healing properties to the butyl hot melt adhesive. With the synergistic effect of the components, the butyl hot melt adhesive of this invention exhibits excellent adhesion to the glass interface and silicone sealants, high strength, good mechanical properties, and superior self-healing performance, making it a suitable sealant for insulating glass units. Furthermore, the electrostatic interactions in the system undergo reversible dissociation at higher temperatures, which does not affect the processing and application performance of butyl hot melt adhesive. Detailed Implementation

[0052] To facilitate understanding of the present invention, a more complete description will be provided below. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the present invention.

[0053] Unless otherwise specified, experimental methods in the following examples are generally performed under standard conditions or as recommended by the manufacturer. All raw materials and chemical reagents used in the examples are commercially available products.

[0054] 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. The term "and / or" as used in this invention includes any and all combinations of one or more of the associated listed items.

[0055] Furthermore, as used herein, the term "or" is an inclusive "or" sign and is equivalent to the term "and / or" unless the context clearly specifies otherwise. The term "based on" is not exclusive and allows for basing on other factors not described unless the context clearly specifies otherwise. Additionally, throughout the specification, the meanings of "an," "a," and "the" include plural indicators. The meaning of "in" includes both "in" and "on."

[0056] The present invention will be further described in detail below with reference to specific embodiments.

[0057] In the following embodiments, the normal temperature or room temperature refers to an indoor temperature of 20℃-30℃.

[0058] Example 1

[0059] 200g of brominated butyl rubber (raw rubber Mooney viscosity ML) 1+8 =33, bromine content 1.9wt%, bromine molar amount 0.048mol, commercially available) was dissolved in 1.3L tetrahydrofuran, then 9.0g HO(CH2)7CH=CHCOOH (0.048mol, commercially available) and 6.7g (0.048mol, commercially available) potassium carbonate were added to the solution. After stirring at room temperature for 12 hours, the solid was filtered and the tetrahydrofuran was removed by rotary evaporation. The obtained product was dissolved in 300mL toluene, and 5.9g HSi(OCH3)3 (0.048mol, commercially available) and 3mg chloroplatinic acid (0.05% of the mass of the hydrogen-containing silane, commercially available) were added. The mixture was heated to 70℃ under nitrogen protection and reacted for 6 hours. Then the temperature was raised to 100℃ and the reaction was continued for 7 hours. Finally, the temperature in the reactor was raised to 110℃ and the solvent was removed by vacuum to obtain the modified butyl rubber.

[0060] At 150°C, modified butyl rubber, polyisobutylene mixture, plasticizer, tackifying resin and antioxidant were added to the kneader in sequence according to Table 1, and mixed for 30 minutes under -0.1MPa vacuum protection; then inorganic filler, reinforcing agent, water absorbent and crosslinking agent were added in sequence, and mixed thoroughly for 120 minutes under -0.1MPa vacuum protection to obtain self-healing butyl hot melt adhesive for insulating glass.

[0061] Table 1

[0062]

[0063] Example 2

[0064] 200g of chlorinated butyl rubber (raw rubber Mooney viscosity ML) 1+8 =38, chlorine content 1.26wt%, chlorine molar amount 0.071mol, commercially available) was dissolved in 1.3L of tetrahydrofuran, and then 13.2g of HO(CH2)7CH=CHCOOH (0.071mol, commercially available) and 9.9g of potassium carbonate (0.071mol, commercially available) were added to the solution. After stirring at room temperature for 18 hours, the solid was filtered and the tetrahydrofuran was removed by rotary evaporation. The obtained product was dissolved in 300mL of toluene, and 11.7g of HSi(OCH2CH3)3 (0.071mol, commercially available) and 5.8mg of chloroplatinic acid (0.05% of the mass of the hydrogen-containing silane, commercially available) were added. The mixture was heated to 70℃ under nitrogen protection and reacted for 3 hours. Then the temperature was raised to 100℃ and the reaction was continued for 7 hours. Finally, the temperature in the reactor was raised to 110℃ and the solvent was removed by vacuum to obtain the modified butyl rubber.

[0065] At 170°C, the modified butyl rubber, polyisobutylene mixture, plasticizer, tackifying resin and antioxidant were added to the kneader in sequence according to Table 2, and mixed for 30 minutes under -0.1MPa vacuum protection; then the inorganic filler, reinforcing agent, water absorbent and crosslinking agent were added in sequence, and mixed thoroughly for 120 minutes under -0.1MPa vacuum protection to obtain a self-healing butyl hot melt adhesive for insulating glass.

[0066] Table 2

[0067]

[0068]

[0069] Example 3

[0070] 200g of brominated butyl rubber (raw rubber Mooney viscosity ML) 1+8=33, bromine content 1.9wt%, bromine molar amount 0.048mol, commercially available) was dissolved in 1.3L tetrahydrofuran, then 5.6g HO(CH2)2CH=CHCOOH (0.048mol, commercially available) and 6.7g potassium carbonate (0.048mol, commercially available) were added to the solution. After stirring at room temperature for 18 hours, the solid was filtered and the tetrahydrofuran was removed by rotary evaporation. The obtained product was dissolved in 300mL toluene, and 7.9g HSi(OCH2CH3)3 (0.048mol, commercially available) and 4.0mg Castella catalyst (mass of 0.05% of the mass of the hydrogen-containing silane, commercially available) were added. The mixture was heated to 70℃ under nitrogen protection and reacted for 3 hours, then heated to 90℃ and reacted for another 5 hours. Finally, the temperature in the reactor was raised to 110℃ and the solvent was removed by vacuum to obtain the modified butyl rubber.

[0071] At 160°C, the modified butyl rubber, polyisobutylene mixture, plasticizer, tackifying resin and antioxidant were added to the kneader in sequence according to Table 3, and mixed for 45 minutes under -0.1MPa vacuum protection; then the inorganic filler, reinforcing agent, water absorbent and crosslinking agent were added in sequence, and mixed thoroughly for 120 minutes under -0.1MPa vacuum protection to obtain a self-healing butyl hot melt adhesive for insulating glass.

[0072] Table 3

[0073]

[0074]

[0075] Example 4

[0076] 200g of brominated butyl rubber (raw rubber Mooney viscosity ML) 1+8 =33, bromine content 1.9wt%, bromine molar amount 0.048mol, commercially available) was dissolved in 1.3L tetrahydrofuran, then 9.0g HO(CH2)7CH=CHCOOH (0.048mol, commercially available) and 6.7g potassium carbonate (0.048mol, commercially available) were added to the solution. After stirring at room temperature for 18 hours, the solid was filtered and the tetrahydrofuran was removed by rotary evaporation. The obtained product was dissolved in 300mL toluene, and 5.1g HSi(CH3)(OCH3)2 (0.048mol, commercially available) and 2.6mg Castella catalyst (mass of 0.05% of the mass of the hydrogen-containing silane, commercially available) were added. The mixture was heated to 70℃ under nitrogen protection and reacted for 4 hours, then heated to 90℃ and reacted for another 5 hours. Finally, the temperature in the reactor was raised to 110℃ and the solvent was removed by vacuum to obtain the modified butyl rubber.

[0077] At 160°C, the modified butyl rubber, polyisobutylene mixture, plasticizer, tackifying resin and antioxidant were added to the kneader in sequence according to Table 4, and mixed for 45 minutes under -0.1MPa vacuum protection; then the inorganic filler, reinforcing agent, water absorbent and crosslinking agent were added in sequence, and mixed thoroughly for 120 minutes under -0.1MPa vacuum protection to obtain a self-healing butyl hot melt adhesive for insulating glass.

[0078] Table 4

[0079]

[0080] Example 5

[0081] 200g of brominated butyl rubber (raw rubber Mooney viscosity ML) 1+8 =33, bromine content 1.9wt%, bromine molar amount 0.048mol, commercially available) was dissolved in 1.3L tetrahydrofuran, then 5.6g HO(CH2)2CH=CHCOOH (0.048mol, commercially available) and 6.7g potassium carbonate (0.048mol, commercially available) were added to the solution. After stirring at room temperature for 18 hours, the solid was filtered and the tetrahydrofuran was removed by rotary evaporation. The obtained product was dissolved in 300mL toluene, and 6.4g HSi(CH3)(OCH2CH3)2 (0.048mol, commercially available) and 3.2mg Castella catalyst (mass of 0.05% of the mass of the hydrogen-containing silane, commercially available) were added. The mixture was heated to 70℃ under nitrogen protection and reacted for 5 hours. Then the temperature was raised to 90℃ and the reaction was continued for 5 hours. Finally, the temperature in the reactor was raised to 110℃ and the solvent was removed by vacuum to obtain the modified butyl rubber.

[0082] At 160°C, the modified butyl rubber, polyisobutylene mixture, plasticizer, tackifying resin and antioxidant were added to the kneader in sequence according to Table 5, and mixed for 45 minutes under -0.1MPa vacuum protection; then the inorganic filler, reinforcing agent, water absorbent and crosslinking agent were added in sequence, and mixed thoroughly for 120 minutes under -0.1MPa vacuum protection to obtain a self-healing butyl hot melt adhesive for insulating glass.

[0083] Table 5

[0084]

[0085]

[0086] Comparative Example 1

[0087] The difference between this comparative example and Example 1 is that no crosslinking agent was added.

[0088] 200g of brominated butyl rubber (raw rubber Mooney viscosity ML) 1+8=33, bromine content 1.9wt%, bromine molar amount 0.048mol, commercially available) was dissolved in 1.3L tetrahydrofuran, then 9.0g HO(CH2)7CH=CHCOOH (0.048mol, commercially available) and 6.7g potassium carbonate (0.048mol, commercially available) were added to the solution. After stirring at room temperature for 12 hours, the solid was filtered and the tetrahydrofuran was removed by rotary evaporation. The obtained product was dissolved in 300mL toluene, and 5.9g HSi(OCH3)3 (0.048mol, commercially available) and 3mg chloroplatinic acid (containing 0.05% of the mass of hydrogen silane, commercially available) were added. The mixture was heated to 70℃ under nitrogen protection and reacted for 6 hours. Then the temperature was raised to 100℃ and the reaction was continued for 7 hours. Finally, the temperature in the reactor was raised to 110℃ and the solvent was removed by vacuum to obtain the modified butyl rubber.

[0089] At 150°C, the modified butyl rubber, polyisobutylene mixture, plasticizer, tackifying resin and antioxidant were added to the kneader in sequence according to Table 6, and mixed for 30 minutes under -0.1MPa vacuum protection; then the inorganic filler, reinforcing agent and water absorbent were added in sequence, and mixed thoroughly for 120 minutes under -0.1MPa vacuum protection to obtain a self-healing butyl hot melt adhesive for insulating glass.

[0090] Table 6

[0091]

[0092]

[0093] Comparative Example 2

[0094] The difference between this comparative example and Example 1 is that the brominated butyl rubber (raw rubber Mooney viscosity ML) was not compared. 1+8 =33, bromine content 1.9wt%, commercially available) was modified.

[0095] At 150°C, brominated butyl rubber, polyisobutylene mixture, plasticizer, tackifying resin and antioxidant were added to the kneader in sequence according to Table 7, and mixed for 30 minutes under -0.1MPa vacuum protection; then inorganic filler, reinforcing agent, water absorbent and crosslinking agent were added in sequence, and mixed thoroughly for 120 minutes under -0.1MPa vacuum protection to obtain self-healing butyl hot melt adhesive for insulating glass.

[0096] Table 7

[0097]

[0098]

[0099] Comparative Example 3

[0100] The difference between this comparative example and Example 1 is that no hydrogen-containing silane and platinum catalyst were added during the preparation of the modified butyl rubber.

[0101] 200g of brominated butyl rubber (raw rubber Mooney viscosity ML) 1+8 =33, bromine content 1.9wt%, bromine molar amount 0.048mol, commercially available) was dissolved in 1.3L of tetrahydrofuran, and then 9.0g of HO(CH2)7CH=CHCOOH (0.048mol, commercially available) and 6.7g of potassium carbonate (0.048mol, commercially available) were added to the solution. After stirring at room temperature for 12 hours, the solid was filtered and then the tetrahydrofuran was removed by rotary evaporation to obtain the modified butyl rubber.

[0102] At 150°C, the modified butyl rubber, polyisobutylene mixture, plasticizer, tackifying resin and antioxidant were added to the kneader in sequence according to Table 8, and mixed for 30 minutes under -0.1MPa vacuum protection; then the inorganic filler, reinforcing agent, water absorbent and crosslinking agent were added in sequence, and mixed thoroughly for 120 minutes under -0.1MPa vacuum protection to obtain a self-healing butyl hot melt adhesive for insulating glass.

[0103] Table 8

[0104]

[0105] Comparative Example 4

[0106] The difference between this comparative example and Example 1 is that no hydroxyl acrylate compounds were added during the preparation of the modified butyl rubber.

[0107] 200g of brominated butyl rubber (raw rubber Mooney viscosity ML) 1+8 =33, bromine content 1.9wt%, bromine molar amount 0.048mol, commercially available) was dissolved in 300mL toluene, and 5.9g HSi(OCH3)3 (0.048mol, commercially available) and 2.9mg chloroplatinic acid (containing 0.05% of the mass of hydrosilane, commercially available) were added. The mixture was heated to 70℃ under nitrogen protection and reacted for 6 hours. Then the temperature was raised to 100℃ and the reaction was continued for 7 hours. Finally, the temperature inside the reactor was raised to 110℃ and the solvent was removed by vacuum to obtain the modified butyl rubber.

[0108] At 150°C, the modified butyl rubber, polyisobutylene mixture, plasticizer, tackifying resin and antioxidant were added to the kneader in sequence according to Table 9, and mixed for 30 minutes under -0.1MPa vacuum protection; then the inorganic filler, reinforcing agent, water absorbent and crosslinking agent were added in sequence, and mixed thoroughly for 120 minutes under -0.1MPa vacuum protection to obtain a self-healing butyl hot melt adhesive for insulating glass.

[0109] Table 9

[0110]

[0111] Comparative Example 5

[0112] The difference between this comparative example and Example 1 is that the hydroxyl acrylate compound is replaced with H2NCOCH=CHCOOH in the preparation process of the modified butyl rubber.

[0113] 200g of brominated butyl rubber (raw rubber Mooney viscosity ML) 1+8 =33, bromine content 1.9wt%, bromine molar amount 0.048mol, commercially available) was dissolved in 1.3L tetrahydrofuran, then 5.0g H2NCOCH=CHCOOH (0.048mol, commercially available) and 6.7g potassium carbonate (0.048mol, commercially available) were added to the solution. After stirring at room temperature for 12 hours, the solid was filtered and the tetrahydrofuran was removed by rotary evaporation. The obtained product was dissolved in 300mL toluene, and 5.9g HSi(OCH3)3 (0.048mol, commercially available) and 2.9mg chloroplatinic acid (containing 0.05% of the mass of hydrogen silane, commercially available) were added. The mixture was heated to 70℃ under nitrogen protection and reacted for 6 hours. Then the temperature was raised to 100℃ and the reaction was continued for 7 hours. Finally, the temperature in the reactor was raised to 110℃ and the solvent was removed by vacuum to obtain the modified butyl rubber.

[0114] At 150°C, the modified butyl rubber, polyisobutylene mixture, plasticizer, tackifying resin and antioxidant were added to the kneader in sequence according to Table 10, and mixed for 30 minutes under -0.1MPa vacuum protection; then the inorganic filler, reinforcing agent, water absorbent and crosslinking agent were added in sequence, and mixed thoroughly for 120 minutes under -0.1MPa vacuum protection to obtain a self-healing butyl hot melt adhesive for insulating glass.

[0115] Table 10

[0116]

[0117]

[0118] The butyl hot melt adhesives prepared in Examples 1-5 and Comparative Examples 1-5 were subjected to the performance tests shown in Table 11. The performance test methods for the samples in Table 11 are as follows:

[0119] 1. Shear strength: Tested according to the method specified in 4.5 of JC / T 914-2014 "Butyl Hot Melt Sealant for Insulating Glass".

[0120] 2. Self-healing test: The fracture surface of the sample that has completed the shear strength test is reassembled, and after being placed at room temperature for 7 days, the shear strength test is carried out again.

[0121] 3. Test method for adhesion to silicone sealant: The substrate is a 75*12*6mm glass sheet. The glass sheet is wiped with alcohol and dried. Butyl hot melt adhesive is pressed into a strip with a thickness greater than 12mm and cut to an appropriate size. After the strip is joined with the glass sheet, it is pressed to 12±1mm. Then, a 3mm thick layer of two-component silicone sealant for insulating glass (commercially available, SS-528 two-component silicone structural adhesive for insulating glass, Baiyun Technology) is applied to the surface of the hot melt adhesive and immediately bonded to another glass sheet to form a sample. The sample is cured for 28 days at a temperature of (23±2)℃ and a relative humidity of (50±5%) and tested according to T / ZBH 024-2023 to measure the adhesion strength between butyl hot melt adhesive and two-component silicone sealant.

[0122] As shown in Table 11, the butyl hot melt adhesives prepared in Examples 1-5 simultaneously introduced hydroxyl olefin compounds and siloxanes. After the siloxanes were applied to the butyl hot melt adhesive system, they could form a first layer of chemical cross-linking network and improve the adhesion of the butyl hot melt adhesive to glass and silicone sealant. Therefore, it had good adhesion to glass and two-component silicone sealant and high shear strength. At the same time, the molecular chains could form a second layer of reversible physical cross-linking network through the electrostatic interaction between the carboxyl groups at the ends and the amine groups of the cross-linking agent. This not only enhanced the mechanical properties of the material but also endowed the butyl hot melt adhesive with good self-healing properties. Therefore, after the fracture surface was spliced, the samples all recovered most of the shear strength, realizing the self-healing of the butyl hot melt adhesive at room temperature.

[0123] In Comparative Example 1, no crosslinking agent was added to the butyl hot melt adhesive, resulting in a lack of self-healing properties, as evidenced by a significant reduction in shear strength at the fractured joints. In Comparative Example 2, no modification was made to the butyl rubber, leading to a lack of self-healing properties and poor shear strength and adhesion to silicone sealant. In Comparative Example 3, only hydroxyl acrylic acid compounds were introduced, without the addition of siloxanes. While possessing some self-healing ability, it failed to form a good chemical bond with the substrate / silicone sealant and lacked a chemical crosslinking network, resulting in strength far lower than Examples 1-5. In Comparative Example 4, the modified butyl rubber lacked hydroxyl acrylic acid compounds, thus lacking self-healing properties, and the siloxanes could not be grafted onto the polymer chains, resulting in shear strength and adhesion strength far lower than Examples 1-5.

[0124] Comparative Example 5 uses amide acrylate compounds to modify butyl rubber. Since it does not react with halogenated butyl rubber, functional groups such as carboxyl and siloxane groups are not grafted onto the butyl rubber polymer chain. The material does not have self-healing properties and its strength is lower than that of Examples 1-5.

[0125] Table 11 Summary of the performance of butyl hot melt adhesives prepared in the examples and comparative examples

[0126]

[0127]

[0128] 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. A self-healing butyl hot melt adhesive for insulating glass, characterized in that, It is prepared from raw materials comprising the following components, in parts by weight: 1-8 parts of modified butyl rubber, 25-45 parts of polyisobutylene 1-5 parts of crosslinking agent 3-15 parts of tackifying resin, Plasticizer 3-15 parts, 1-6 parts absorbent 5-30 parts of inorganic filler 5-30 parts of reinforcing agent Antioxidant 0.5-5 parts; The modified butyl rubber is obtained by reacting halogenated butyl rubber with hydroxyl olefin compounds and hydrogen-containing silanes in sequence. The structural formula of the hydroxyolefin compound is HO(CH2). m CH=CHCOOH, where m is selected from: 2, 3, 4, 5, 6, 7, 8; The structural formula of the hydrogen-containing silane is HSi(R1)(OR2)2, wherein R1 is selected from: C1~C6 alkoxy, C1~C6 alkyl, and R2 is selected from: C1~C6 alkyl. The preparation method of the modified butyl rubber includes the following steps: (1) The halobutyl rubber and hydroxyolefin compounds are reacted in an organic solvent under the action of an inorganic base to obtain an intermediate product; (2) The intermediate product and the hydrogen-containing silane are reacted in an organic solvent under the action of a platinum catalyst to obtain the modified butyl rubber; The crosslinking agent is an amine compound with difunctionality or higher.

2. The self-healing butyl hot melt adhesive for insulating glass according to claim 1, characterized in that, It is prepared from raw materials comprising the following components, in parts by weight: The modified butyl rubber is 1-4 parts. 30-40 parts of polyisobutylene 1-3 parts of crosslinking agent 5-10 parts of tackifying resin, 5-10 parts plasticizer 1-4 parts absorbent 8-15 parts of inorganic filler 8-15 parts of reinforcing agent Antioxidant 1-3 parts.

3. The self-healing butyl hot melt adhesive for insulating glass according to claim 2, characterized in that, The self-healing butyl hot melt adhesive for insulating glass is prepared from raw materials comprising the following components, by weight: 2-3 parts of the modified butyl rubber 32-35 parts of polyisobutylene 2-3 parts of crosslinking agent 7-9 parts of tackifying resin, Plasticizer 6-8 parts, 2-3 parts absorbent 8-12 parts of inorganic filler 8-12 parts of reinforcing agent, Antioxidant 1-3 parts.

4. The self-healing butyl hot melt adhesive for insulating glass according to any one of claims 1-3, characterized in that, The halogenated butyl rubber is brominated butyl rubber and / or chlorinated butyl rubber; and / or... The raw rubber Mooney viscosity (ML) of the halogenated butyl rubber 1+8 27~50; and / or, The halogenated butyl rubber contains 1-2.2% halogen groups by mass.

5. The self-healing butyl hot melt adhesive for insulating glass according to claim 4, characterized in that, The raw rubber Mooney viscosity (ML) of the halogenated butyl rubber 1+8 It is 30~40.

6. The self-healing butyl hot melt adhesive for insulating glass according to any one of claims 1-3, characterized in that, R1 is selected from: -OCH3, -OCH2CH3, -CH3, -CH2CH3, and R2 is -CH3 or -CH2CH3.

7. The self-healing butyl hot melt adhesive for insulating glass according to any one of claims 1-3, characterized in that, The molar ratio of halogen groups, hydroxyl olefin compounds, and hydrogen-containing silanes in the halogenated butyl rubber is 1:0.8 to 3:0.8 to 3.

8. The self-healing butyl hot melt adhesive for insulating glass according to claim 7, characterized in that, The molar ratio of halogen groups, hydroxyl olefin compounds, and hydrogen-containing silanes in the halogenated butyl rubber is 1:0.9-1.1:0.9-1.

1.

9. The self-healing butyl hot melt adhesive for insulating glass according to any one of claims 1-3, characterized in that, The organic solvent in step (1) is tetrahydrofuran; and / or, The inorganic base in step (1) is potassium carbonate; and / or, The reaction temperature in step (1) is 15℃~35℃, and the reaction time is 10 hours~20 hours; and / or, The platinum catalyst in step (2) is chloroplatinic acid or a castor catalyst; and / or, The mass ratio of the hydrogen-containing silane to the platinum catalyst is 1:0.02% to 0.08%; and / or, The organic solvent in step (2) is toluene; and / or, The reaction in step (2) includes: reacting at a temperature of 60℃~90℃ for 2 hours to 8 hours, and then raising the temperature to 70℃~100℃ to continue the reaction for 3 hours to 9 hours.

10. The self-healing butyl hot melt adhesive for insulating glass according to claim 9, characterized in that, The molar ratio of the halogen groups to potassium carbonate in the halogenated butyl rubber is 1:1~2.

11. The self-healing butyl hot melt adhesive for insulating glass according to any one of claims 1-3, characterized in that, The crosslinking agent is selected from at least one of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, N,N'-dimethyl-1,6-diaminohexane, and N,N'-dimethyl-1,8-octanediamine; and / or The plasticizer is one or more of polybutene, phthalate, di-n-octyl adipate, and diisooctyl adipate; 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, and rosin resin; and / or, The water-absorbing agent 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 inorganic filler is selected from one or more combinations of mica powder, silica fume, kaolin, calcium carbonate, talc, kaolin, clay, and diatomaceous earth; and / or, The reinforcing agent is selected from one or a combination of two of carbon black and fumed silica; and / or, The antioxidant is selected from one or more combinations of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl tetrakis[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.

12. The self-healing butyl hot melt adhesive for insulating glass according to any one of claims 1-3, characterized in that, The polyisobutylene is composed of low molecular weight polyisobutylene and high molecular weight polyisobutylene, wherein the viscosity-average molecular weight of the low molecular weight polyisobutylene is 30,000 to 100,000, and the viscosity-average molecular weight of the high molecular weight polyisobutylene is 150,000 to 2,000,000.

13. The self-healing butyl hot melt adhesive for insulating glass according to claim 12, characterized in that, The low molecular weight polyisobutylene has a viscosity-average molecular weight of 50,000 to 80,000; the high molecular weight polyisobutylene has a viscosity-average molecular weight of 150,000 to 250,000.

14. The self-healing butyl hot melt adhesive for insulating glass according to claim 13, characterized in that, The low molecular weight polyisobutylene has a viscosity-average molecular weight of 60,000 to 70,000; the high molecular weight polyisobutylene has a viscosity-average molecular weight of 150,000 to 200,000.

15. The self-healing butyl hot melt adhesive for insulating glass according to claim 12, characterized in that, The polyisobutylene is composed of low molecular weight polyisobutylene and high molecular weight polyisobutylene in a mass ratio of 1-3:

1.

16. A method for preparing a self-healing butyl hot melt adhesive for insulating glass according to any one of claims 1-15, characterized in that, Includes the following steps: At 110℃~160℃, the modified butyl rubber, polyisobutylene, plasticizer, tackifying resin and antioxidant are added sequentially to a kneader and mixed under vacuum for 20 minutes to 130 minutes; then the inorganic filler, reinforcing agent, water absorbent and crosslinking agent are added sequentially and mixed under vacuum for 60 minutes to 180 minutes to obtain the self-healing butyl hot melt adhesive for insulating glass.

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