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

Abstract

The invention relates to a self-repairing butyl hot melt adhesive for hollow glass and a preparation method of the self-repairing butyl hot melt adhesive. The butyl hot melt adhesive is prepared from the following raw materials: modified butyl rubber, polyisobutene, a cross-linking agent, tackifying resin, a plasticizer, a water absorbent, an inorganic filler, a reinforcing agent and an antioxidant, the modified butyl rubber is obtained by sequentially reacting halogenated butyl rubber with a hydroxyl olefine acid compound and hydrogen-containing silane; the structural formula of the hydroxyl olefine acid compound is HO (CH2) mCH = CHCOOH; the structural formula of the hydrogen-containing silane is HSi (R1) (OR2) 2; the cross-linking agent is an amine compound with two or more degrees of functionality. The butyl hot melt adhesive has excellent bonding performance with glass and silicone adhesive, and also has good self-repairing performance.

Description

Technical Field

[0001] The invention belongs to the technical field of sealants, and in particular relates to a self-repairing butyl hot melt adhesive for insulating glass and a preparation method thereof. Background Art

[0002] The regular molecular structure of butyl rubber gives it excellent air tightness and very low water vapor permeability. It is widely used in the fields of tire inner tube airtight layer, first seal of hollow glass, building waterproof membrane, special waterproof tape and photovoltaic modules. Among them, butyl hot melt adhesive is a single-component, solvent-free, non-fogging, non-vulcanized thermoplastic material based on butyl rubber and polyisobutylene. It can be used as the inner sealant (first sealant) of hollow glass during use, for example, in combination with polysulfide adhesive or silicone adhesive to achieve long-term structural bonding effect. However, traditional butyl hot melt adhesive has poor adhesion to glass or silicone adhesive and cannot play a good fixing and bonding role.

[0003] In addition, during the use of sealant, improper construction operation or mistakes may easily cause sealant damage, defects or bubbles, resulting in a decrease in the mechanical properties of butyl hot melt sealant. In severe cases, it may even cause the sealing performance to fail, accelerate the leakage of inert gas, and greatly reduce the service life of insulating glass. As the first sealing system, if the damage or bubbles inside the colloid are not discovered in time before the second coat of silicone sealant is applied, the first coat of sealant will be difficult to repair, which will greatly reduce the qualified rate of insulating glass products and increase the cost of insulating glass products. Summary of the invention

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

[0005] The technical solutions for achieving the above-mentioned purpose include the following.

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

[0007]

[0008] The modified butyl rubber is obtained by sequentially reacting halogenated butyl rubber with a hydroxy olefinic acid compound and a hydrogen-containing silane;

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

[0010] The structural formula of the hydrosilane 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 cross-linking agent is an amine compound with difunctionality or more.

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

[0013]

[0014] In some of the embodiments, the self-repairing butyl hot melt adhesive for insulating glass is prepared from raw materials comprising the following components, in parts 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 rubber Mooney viscosity ML of the halogenated butyl rubber is 1+8 It is 27 to 50, preferably 30 to 40.

[0018] In some of the embodiments, the mass content of halogen groups in the halogenated butyl rubber is 1-2.2%.

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

[0020] In some of the embodiments, the molar ratio of the halogen group, the hydroxy olefinic acid compound and the hydrogen-containing silane 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 comprises the following steps:

[0022] (1) reacting the halogenated butyl rubber and the hydroxy olefinic acid compound in an organic solvent under the action of an inorganic base to obtain an intermediate product;

[0023] (2) reacting the intermediate product with the hydrosilane in an organic solvent under the action of a platinum catalyst to obtain the modified butyl rubber.

[0024] In some 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 of the embodiments, the molar ratio of the halogen group of the halogenated butyl rubber to potassium carbonate is 1:1-2.

[0027] In some embodiments, the reaction temperature of 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 Castel catalyst.

[0029] In some of the embodiments, the mass ratio of the hydrosilane 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) comprises: reacting at a temperature of 60°C to 90°C for 2 hours to 8 hours, then raising the temperature to 70°C to 100°C and continuing the reaction for 3 hours to 9 hours.

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

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

[0034] The halogenated butyl rubber is dissolved in tetrahydrofuran, and the hydroxy olefinic acid compound and the inorganic base are added to the solution, stirred at 15°C to 35°C for 10 to 20 hours, the solid is removed and then the tetrahydrofuran is removed, the intermediate product is dissolved in toluene, the hydrosilane and the platinum catalyst are added, the temperature is raised to 60°C to 90°C, the reaction is carried out for 2 to 8 hours, and then the temperature is raised to 70°C to 100°C and the reaction is continued for 3 to 9 hours, and 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 of the embodiments, the polyisobutylene is composed of low molecular weight polyisobutylene and high molecular weight polyisobutylene; 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 100,000 to 2,000,000.

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

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

[0039] In some of the 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 a combination of one or more of polybutene, phthalate, di-n-octyl adipate and di-2-octyl 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 water absorbent is selected from one or more combinations of calcium oxide, molecular sieves, 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 carbon black and fumed silica.

[0045] In some embodiments, the antioxidant is selected from 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 a combination of one or more of 2,2,4-trimethyl-1,2-dihydroquinoline polymers.

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

[0047] At 110° C. to 160° C., the modified butyl rubber, polyisobutylene, tackifying resin and antioxidant are added to a kneader in sequence, and mixed under vacuum protection for 20 minutes to 130 minutes; then the inorganic filler, reinforcing agent, water absorbent and cross-linking agent are added in sequence, and mixed under vacuum protection for 60 minutes to 180 minutes to obtain the self-repairing butyl hot melt adhesive for insulating glass.

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

[0049] At 140° C. to 170° C., the modified butyl rubber, polyisobutylene, plasticizer, tackifying resin and antioxidant are added to a kneader in sequence, and mixed for 20 to 60 minutes under vacuum protection; then the inorganic filler, reinforcing agent, water absorbent and cross-linking agent are added in sequence, and mixed for 100 to 150 minutes under vacuum protection to obtain the self-repairing butyl hot-melt adhesive for insulating glass.

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

[0051] The present invention modifies halogenated butyl rubber with hydroxyl olefinic acid compounds and hydrogen-containing silane to obtain modified butyl rubber with siloxane groups and carboxyl groups, and prepares the modified butyl rubber with components such as polyisobutylene and multifunctional amine crosslinking agents through appropriate formulas to form a reactive butyl hot melt adhesive with self-repairing properties. In the butyl hot melt adhesive system, the siloxane group is used for the dealcoholization reaction of the butyl hot melt adhesive system after the adhesive is applied to form the first layer of chemical crosslinking network, and on the other hand, it can improve the adhesion of the butyl hot melt adhesive to glass and silicone adhesive, and the carboxyl group and the multifunctional amine crosslinking agent form a second layer of physical crosslinking network through electrostatic interaction of acid-base complexation, which enhances the mechanical properties of the material and also gives the butyl hot melt adhesive good self-repairing properties. Under the coordinated cooperation of various components, the butyl hot melt adhesive of the present invention has good adhesion to the glass interface and silicone adhesive, high strength, good mechanical properties, and excellent self-repairing properties, and can be used as a good sealant for insulating glass. In addition, the electrostatic interaction in the system will undergo reversible dissociation at higher temperatures and will not affect the processing and construction performance of butyl hot melt adhesive. DETAILED DESCRIPTION

[0052] In order to facilitate the understanding of the present invention, the present invention will be described more fully below. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0053] The experimental methods in the following examples without specifying specific conditions are usually carried out under conventional conditions or under conditions recommended by the manufacturers. The raw materials and various chemical reagents used in the examples are all commercially available products.

[0054] Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. The terms used in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used in the present invention includes any and all combinations of one or more of the related listed items.

[0055] In addition, as used in the present invention, the term "or" is an inclusive "or" symbol and is equivalent to the term "and / or", unless the context clearly dictates otherwise. The term "based on" is not exclusive and allows for being based on other factors not described, unless the context clearly dictates otherwise. In addition, throughout the specification, the meanings of "a", "an", and "the" include plural referents. The meaning of "in..." includes "in..." and "on...".

[0056] The present invention is 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°C-30°C.

[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, and 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, and stirred at room temperature for 12 hours. The tetrahydrofuran was removed by rotary evaporation after filtering the solid, and the resulting product was dissolved in 300mL toluene. 5.9g HSi(OCH3)3 (0.048mol, commercially available) and 3mg chloroplatinic acid (the mass is 0.05% of the mass of hydrogen-containing silane, commercially available) were added, and the temperature was raised to 70°C under nitrogen protection, and the reaction was continued for 6 hours, and then the temperature was raised to 100°C for continued reaction for 7 hours. Finally, the temperature in the reactor was raised to 110°C 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 blended for 30 minutes under -0.1 MPa vacuum protection; then inorganic filler, reinforcing agent, water absorbent and cross-linking agent were added in sequence, and fully mixed for 120 minutes under -0.1 MPa vacuum protection to obtain a self-repairing 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 tetrahydrofuran, and then 13.2g HO(CH2)7CH=CHCOOH (0.071mol, commercially available) and 9.9g potassium carbonate (0.071mol, commercially available) were added to the solution, and stirred at room temperature for 18 hours. The tetrahydrofuran was removed by rotary evaporation after filtering the solid, and the resulting product was dissolved in 300mL toluene. 11.7g HSi(OCH2CH3)3 (0.071mol, commercially available) and 5.8mg chloroplatinic acid (the mass is 0.05% of the mass of hydrogen-containing silane, commercially available) were added, and the temperature was raised to 70°C under nitrogen protection, and the reaction was continued for 3 hours, and then the temperature was raised to 100°C for continued reaction for 7 hours. Finally, the temperature in the reactor was raised to 110°C and the solvent was removed by vacuum to obtain the modified butyl rubber.

[0065] At 170°C, modified butyl rubber, polyisobutylene mixture, plasticizer, tackifying resin and antioxidant were added to the kneader in sequence according to Table 2, and blended for 30 minutes under -0.1 MPa vacuum protection; then inorganic filler, reinforcing agent, water absorbent and cross-linking agent were added in sequence, and the mixture was fully mixed for 120 minutes under -0.1 MPa vacuum protection to obtain a self-repairing 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, and 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, and after stirring at room temperature for 18 hours, the solid was filtered and then the tetrahydrofuran was removed by rotary evaporation. The resulting product was dissolved in 300mL toluene, and 7.9g HSi(OCH2CH3)3 (0.048mol, commercially available) and 4.0mg Custer catalyst (the mass is 0.05% of the mass of hydrogen-containing silane, commercially available) were added. The temperature was raised to 70°C under nitrogen protection, and the reaction was continued for 3 hours, and then the temperature was raised to 90°C for continuous reaction for 5 hours. Finally, the temperature in the reactor was raised to 110°C 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 blended for 45 minutes under -0.1 MPa vacuum protection; then the inorganic filler, reinforcing agent, water absorbent and cross-linking agent were added in sequence, and the mixture was fully mixed for 120 minutes under -0.1 MPa vacuum protection to obtain a self-repairing 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, and 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, and after stirring at room temperature for 18 hours, the solid was filtered and then the tetrahydrofuran was removed by rotary evaporation. The resulting product was dissolved in 300mL toluene, and 5.1g HSi(CH3)(OCH3)2 (0.048mol, commercially available) and 2.6mg Custer catalyst (the mass is 0.05% of the mass of hydrogen-containing silane, commercially available) were added. The temperature was raised to 70°C under nitrogen protection, and the reaction was continued for 4 hours, and then the temperature was raised to 90°C for continued reaction for 5 hours. Finally, the temperature in the reactor was raised to 110°C 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 blended for 45 minutes under -0.1 MPa vacuum protection; then the inorganic filler, reinforcing agent, water absorbent and cross-linking agent were added in sequence, and the mixture was fully mixed for 120 minutes under -0.1 MPa vacuum protection to obtain a self-repairing 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, and 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, and after stirring at room temperature for 18 hours, the solid was filtered and then the tetrahydrofuran was removed by rotary evaporation. The resulting product was dissolved in 300mL toluene, and 6.4g HSi(CH3)(OCH2CH3)2 (0.048mol, commercially available) and 3.2mg Custer catalyst (the mass is 0.05% of the mass of hydrogen-containing silane, commercially available) were added. The temperature was raised to 70°C under nitrogen protection, and the reaction was continued for 5 hours, and then the temperature was raised to 90°C for further reaction for 5 hours. Finally, the temperature in the reactor was raised to 110°C 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 blended for 45 minutes under -0.1 MPa vacuum protection; then the inorganic filler, reinforcing agent, water absorbent and cross-linking agent were added in sequence, and the mixture was fully mixed for 120 minutes under -0.1 MPa vacuum protection to obtain a self-repairing 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 cross-linking agent is 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) is dissolved in 1.3L tetrahydrofuran, and then 9.0g HO(CH2)7CH=CHCOOH (0.048mol, commercially available) and 6.7g potassium carbonate (0.048mol, commercially available) are added to the solution, and after stirring at room temperature for 12 hours, the solid is filtered and then the tetrahydrofuran is removed by rotary evaporation. The resulting product is dissolved in 300mL toluene, and 5.9g HSi(OCH3)3 (0.048mol, commercially available) and 3mg chloroplatinic acid (0.05% of the mass of hydrogen-containing silane, commercially available) are added. The temperature is raised to 70°C under nitrogen protection, and the reaction is continued for 6 hours, and then the temperature is raised to 100°C for continued reaction for 7 hours. Finally, the temperature in the reactor is raised to 110°C and the solvent is 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 blended for 30 minutes under -0.1 MPa vacuum protection; then the inorganic filler, reinforcing agent and water absorbent were added in sequence, and the mixture was fully mixed for 120 minutes under -0.1 MPa vacuum protection to obtain a self-repairing 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 there is no bromobutyl rubber (raw rubber Mooney viscosity ML 1+8 =33, bromine content 1.9wt%, commercially available) was modified.

[0095] At 150°C, add brominated butyl rubber, polyisobutylene mixture, plasticizer, tackifying resin and antioxidant to the kneader in sequence according to Table 7, and blend for 30 minutes under -0.1 MPa vacuum protection; then add inorganic filler, reinforcing agent, water absorbent and cross-linking agent in sequence, and mix thoroughly for 120 minutes under -0.1 MPa vacuum protection to obtain a self-repairing 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 are 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 tetrahydrofuran, and 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 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 blended for 30 minutes under -0.1 MPa vacuum protection; then the inorganic filler, reinforcing agent, water absorbent and cross-linking agent were added in sequence, and the mixture was fully mixed for 120 minutes under -0.1 MPa vacuum protection to obtain a self-repairing 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 hydroxy olefinic acid compound is 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, 5.9g HSi(OCH3)3 (0.048mol, commercially available) and 2.9mg chloroplatinic acid (0.05% of the mass of hydrogen silane, commercially available) were added, the temperature was raised to 70°C under nitrogen protection, the reaction was continued for 6 hours, and then the temperature was raised to 100°C to continue the reaction for 7 hours, and finally the temperature in the reactor was raised to 110°C 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 blended for 30 minutes under -0.1 MPa vacuum protection; then the inorganic filler, reinforcing agent, water absorbent and cross-linking agent were added in sequence, and the mixture was fully mixed for 120 minutes under -0.1 MPa vacuum protection to obtain a self-repairing 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 hydroxy olefinic acid compound is replaced by H2NCOCH=CHCOOH during the preparation 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, and then 5.0g H2NCOCH=CHCOOH (0.048mol, commercially available) and 6.7g potassium carbonate (0.048mol, commercially available) were added to the solution, and stirred at room temperature for 12 hours. The tetrahydrofuran was removed by rotary evaporation after filtering the solid, and the resulting product was dissolved in 300mL toluene. 5.9g HSi(OCH3)3 (0.048mol, commercially available) and 2.9mg chloroplatinic acid (0.05% of the mass of hydrogen-containing silane, commercially available) were added, and the temperature was raised to 70°C under nitrogen protection, and the reaction was continued for 6 hours, and then the temperature was raised to 100°C and the reaction was continued for 7 hours. Finally, the temperature in the reactor was raised to 110°C 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 blended for 30 minutes under -0.1 MPa vacuum protection; then the inorganic filler, reinforcing agent, water absorbent and cross-linking agent were added in sequence, and the mixture was fully mixed for 120 minutes under -0.1 MPa vacuum protection to obtain a self-repairing butyl hot melt adhesive for insulating glass.

[0115] Table 10

[0116]

[0117]

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

[0119] 1. Shear strength: 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: Reassemble the fractured parts of the sample that has completed the shear strength test, place it at room temperature for 7 days, and then re-test the shear strength.

[0121] 3. Test method for adhesion with silicone adhesive: Use a 75*12*6mm glass sheet as the substrate, wipe the glass sheet with alcohol and dry it; press the butyl hot melt adhesive into a strip with a thickness greater than 12mm, and cut it into a suitable size to meet the glass sheet. Press the strip into 12±1mm, then apply 3mm thick two-component silicone adhesive for insulating glass (commercially available, SS-528 two-component silicone structural adhesive for insulating glass, Baiyun Technology) on the surface of the hot melt adhesive, and immediately glue it with another piece of glass to make a test sample, maintain it at a temperature of (23±2)℃ and a relative humidity of (50±5%) for 28 days, and test it according to T / ZBH 024-2023 to measure the bonding strength between the butyl hot melt adhesive and the two-component silicone adhesive.

[0122] As shown in Table 11, the butyl hot melt adhesive prepared in Examples 1 to 5 simultaneously introduces hydroxy olefinic acid compounds and siloxane. Siloxane can form a first layer of chemical cross-linking network after the butyl hot melt adhesive system is applied, and can improve the adhesion of the butyl hot melt adhesive to glass and silicone adhesive. Therefore, it has good adhesion to glass and two-component silicone adhesive and high shear strength. At the same time, the molecular chain can form a second layer of reversible physical cross-linking network through the electrostatic interaction between the terminal carboxyl group and the amine group of the cross-linking agent, which not only enhances the mechanical properties of the material, but also gives the butyl hot melt adhesive good self-healing properties. Therefore, after fracture splicing, the samples all restored most of the shear strength, realizing the self-healing of the butyl hot melt adhesive at room temperature.

[0123] In the butyl hot melt adhesive of Comparative Example 1, no crosslinking agent is added, and the butyl hot melt adhesive does not have self-healing properties, which is manifested in that the shear strength of the fracture spliced ​​sample is greatly reduced; in the butyl hot melt adhesive of Comparative Example 2, no butyl rubber is modified, and the butyl hot melt adhesive does not have self-healing properties, and the shear strength and adhesion to silicone adhesive are poor. In the butyl hot melt adhesive of Comparative Example 3, only hydroxy olefinic acid compounds are introduced without siloxane. Although it also has a certain self-healing ability, it does not form a good chemical bond with the substrate / silicone adhesive, and lacks a chemical crosslinking network, and the strength is much lower than that of Examples 1 to 5; in the modified butyl rubber of Comparative Example 4, no hydroxy olefinic acid compounds are introduced, and it does not have self-healing properties, and siloxane cannot be grafted onto the polymer chain, and the shear strength and adhesion strength are much lower than those of Examples 1 to 5.

[0124] Comparative Example 5 uses amide olefinic acid compounds to modify butyl rubber. Since it does not react with halogenated butyl rubber, functional groups such as carboxyl and siloxane groups cannot be 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 to 5.

[0125] Table 11 Summary of properties of butyl hot melt adhesives prepared in Examples and Comparative Examples

[0126]

[0127]

[0128] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A self-repairing butyl hot melt adhesive for insulating glass, characterized in that: The composition is prepared from the following raw materials in parts by weight: The modified butyl rubber is obtained by sequentially reacting halogenated butyl rubber with a hydroxy olefinic acid compound and a hydrogen-containing silane; The structural formula of the hydroxy olefinic acid compound is HO(CH2) m CH=CHCOOH, wherein m is selected from: 2, 3, 4, 5, 6, 7, 8; The structural formula of the hydrosilane 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 cross-linking agent is an amine compound with difunctionality or more.

2. The self-repairing butyl hot melt adhesive for insulating glass according to claim 1, characterized in that: The composition is prepared from the following raw materials in parts by weight: Preferably, the self-repairing butyl hot melt adhesive for insulating glass is prepared from raw materials comprising the following components in parts by weight:

3. The self-repairing butyl hot melt adhesive for insulating glass according to claim 1 or 2, characterized in that: The halogenated butyl rubber is brominated butyl rubber and / or chlorinated butyl rubber; and / or, The raw Mooney viscosity ML of the halogenated butyl rubber 1+8 is 27 to 50, preferably 30 to 40; and / or, The mass content of halogen groups in the halogenated butyl rubber is 1 to 2.2%.

4. The self-repairing butyl hot melt adhesive for insulating glass according to claim 1 or 2, characterized in that: R1 is selected from: -OCH3, -OCH2CH3, -CH3, -CH2CH3, and R2 is -CH3 or -CH2CH3.

5. The self-repairing butyl hot melt adhesive for insulating glass according to claim 1 or 2, characterized in that: The molar ratio of the halogen group, the hydroxy olefinic acid compound and the hydrogen-containing silane in the halogenated butyl rubber is 1:0.8-3:0.8-3, preferably 1:0.9-1.1:0.9-1.

1.

6. The self-repairing butyl hot melt adhesive for insulating glass according to claim 1 or 2, characterized in that: The preparation method of the modified butyl rubber comprises the following steps: (1) reacting the halogenated butyl rubber and the hydroxy olefinic acid compound in an organic solvent under the action of an inorganic base to obtain an intermediate product; (2) reacting the intermediate product with the hydrosilane in an organic solvent under the action of a platinum catalyst to obtain the modified butyl rubber.

7. The self-repairing butyl hot melt adhesive for insulating glass according to claim 6, 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°C to 35°C, and the reaction time is 10 hours to 20 hours; and / or, The platinum catalyst in step (2) is chloroplatinic acid or a Custer catalyst; and / or, The mass ratio of the hydrosilane 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) comprises: reacting at a temperature of 60° C. to 90° C. for 2 to 8 hours, then raising the temperature to 70° C. to 100° C. and continuing the reaction for 3 to 9 hours; Preferably, the molar ratio of the halogen group of the halogenated butyl rubber to potassium carbonate is 1:1-2.

8. The self-repairing butyl hot melt adhesive for insulating glass according to claim 1 or 2, characterized in that: The cross-linking 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 a combination of one or more of polybutene, phthalate, di-n-octyl adipate and di-2-octyl 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 sieves, 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 powder, kaolin, calcium carbonate, talc, kaolin, clay and diatomaceous earth; and / or, The reinforcing agent is selected from one or a combination of carbon black and fumed silica; and / or, The antioxidant is selected from the group consisting 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 a combination of one or more of a 2,2,4-trimethyl-1,2-dihydroquinoline polymer.

9. The self-repairing butyl hot melt adhesive for insulating glass according to claim 1 or 2, characterized in that: The polyisobutylene is composed of low molecular weight polyisobutylene and high molecular weight polyisobutylene, 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 100,000 to 2,000,000; Preferably, the viscosity average molecular weight of the low molecular weight polyisobutylene is 50,000 to 80,000; the viscosity average molecular weight of the high molecular weight polyisobutylene is 150,000 to 250,000; Preferably, the viscosity average molecular weight of the low molecular weight polyisobutylene is 60,000 to 70,000; the viscosity average molecular weight of the high molecular weight polyisobutylene is 150,000 to 200,000; Preferably, the polyisobutylene consists of low molecular weight polyisobutylene and high molecular weight polyisobutylene in a mass ratio of 1-3:

1.

10. A method for preparing the self-repairing butyl hot melt adhesive for insulating glass according to any one of claims 1 to 9, characterized in that: The following steps are involved: At 110° C. to 160° C., the modified butyl rubber, polyisobutylene, plasticizer, tackifying resin and antioxidant are added to a kneader in sequence, and blended under vacuum protection for 20 minutes to 130 minutes; then the inorganic filler, reinforcing agent, water absorbent and cross-linking agent are added in sequence, and mixed under vacuum protection for 60 minutes to 180 minutes to obtain the self-repairing butyl hot melt adhesive for insulating glass.

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