Butyl hot melt adhesive as well as preparation method and application thereof

Abstract

The invention relates to a butyl hot melt adhesive, which is prepared from the following raw materials in parts by weight: 10 to 30 parts of butyl rubber, 5 to 15 parts of polyisobutene, 25 to 50 parts of amorphous polyolefin, 10 to 30 parts of organic silicon modified polymer, 0.1 to 1 part of lubricant, 0.1 to 1 part of antioxidant, 1 to 30 parts of modified filler and 1 to 20 parts of carbon black, the organic silicon modified polymer comprises a polyurethane polymer terminated by a silane coupling agent. The butyl hot melt adhesive provided by the invention has the characteristics of difficulty in flowing after being heated, good high-temperature stability and excellent bonding performance, can be used for bonding and sealing a car lamp, and can ensure that the car lamp is stable in structure in a high-temperature environment, so that the car lamp can still work normally in hot weather or when the car lamp is close to high-temperature parts such as an engine, and the service life of the car lamp is prolonged.

Description

Technical Field

[0001] The invention belongs to the technical field of hot melt adhesives, and in particular relates to a butyl hot melt adhesive and a preparation method and application thereof. Background Art

[0002] As the core components to ensure vehicle driving safety, automotive lamps are an important part of the manufacturing process for bonding and sealing. The bonding of automotive lamps should be able to ensure that there will be no problems such as debonding, water and oil seepage, discoloration and fogging when the lamps are used in various adverse environments. The bonding and sealing technology is directly related to the reliability of the product under complex working conditions.

[0003] Ordinary hot melt adhesives and two-component silicone adhesive systems widely used in traditional car lamp manufacturing have exposed significant performance defects in actual applications. Ordinary hot melt adhesives are mainly composed of thermoplastic polyolefins. Although they have the advantages of fast curing speed and strong initial adhesion, they have obvious temperature sensitivity problems. They soften and flow at temperatures above 80°C. At the same time, their high-temperature stability is poor. When heated at high temperatures for a long time (200°C), they are prone to decomposition and the viscosity becomes low, resulting in flow during use and increased risk of failure during high-temperature service. More importantly, this type of adhesive has insufficient bonding performance to polycarbonate materials, especially polycarbonate that has undergone surface hardening and wear-resistant treatment is more prone to debonding, making it difficult to meet users' requirements for the bonding strength of car lamps. Although the two-component silicone adhesive system has good weather resistance, it is limited by curing conditions, has a high cost, and requires precise proportions during construction, making it difficult to adapt to the needs of automated production.

[0004] With the continuous development of automobile technology, especially the rise of new energy vehicles and intelligent driving technology, the working environment of headlights has become more demanding. For example, the temperature near the battery compartment of new energy vehicles may exceed 150°C, which requires adhesives to be able to work stably and long-term in such high temperature environments. At the same time, modern headlights are adopting more and more lightweight designs and integrated structures, which puts higher requirements on the bonding strength of adhesives.

[0005] Therefore, developing adhesive for car lights that is not easy to flow when heated, has good high-temperature stability, and has excellent bonding is the key to the application of car light bonding. Summary of the invention

[0006] In view of the deficiencies in the prior art, the present invention aims to provide a butyl hot melt adhesive and a preparation method and application thereof.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a butyl hot melt adhesive, wherein the raw materials for preparing the butyl hot melt adhesive include, by weight:

[0009]

[0010] The silicone-modified polymer includes a polyurethane polymer capped with a silane coupling agent.

[0011] The butyl hot-melt adhesive provided by the present invention, through the screening of the preparation raw materials, makes the obtained butyl hot-melt adhesive not easy to flow when heated, has good high-temperature stability, and excellent bonding performance. The butyl hot-melt adhesive provided by the present invention has a flowability of only 3.2 - 5.3 mm at 120°C for 24 h, is stable in form at high temperature, can ensure the structural stability of the car lamp in a high-temperature environment, and avoid problems such as deformation and function damage of the car lamp caused by the flow of the adhesive; when heated at 200°C for 72 h, the viscosity change rate is only -4.7% to -8.7% and the surface carbonization situation is normal, can maintain stable performance at high temperature, so that the car lamp can still work normally when in hot weather or near high-temperature parts such as the engine, and extend the service life of the car lamp; the adhesive force is as high as 117 - 138 N, can form a firm bond with the car lamp material, and ensure the sealing and optical performance of the car lamp.

[0012] The weight parts of the butyl rubber can be 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, etc.

[0013] The weight parts of the polyisobutene can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, etc.

[0014] The weight parts of the amorphous polyolefin can be 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, etc.

[0015] The weight parts of the silicone-modified polymer can be 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, etc.

[0016] The weight parts of the lubricant can be 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, etc.

[0017] The weight parts of the antioxidant can be 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, etc.

[0018] The weight parts of the modified filler can be 1 part, 3 parts, 5 parts, 7 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 23 parts, 25 parts, 27 parts, 30 parts, etc.

[0019] The weight parts of the carbon black can be 1 part, 3 parts, 5 parts, 7 parts, 9 parts, 11 parts, 13 parts, 15 parts, 17 parts, 19 parts, 20 parts, etc.

[0020] Other specific point values within the above numerical ranges can be selected and will not be elaborated one by one here.

[0021] Preferably, the Mooney viscosity ML(1+8)125℃ of the butyl rubber is 30 - 60, such as 30, 33, 36, 39, 42, 45, 48, 51, 54, 56, 58, 60, etc. Other specific point values within this numerical range can be selected and will not be elaborated one by one here.

[0022] In the present invention, the butyl rubber can be obtained by purchase. Exemplarily, it can be purchased from Zhejiang XinHui CENWAY CB-01 and CENWAY IIR-532.

[0023] Preferably, the polyisobutylene includes medium molecular weight polyisobutylene and high molecular weight polyisobutylene.

[0024] Preferably, the molecular weight of the medium molecular weight polyisobutylene is 30000 - 100000, such as 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, etc. Other specific point values within this numerical range can be selected and will not be elaborated one by one here.

[0025] In the present invention, the medium molecular weight polyisobutylene can be obtained by purchase. Exemplarily, it can be purchased from Hongrui Medium Molecular Weight Polyisobutylene HRD-350, HRD-450, HRD-500, HRD-550, HRD-600, HRD-650, HRD-750, HRD-850, HRD-950.

[0026] Preferably, the molecular weight of the high molecular weight polyisobutylene is 100000 - 2000000, such as 100000, 300000, 500000, 700000, 900000, 1000000, 1200000, 1400000, 1600000, 1800000, 2000000, etc. Other specific point values within this numerical range can be selected and will not be elaborated one by one here.

[0027] In the present invention, the high molecular weight polyisobutylene can be obtained by purchase. Exemplarily, it can be purchased from BASF Polyisobutylene Oppanol B50, B80, B100.

[0028] Preferably, the silane coupling agent includes any one or a combination of at least two of bis-(γ-trimethoxysilylpropyl)amine, γ-mercaptopropyltrimethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane.

[0029] Preferably, the polyurethane polymer includes isocyanate-terminated hydroxyl polybutadiene.

[0030] Preferably, the molar ratio of the reaction of the hydroxyl polybutadiene with the isocyanate is 1:(1.2 - 1.5), such as 1:1.2, 1:1.25, 1:1.3, 1:1.35, 1:1.4, 1:1.45, 1:1.5, etc. Other specific point values within this numerical range can be selected and will not be elaborated one by one here.

[0031] Preferably, the ratio of the sum of the molar numbers of the silane coupling agent and the hydroxyl groups in the hydroxyl polybutadiene to the molar number of the isocyanate is (1 - 1.5):1, such as 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, etc. Other specific point values within this numerical range can be selected and will not be elaborated one by one here.

[0032] Preferably, the organosilicon-modified polymer is prepared by the following method:

[0033] Dehydrate the hydroxyl polybutadiene for 1 - 3 h (such as 1 h, 1.5 h, 2 h, 2.5 h, 3 h, etc.), then add diphenylmethane diisocyanate and react for 1 - 2 h (such as 1 h, 1.2 h, 1.4 h, 1.6 h, 1.8 h, 2 h, etc.) to obtain a polyurethane polymer, and then add a silane coupling agent and react for 0.5 - 2 h (such as 0.5 h, 0.7 h, 0.9 h, 1.1 h, 1.3 h, 1.5 h, 1.7 h, 1.9 h, 2 h, etc.) to obtain an organosilicon-modified polymer. Other specific point values within the above numerical range can be selected and will not be elaborated one by one here.

[0034] Preferably, the amorphous polyolefin includes an α-olefin polymer.

[0035] Preferably, the α-olefin includes any combination of at least two of ethylene, propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-octene, or 4-methyl-1-pentene.

[0036] Preferably, the softening point of the polyolefin is 80 - 120 °C, and the melt viscosity at 190 °C is 2000 - 30000 mPa·s.

[0037] In the present invention, the amorphous polyolefin can be obtained by purchase. Exemplarily, it can be purchased from Evonik Vestoplast 508, Vestoplast 704, Vestoplast 708.

[0038] Preferably, the lubricant comprises any one or a combination of at least two of Fischer-Tropsch wax C80, Fischer-Tropsch wax C100, oleic acid amide or erucic acid amide.

[0039] Preferably, the antioxidant comprises a primary antioxidant and a secondary antioxidant.

[0040] Preferably, the primary antioxidant comprises an aromatic amine antioxidant and / or a hindered phenol antioxidant.

[0041] Preferably, the aromatic antioxidant comprises any one or a combination of at least two of diaryl secondary amine, p-phenylenediamine, ketoamine or aldehyde amine.

[0042] Preferably, the hindered phenol antioxidant comprises any one or a combination of at least two of 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] or n-octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0043] Preferably, the secondary antioxidant comprises a thioester secondary antioxidant and / or a phosphite secondary antioxidant.

[0044] Preferably, the thioester secondary antioxidant comprises distearyl thiodipropionate and / or dilauryl thiodipropionate.

[0045] Preferably, the phosphite secondary antioxidant comprises tris(2,4-di-tert-butylphenyl) phosphite and / or bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite.

[0046] Preferably, the preparation raw materials of the modified filler comprise an organosilicon modifier and a filler.

[0047] Preferably, the organosilicon modifier comprises any one or a combination of at least two of γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0048] Preferably, the filler comprises talcum powder and / or silica powder.

[0049] Preferably, the mass ratio of the modifier to the filler is (0.1-0.5):100, such as 0.1:100, 0.2:100, 0.3:100, 0.4:100, 0.5:100, etc. Other specific point values within this numerical range can be selected and will not be elaborated one by one here.

[0050] Preferably, the modified filler includes silicone-modified talcum powder and / or silicone-modified silica powder.

[0051] Preferably, the modified filler is prepared by the following method:

[0052] Stir the filler at 130 - 160 °C (such as 130 °C, 133 °C, 136 °C, 139 °C, 142 °C, 145 °C, 148 °C, 150 °C, 155 °C, 160 °C, etc.), mix it with a silicone modifier, and stir for 1 - 2 h (such as 1 h, 1.1 h, 1.2 h, 1.3 h, 1.4 h, 1.5 h, 1.6 h, 1.7 h, 1.8 h, 1.9 h, 2 h, etc.) to obtain the modified filler. Other specific point values within this numerical range can be selected and will not be elaborated one by one here.

[0053] Preferably, the specific surface area of the carbon black > 100 m 2 / g (such as 110 m 2 / g, 115 m 2 / g, 120 m 2 / g, 125 m 2 / g, 130 m 2 / g, 135 m 2 / g, 140 m 2 / g, 145 m 2 / g, 150 m 2 / g, 250 m 2 / g, 350 m 2 / g, etc.), and the volatile matter ≤ 1% (such as 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, etc.). Other specific point values within the above numerical ranges can be selected and will not be elaborated one by one here.

[0054] In the present invention, the carbon black can be obtained by purchase. Exemplarily, it can be purchased from Orion PRINTEX L (specific surface area 150 m 2 / g, volatile matter 0.8%), PRINTEX 95 (specific surface area 250 m 2 / g, volatile matter 1.0%), HIBLACK 30 (specific surface area 110 m 2 / g, volatile matter 1.0%), PRINTEX 90 (specific surface area 350 m 2 / g, volatile matter 1.0%), PRINTEX HV (specific surface area 125 m 2 / g, volatile matter 0.7%).

[0055] Second aspect, the present invention provides a preparation method of the butyl hot melt adhesive described in the first aspect, characterized in that the preparation method comprises the following steps:

[0056] Blend rubber, polyisobutylene, organosilicon modified polymer, amorphous polyolefin, lubricant, antioxidant, and then mix with carbon black and modified filler to obtain butyl hot melt adhesive.

[0057] Preferably, the preparation method is carried out at 130 - 160 °C (such as 130 °C, 133 °C, 136 °C, 139 °C, 142 °C, 145 °C, 148 °C, 150 °C, 155 °C, 160 °C, etc.), and other specific point values within this numerical range can be selected and will not be elaborated one by one here.

[0058] Preferably, the blending time is 20 - 130 min, such as 20 min, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 130 min, etc., and other specific point values within this numerical range can be selected and will not be elaborated one by one here.

[0059] Preferably, the mixing time is 60 - 180 min, such as 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min, 130 min, 140 min, 150 min, 160 min, 170 min, 180 min, etc., and other specific point values within this numerical range can be selected and will not be elaborated one by one here.

[0060] Third aspect, the present invention provides an application of the hot melt adhesive for vehicle lamps described in the first aspect in bonding vehicle lamps.

[0061] Compared with the prior art, the present invention has the following beneficial effects:

[0062] The butyl hot melt adhesive provided by the present invention, through the screening of preparation raw materials, makes the obtained butyl hot melt adhesive not easy to flow when heated, has good high-temperature stability, and excellent bonding performance. The butyl hot melt adhesive provided by the present invention has a flowability of only 3.2 - 5.3 mm at 120 °C for 24 h, is morphologically stable at high temperatures, can ensure the structural stability of vehicle lamps in high-temperature environments, and avoid problems such as deformation and functional damage of vehicle lamps caused by the flow of the adhesive; when heated at 200 °C for 72 h, the viscosity change rate is only -4.7% to -8.7% and there is no abnormality in the surface carbonization situation, can maintain stable performance at high temperatures, enable vehicle lamps to still work normally when in hot weather or near high-temperature parts such as the engine, and extend the service life of vehicle lamps; the adhesive force is as high as 117 - 138 N, can form a firm bond with vehicle lamp materials, and ensure the sealing and optical performance of vehicle lamps. Detailed Implementation Modes

[0063] To further elaborate on the technical means and effects adopted by the present invention, the following further illustrates the technical solution of the present invention in conjunction with the preferred embodiments of the present invention. However, the present invention is not limited to the scope of the embodiments.

[0064] In the following embodiments, unless otherwise specified, the reagents and consumables used are purchased from conventional reagent manufacturers in the art; unless otherwise specified, the experimental methods and technical means used are conventional methods and means in the art.

[0065] Example 1

[0066] This example provides a butyl hot melt adhesive, and the preparation method is as follows:

[0067] (1) Preparation of organosilicon-modified polymer:

[0068] Add 280 g of hydroxyl-terminated polybutadiene (Krewele Poly BD R45V) to a reactor equipped with mechanical stirring, vacuum, nitrogen protection, and heating devices. Stir at 90 °C and vacuum dry for 3 h; then cool to 70 °C and add 15 g of diphenylmethane diisocyanate (MDI). React for 2 h under N 2 atmosphere to obtain an isocyanate-terminated polymer. The R value (the R value is the molar ratio of isocyanate groups to hydroxyl groups in the isocyanate-terminated polymer system) of the isocyanate-terminated polymer is 1.344;

[0069] Continue to add 15 g of γ-mercaptopropyltrimethoxysilane to the above isocyanate-terminated polymer and react at 70 °C for 1 h to obtain organosilicon-modified polymer 1.

[0070] (2) Preparation of modified filler:

[0071] Dry 2000 g of talc at 120 °C for 48 h, then add it to a kneader, knead and stir at 140 °C, add 3 g of glycidyl ether oxypropyltrimethoxysilane, and stir for 1 h to obtain modified filler 1.

[0072] (3) Preparation of butyl hot melt adhesive:

[0073] At 140 °C, sequentially add butyl rubber, polyisobutylene, organosilicon-modified polymer, amorphous polyolefin, lubricant, and antioxidant to a kneader, and blend under vacuum protection for 90 min; then add carbon black and modified filler, and mix thoroughly under vacuum protection for 100 min to obtain butyl hot melt adhesive.

[0074] The feeding amounts of each raw material are shown in the following table.

[0075]

[0076] Example 2

[0077] This embodiment provides a butyl hot melt adhesive, and the preparation method is as follows:

[0078] (1) Preparation of silicone-modified polymers:

[0079] 280g of hydroxy polybutadiene (Crayway Poly BD R45V) was added to a reactor equipped with mechanical stirring, vacuum, nitrogen protection and heating devices, stirred at 90°C, and vacuum dried for 3h; then cooled to 70°C, 15g of MDI, N 2 The reaction was carried out under atmosphere for 2 hours to obtain an isocyanate-terminated polymer, wherein the R value of the isocyanate-terminated polymer was 1.344;

[0080] 20 g of N-phenyl-γ-aminopropyltrimethoxysilane was further added to the above isocyanate-terminated polymer, and the mixture was reacted at 60° C. for 1 h to obtain an organosilicon-modified polymer 2.

[0081] (2) Preparation of modified filler:

[0082] 2000 g of silicon micropowder was dried at 120° C. for 48 h, then added to a kneader, kneaded and stirred at 140° C., 3 g of glycidyloxypropyltrimethoxysilane was added, and stirred for 1 h to obtain modified filler 2.

[0083] (3) Preparation of butyl hot melt adhesive:

[0084] At 140° C., butyl rubber, polyisobutylene, silicone-modified polymer, amorphous polyolefin, lubricant and antioxidant were added to a kneader in sequence and blended for 90 minutes under vacuum protection; then carbon black and modified filler were added and fully mixed for 100 minutes under vacuum protection to obtain a butyl hot melt adhesive.

[0085] The feeding amount of each raw material is shown in the following table.

[0086]

[0087] Example 3

[0088] This embodiment provides a butyl hot melt adhesive, and the preparation method is as follows:

[0089] (1) Preparation of silicone-modified polymers:

[0090] 280g of hydroxy polybutadiene (Crayway Poly BD R45V) was added to a reactor equipped with mechanical stirring, vacuum, nitrogen protection and heating devices, stirred at 90°C, and vacuum dried for 3h; then cooled to 70°C, 14g of MDI, N 2React for 2 h under the atmosphere to obtain an isocyanate-terminated polymer, and the R value of the isocyanate-terminated polymer is 1.254.

[0091] Continuously add 15 g of N-phenyl-γ-aminopropyltrimethoxysilane to the above isocyanate-terminated polymer, and react at 60 °C for 1 h to obtain organosilicon-modified polymer 3.

[0092] Preparation of modified filler:

[0093] Dry 2000 g of silica powder at 120 °C for 48 h, then add it to a kneader, knead and stir at 140 °C, add 5 g of glycidyl ether oxypropyltrimethoxysilane, and stir for 1 h to obtain modified filler 3.

[0094] Preparation of butyl hot melt adhesive:

[0095] At 140 °C, successively add butyl rubber, polyisobutylene, organosilicon-modified polymer, amorphous polyolefin, lubricant, and antioxidant to the kneader, and blend under vacuum protection for 90 min; then add carbon black and modified filler, and mix thoroughly under vacuum protection for 100 min to obtain butyl hot melt adhesive.

[0096] The feeding amounts of each raw material are shown in the following table.

[0097]

[0098] Example 4

[0099] This example provides a butyl hot melt adhesive, and the preparation method is as follows:

[0100] (1) Preparation of organosilicon-modified polymer:

[0101] Add 280 g of hydroxyl-terminated polybutadiene (Kreweley poly BD R45V) to a reactor equipped with mechanical stirring, vacuum, nitrogen protection, and heating devices, stir at 90 °C, and vacuum dry for 3 h; then cool down to 70 °C, add 15 g of MDI, N 2 React for 2 h under the atmosphere to obtain an isocyanate-terminated polymer, and the R value of the isocyanate-terminated polymer is 1.344;

[0102] Continuously add 20 g of N-phenyl-γ-aminopropyltrimethoxysilane to the above isocyanate-terminated polymer, and react at 70 °C for 1 h to obtain organosilicon-modified polymer 4.

[0103] (2) Preparation of butyl hot melt adhesive:

[0104] At 140 °C, butyl rubber, polyisobutylene, organosilicon-modified polymer, amorphous polyolefin, lubricant, and antioxidant were successively added to a kneader and blended under vacuum protection for 90 min; then carbon black and modified filler were added, and the mixture was thoroughly mixed under vacuum protection for 100 min to obtain butyl hot melt adhesive.

[0105] The feeding amounts of each raw material are shown in the following table.

[0106]

[0107] Example 5

[0108] This example provides a butyl hot melt adhesive, and the preparation method is as follows:

[0109] (1) Preparation of organosilicon-modified polymer:

[0110] Add 280 g of hydroxyl-terminated polybutadiene (Krewele Poly BD R45V) to a reactor equipped with mechanical stirring, vacuum, nitrogen protection, and heating devices, stir at 90 °C, and vacuum dry for 3 h; then cool to 70 °C, add 15 g of MDI, and react for 2 h under N 2 atmosphere to obtain an isocyanate-terminated polymer with an R value of 1.344;

[0111] Continue to add 15 g of γ-mercaptopropyltrimethoxysilane to the above isocyanate-terminated polymer and react at 70 °C for 1 h to obtain organosilicon-modified polymer 5.

[0112] (2) Preparation of butyl hot melt adhesive:

[0113] At 140 °C, butyl rubber, polyisobutylene, organosilicon-modified polymer, amorphous polyolefin, lubricant, and antioxidant were successively added to a kneader and blended under vacuum protection for 90 min; then carbon black and modified filler were added, and the mixture was thoroughly mixed under vacuum protection for 100 min to obtain butyl hot melt adhesive.

[0114] The feeding amounts of each raw material are shown in the following table.

[0115]

[0116] Example 6

[0117] This comparative example provides a butyl hot melt adhesive, which is different from Example 1 only in that the modified filler 1 is replaced with talc in equal mass, and other conditions remain unchanged.

[0118] Comparative Example 1

[0119] This comparative example provides a butyl hot melt adhesive, which is different from Example 1 only in that the organosilicon-modified polymer 1 is replaced with the organosilicon-modified polymer 6 in equal mass, and other conditions remain unchanged.

[0120] Preparation of organosilicon-modified polymer 6:

[0121] Add 280 g of polyether diol PPG2000 to a reactor equipped with mechanical stirring, vacuum, nitrogen protection, and heating devices, stir at 100 °C, and vacuum dry for 2 h; then cool down to 70 °C, add 16.8 g of MDI, and react under N 2 atmosphere for 1.5 h to obtain an isocyanate-terminated polymer, and the R value of the isocyanate-terminated polymer is 1.344.

[0122] Continue to add 15 g of γ-mercaptopropyltrimethoxysilane to the above isocyanate-terminated polymer, and react at 70 °C for 1 h to obtain the organosilicon-modified polymer 6.

[0123] Comparative Example 2

[0124] This comparative example provides a butyl hot melt adhesive, which is different from Example 1 only in that the organosilicon-modified polymer 1 is replaced with terpene phenol resin in equal mass, and other conditions remain unchanged.

[0125] Comparative Example 3

[0126] This comparative example provides a butyl hot melt adhesive, which is different from Example 1 only in that the organosilicon-modified polymer 1 is replaced with C5 petroleum resin H5-1000 in equal mass, and other conditions remain unchanged.

[0127] Comparative Example 4

[0128] This comparative example provides a butyl hot melt adhesive, and the preparation method is as follows:

[0129] (1) Preparation of organosilicon-modified polymer:

[0130] Add 280 g of hydroxyl-terminated polybutadiene (Kreweil Poly BD R45V) to a reactor equipped with mechanical stirring, vacuum, nitrogen protection, and heating devices, stir at 90 °C, and vacuum dry for 3 h; then cool down to 70 °C, add 15 g of diphenylmethane diisocyanate (MDI), and react under N 2 atmosphere for 2 h to obtain an isocyanate-terminated polymer, and the R value (the R value is the molar ratio of isocyanate groups to hydroxyl groups in the isocyanate-terminated polymer system) of the isocyanate-terminated polymer is 1.344;

[0131] Continue to add 15 g of γ-mercaptopropyltrimethoxysilane to the above isocyanate-terminated polymer, and react at 70 °C for 1 h to obtain the organosilicon-modified polymer 1.

[0132] (2) Preparation of modified filler:

[0133] Dry 2000 g of talcum powder at 120 °C for 48 h, then add it to a kneader, knead and stir at 140 °C, add 3 g of glycidyl ether oxypropyltrimethoxysilane, and stir for 1 h to obtain modified filler 1.

[0134] (3) Preparation of butyl hot melt adhesive:

[0135] At 140 °C, successively add butyl rubber, organosilicon modified polymer, amorphous polyolefin, lubricant, and antioxidant to the kneader, and blend under vacuum protection for 90 min; then add carbon black and modified filler, and mix thoroughly under vacuum protection for 100 min to obtain butyl hot melt adhesive.

[0136] The feeding amounts of each raw material are shown in the following table.

[0137]

[0138] Test Example 1

[0139] In this test example, the butyl hot melt adhesives prepared in Examples 1-6 and Comparative Examples 1-4 were subjected to performance tests, and the test methods were as follows:

[0140] High-temperature flow test method: Stick a 1.0 g cube (10×10×10 mm) of butyl rubber tightly on a PC board, and place the board vertically and statically in an oven at 120 °C. After 24 hours, observe the flow state of the hot melt adhesive and record the flow distance.

[0141] High-temperature stability test method: Place the container filled with the sample in a drying oven at 200 ± 1 °C and heat and dry for 72 hours. After 72 hours, measure the viscosity and calculate the viscosity change rate. Measure using a Brookfield viscometer, the test temperature is 190 °C, and the rotation speed is 10 rpm.

[0142] Surface carbonization: Put about 70 g of the sample into a small aluminum foil box, dry it at 200 ± 1 °C for 72 hours, then cut the sample in half after cooling, and measure the thickness of the carbonized part on the surface of the sample. If it is less than 1 mm, there is no abnormality.

[0143] Adhesion test method: Conduct the test according to GB / T 7124. The substrate is PC / PP, the substrate size is 100×25×2.5 mm; the bonding area is 25×25×0.8 mm, the gluing temperature is 180 °C, and after sample preparation, cure under standard conditions for 24 h and then conduct the adhesion force test. The test speed is 12.7 mm / min, and record the maximum tensile force.

[0144] The test results are shown in Table 1.

[0145] Table 1

[0146]

[0147] As can be seen from the data in Table 1, the butyl hot-melt adhesives prepared in Examples 1-5 have a flowability of only 3.2-5.3 mm at 120°C for 24 h, a viscosity change rate of only -4.7% to -8.7% when heated at 200°C for 72 h, no abnormal surface carbonization after drying at 200°C for 72 h, and an adhesion force as high as 117-138 N. The above data show that the butyl hot-melt adhesives prepared in Examples 1-5 are not easily flowed by heat, have good high-temperature stability, and excellent adhesion, meeting the requirements for the adhesion and sealing of vehicle lamps.

[0148] By comparing Example 1 with Example 6, it can be seen that after modifying the filler with a silicone modifier, the high-temperature stability and adhesiveness of the butyl hot-melt adhesive can be significantly improved, and its heat-induced flowability can be reduced.

[0149] By comparing Example 1 with Comparative Examples 1-3, it can be seen that using a silicone-modified polymer as a tackifying resin can significantly improve the high-temperature stability and adhesiveness of the butyl hot-melt adhesive and reduce its heat-induced flowability compared with traditional terpene-phenol resins and C5 resins. When the silicone-modified polymer is a polyurethane polymer capped with a silane coupling agent, the performance of the prepared butyl rubber can be better improved.

[0150] By comparing Example 1 with Comparative Example 4, it can be seen that adding polyisobutylene to the preparation of butyl rubber can significantly improve the high-temperature stability and adhesiveness of the butyl hot-melt adhesive and reduce its heat-induced flowability.

[0151] The applicant declares that the present invention uses the above examples to illustrate the technical solutions of the present invention, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must rely on the above examples to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent substitution of each raw material of the products of the present invention, the addition of auxiliary components, and the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

[0152] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0153] In addition, it should be noted that in the various specific technical features described in the above specific embodiments, they can be combined in any appropriate manner without contradiction. To avoid unnecessary repetition, the present invention will not separately describe various possible combination methods.

Claims

1. A butyl hot melt adhesive, characterized in that: In parts by weight, the raw materials for preparing the butyl hot melt adhesive include: The organosilicon-modified polymer includes a polyurethane polymer terminated with a silane coupling agent.

2. The butyl hot melt adhesive according to claim 1, characterized in that: The Mooney viscosity ML (1+8) of the butyl rubber at 125° C. is 30-60.

3. The butyl hot melt adhesive according to claim 1 or 2, characterized in that: The polyisobutylene includes medium molecular weight polyisobutylene and high molecular weight polyisobutylene; Preferably, the molecular weight of the medium molecular weight polyisobutylene is 30000-100000; Preferably, the molecular weight of the high molecular weight polyisobutylene is 100,000-2,000,000.

4. The butyl hot melt adhesive according to any one of claims 1 to 3, characterized in that: The silane coupling agent includes any one of bis-(γ-trimethoxysilylpropyl)amine, γ-mercaptopropyltrimethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane, or a combination of at least two thereof; Preferably, the polyurethane polymer comprises isocyanate-terminated hydroxyl polybutadiene; Preferably, the molar ratio of the reaction of the hydroxy polybutadiene and the isocyanate is 1:(1.2-1.5); Preferably, the ratio of the sum of the molar numbers of hydroxyl groups in the silane coupling agent and the hydroxypolybutadiene to the molar number of isocyanate is (1-1.5):

1.

5. The butyl hot melt adhesive according to any one of claims 1 to 4, characterized in that: The amorphous polyolefin comprises an alpha-olefin polymer; Preferably, the α-olefin comprises a combination of any at least two of ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-octene or 4-methyl-1-pentene; Preferably, the polyolefin has a softening point of 80-120° C. and a melt viscosity of 2000-30000 mPa·s at 190° C.

6. The butyl hot melt adhesive according to any one of claims 1 to 5, characterized in that: The lubricant includes any one of Fischer-Tropsch wax C80, Fischer-Tropsch wax C100, oleamide or erucamide, or a combination of at least two of them.

7. The butyl hot melt adhesive according to any one of claims 1 to 6, characterized in that: The antioxidants include primary antioxidants and auxiliary antioxidants; Preferably, the primary antioxidant comprises an aromatic amine antioxidant and / or a hindered phenol antioxidant; Preferably, the aromatic antioxidant includes any one or a combination of at least two of diaryl secondary amines, p-phenylenediamine, ketoamines or aldehyde amines; Preferably, the hindered phenol antioxidant includes any one of 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate or n-octadecylβ-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate or a combination of at least two thereof; Preferably, the auxiliary antioxidant includes a thioester auxiliary antioxidant and / or a phosphite auxiliary antioxidant; Preferably, the thioester auxiliary antioxidant includes distearyl thiodipropionate and / or didodecyl thiodipropionate; Preferably, the phosphite auxiliary antioxidant includes tris(2,4-di-tert-butylphenyl) phosphite and / or bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite.

8. The butyl hot melt adhesive according to any one of claims 1 to 7, characterized in that: The raw materials for preparing the modified filler include an organosilicon modifier and a filler; Preferably, the organosilicon modifier includes any one or a combination of at least two of γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)-ethyltriethoxysilane, and β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane; Preferably, the filler comprises talc and / or silica powder; Preferably, the mass ratio of the modifier to the filler is (0.1-0.5):100; Preferably, the modified filler comprises organosilicon-modified talc and / or organosilicon-modified silica powder; Preferably, the specific surface area of ​​the carbon black is greater than 100 m 2 / g, volatile matter ≤1%.

9. A method for preparing the butyl hot melt adhesive according to any one of claims 1 to 9, characterized in that: The preparation method comprises the following steps: Rubber, polyisobutylene, silicone modified polymer, amorphous polyolefin, lubricant, antioxidant are blended, and then mixed with carbon black and modified filler to obtain butyl hot melt adhesive; Preferably, the preparation method is carried out at 130-160°C; Preferably, the blending time is 20-130 min; Preferably, the mixing time is 60-180 min.

10. Use of the hot melt adhesive for vehicle lamps as claimed in any one of claims 1 to 8 in bonding vehicle lamps.

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