A heat-resistant and flame-retardant double-sided butyl adhesive material and its preparation method and application

Abstract

The present invention relates to a double-sided butyl adhesive material resistant to moisture and heat, and a preparation method and application thereof. The adhesive material comprises a flame-retardant butyl adhesive layer and an isolation layer. The flame-retardant butyl adhesive layer comprises the following components in parts by weight: 100 parts of a butyl rubber matrix, 154 to 176 parts of modified polyisobutylene, 36 to 42 parts of a flame-retardant acrylate polymer, 35 to 40 parts of a tackifier, 15 to 25 parts of a vulcanizer, 55 to 75 parts of a nano flame-retardant fiber material, and 5 to 8 parts of an auxiliary agent. The present invention greatly improves the flame retardancy of the double-sided butyl adhesive material by compounding flame-retardant modified polyisobutylene, flame-retardant acrylate polymer and nano flame-retardant fiber material in a butyl rubber matrix, and its UL94 flame retardancy reaches V-0 level. At the same time, the butyl adhesive material maintains excellent high and low temperature resistance, acid and alkali resistance and moisture and heat resistance.

Description

Technical Field

[0001] The present invention relates to the field of new materials, and in particular to a moisture-heat-resistant and flame-retardant double-sided butyl adhesive material and a preparation method and application thereof. Background Art

[0002] At present, in the automation and intelligent production of industries such as automobiles, electronics, and electrical appliances, traditional structural bonding methods have been gradually replaced by pressure-sensitive bonding. For example, adhesive materials are widely used for fixing automobile interiors, circuit interiors, screen cable fixation, wire and cable fixation, and installation of new energy batteries. Among them, butyl rubber adhesive materials have excellent water and air tightness and are suitable for use in industries such as automobiles, solar energy, lithium batteries, and hydrogen batteries. However, butyl rubber has low cohesion, poor heat resistance, poor aging resistance, poor initial adhesion, low peel strength, and poor water vapor resistance. It cannot be used in high temperature environments, especially it is difficult to meet the use requirements of bonded products in high temperature and high humidity environments. In addition, in the above-mentioned application fields, high requirements are also placed on the flame retardancy of adhesive materials. However, the existing butyl tape is a flammable material with a limiting oxygen index (LOI) of 21.3%, a fast burning speed, a large amount of heat release and smoke release, and will produce molten droplets, which seriously endangers safety and greatly limits the application of butyl rubber in the fields of automobiles, electronics, and new energy.

[0003] The prior art discloses some modifications to the flame retardancy of butyl rubber adhesives, such as patent CN117417702A discloses a flame retardant and heat-insulating butyl rubber self-adhesive waterproof membrane, wherein the butyl rubber self-adhesive layer uses hollow glass microspheres, and the hollow glass microspheres are modified by N-(2-aminoethyl)-11-aminoundecyltrimethoxysilane and titanate coupling agent, thereby improving the peel strength, heat stability and flame retardancy of the butyl rubber self-adhesive layer. However, the patent is for a butyl rubber self-adhesive waterproof membrane, which is mainly used for outdoor exposed roof waterproof membranes. It is formed by combining with an isolation layer, a heat insulation layer, a fiber reinforcement layer, a PTFE film layer, etc. to form a waterproof membrane with better performance, which is not suitable for use in precision automotive, solar energy, lithium battery, hydrogen power and other electronic and electrical industries. Summary of the invention

[0004] The purpose of the present invention is to provide a moisture-heat-resistant and flame-retardant double-sided butyl adhesive material and a preparation method and application thereof in order to solve the above problems.

[0005] The purpose of the present invention is achieved through the following technical solutions:

[0006] A moisture-heat-resistant and flame-retardant double-sided butyl adhesive material comprises a flame-retardant butyl adhesive layer and an isolation layer. The flame-retardant butyl adhesive layer comprises the following components in parts by weight: 100 parts of a butyl rubber matrix, 154 to 176 parts of modified polyisobutylene, 36 to 42 parts of a flame-retardant acrylate polymer, 35 to 40 parts of a tackifier, 15 to 25 parts of a vulcanizer, 55 to 75 parts of a nano flame-retardant fiber material, and 5 to 8 parts of an auxiliary agent.

[0007] As a preferred technical solution of the present invention, the flame retardant butyl adhesive layer includes the following components in parts by weight: 100 parts of butyl rubber matrix, 166 parts of modified polyisobutylene, 38 parts of flame retardant acrylate polymer, 39 parts of tackifier, 20 parts of vulcanizer, 65 parts of nano flame retardant fiber material, and 7 parts of additives.

[0008] As a preferred technical solution of the present invention, the butyl rubber matrix is ​​selected from one or more of butyl rubber, brominated butyl rubber, and chlorinated butyl rubber, preferably chlorinated butyl rubber;

[0009] The modified polyisobutylene is a mixture of low molecular weight polyisobutylene grafted with nitrogen functional groups and high molecular weight polyisobutylene, wherein the weight ratio of the low molecular weight polyisobutylene to the high molecular weight polyisobutylene is 0.5-0.8:1-2.

[0010] The average number average molecular weight of the low molecular weight polyisobutylene is 200 to 3000 g / mol. As a preferred embodiment, the low molecular weight polyisobutylene PB1300 produced by Daelim of South Korea is preferably used;

[0011] The high molecular weight polyisobutylene has an average number average molecular weight of 100,000 to 900,000 g / mol. As a preferred embodiment, Oppanol B 200 produced by BASF is preferably used.

[0012] Specifically, the preparation method is as follows: by weight, 1 to 1.5 parts of polyisobutylene are dissolved in 5 to 6 parts of xylene solvent, 0.2 to 0.3 parts of melamine and 0.01 to 0.05 parts of benzoyl peroxide are added as initiators, and the mixture is stirred evenly. The reaction mixture is reacted at 82 to 86° C. for 1 to 2 hours. After the reaction is completed, the product is separated from the solvent to obtain the modified polyisobutylene.

[0013] Low molecular weight polyisobutylene has good heat resistance, oxygen resistance, acid and alkali resistance, good compatibility with polymer materials, good compatibility with general non-polar substances, and low-temperature dispersibility. High molecular weight polyisobutylene is a typical saturated linear polymer with good heat resistance, light resistance, and aging resistance, and has ideal chemical stability. It still has excellent waterproofness and air tightness at higher temperatures. The present invention is mainly based on high molecular weight polyisobutylene, and has better flame retardancy. This is because high molecular weight polyisobutylene has higher crystallinity and a tighter molecular structure, and is more difficult to decompose and burn during combustion; in addition, the flame retardancy is improved by grafting nitrogen functional groups on polyisobutylene molecules through chemical reactions, while other mechanical properties are not reduced.

[0014] As a preferred technical solution of the present invention, the flame-retardant acrylate polymer is a water-based acrylic pressure-sensitive adhesive containing a phosphorus-based flame retardant, which is specifically prepared by the following method:

[0015] (1) Preparing a phosphorus-containing monomer prepolymer: First, 5.6 parts of melamine polyphosphate and 15-18 parts of dichloromethane are added to a reaction kettle by weight, and 4.8 parts of hydroxyethyl acrylate and 5.4 parts of triethylamine are added dropwise at 0-4° C. After the addition is complete, the mixture is reacted for 2-3 hours, and then 2-3 parts of triethylamine is added and kept for 1-2 hours to obtain a light yellow transparent liquid phosphorus-containing monomer prepolymer;

[0016] (2) allowing the phosphorus-containing monomer prepolymer obtained in step (1) to participate in emulsion polymerization to prepare a water-based pressure-sensitive adhesive.

[0017] As a preferred technical solution of the present invention, it is prepared by the following method:

[0018] (1) adding 32-36 parts of water and 2.2 parts of sodium dodecylbenzene sulfonate by weight into a reaction kettle, stirring and heating to 85° C. to obtain a bottom liquid;

[0019] (2) adding 31 to 43 parts of water and 3.1 parts of sodium succinate sulfonate by weight into an emulsification tank and stirring, and then adding 3.5 parts of hard monomer, 37 parts of soft monomer, 2.59 parts of phosphorus-containing monomer prepolymer, 1.36 parts of glycidyl methacrylate, and 0.95 parts of acrylic acid, and stirring uniformly to prepare a pre-emulsion;

[0020] (3) adding 4-5 wt% of the total amount of the pre-emulsion into a reaction kettle, adding 0.3 parts of sodium persulfate, and carrying out polymerization reaction for 10-12 minutes;

[0021] (4) Add the remaining pre-emulsion and 0.35 parts of ammonium persulfate to the reaction kettle simultaneously within 3 to 4 hours, and keep warm for 30 to 45 minutes after the addition is completed to obtain a flame-retardant acrylic polymer.

[0022] The present invention utilizes the characteristics of acrylic pressure-sensitive adhesive having excellent bonding performance and good interfacial stress dispersion ability to the substrate, as well as weather resistance, heat resistance, no phase separation and migration phenomenon, etc., which helps to improve the performance of the double-sided butyl adhesive material resistant to moisture and heat, especially moisture and heat resistance. However, the flame retardancy of traditional acrylic pressure-sensitive adhesive is poor. The present invention uses a water-based acrylic pressure-sensitive adhesive containing a phosphorus-based flame retardant. In the preparation process of the acrylic pressure-sensitive adhesive, a phosphorus-containing monomer prepolymer is first prepared and then participates in emulsion polymerization. The acrylic ester polymer obtained in this way has flame retardancy and effectively avoids the adverse effects of the addition of flame retardants on the performance. At the same time, the presence of epoxy groups in glycidyl methacrylate improves the wet surface bonding performance and meets the application requirements in high temperature and high humidity scenes such as automobiles and new energy batteries.

[0023] As a preferred technical solution of the present invention, the hard monomer is selected from one or more of styrene, methyl methacrylate, methyl acrylate, and vinyl acetate, preferably styrene;

[0024] The soft monomer is selected from one or more of butyl acrylate, isooctyl acrylate, and ethyl acrylate, and butyl acrylate is preferred.

[0025] As a preferred technical solution of the present invention, the tackifier is selected from one or more of terpene resin, rosin, and C5 petroleum resin;

[0026] And / or, the vulcanizing agent is nano zinc oxide.

[0027] As a preferred technical solution of the present invention, the nano flame retardant fiber material is selected from one or more of aramid fiber, polybenzimidazole fiber, polyimide fiber, phenolic fiber, and polyacrylonitrile pre-oxidized fiber. The nano flame retardant fiber material not only provides basic mechanical properties, but also has excellent flame retardant properties.

[0028] And / or, the auxiliary agent includes an antioxidant, and the antioxidant is antioxidant 1010.

[0029] As a preferred technical solution of the present invention, the flame retardant butyl adhesive layer is prepared by the following method: a butyl rubber matrix, polyisobutylene, a flame retardant acrylate polymer, a tackifier, a vulcanizer, a modified nano flame retardant fiber material, and an additive are added to a rubber mixer and mixed evenly, mixed for 1 to 3 hours under a vacuum condition of -0.06 to -0.1 MPa and a temperature of 60 to 85°C, and naturally cooled to room temperature to obtain a flame retardant butyl adhesive layer.

[0030] As a preferred technical solution of the present invention, a method for preparing a moisture-heat-resistant flame-retardant double-sided butyl adhesive material comprises the following steps: uniformly extruding a flame-retardant butyl adhesive layer through an extruder and coating it on an isolation layer at the mouth of a molding die, with a thickness of 0.1 to 0.6 mm; laminating the isolation layer on the surface of the flame-retardant butyl adhesive layer; and using a double-roller machine to press and grind the composite, automatically rewind after cooling, and slit and shape to obtain a moisture-heat-resistant flame-retardant double-sided butyl adhesive material;

[0031] The isolation layer comprises release paper with a thickness of 0.05 to 0.5 mm.

[0032] The application of the above-mentioned moisture-resistant, heat-resistant and flame-retardant double-sided butyl adhesive material is used for fixing automobile interiors, internal wiring, screen cable fixing, wire and cable fixing, and installation of new energy batteries. When using it, just tear off the isolation layer and adhere directly.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] Compared with the traditional method of directly adding various flame retardants to improve the flame retardancy of butyl adhesive materials (flame retardancy is improved, but other mechanical properties are reduced), the present invention compounds flame retardant modified polyisobutylene, flame retardant acrylate polymer and nano flame retardant fiber material in the butyl rubber matrix, while improving the flame retardancy of double-sided butyl adhesive materials (UL94 flame retardancy reaches V-0 level), while the butyl adhesive material maintains excellent high and low temperature resistance, acid and alkali resistance and moisture and heat resistance. The present invention mainly uses chemical modification means to perform flame retardant modification from the perspective of polymer molecules, and takes into account both flame retardancy and mechanical properties through reasonable formula design. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 These are photos of the relevant products prepared by the present invention. DETAILED DESCRIPTION

[0036] The present invention is further described below by means of specific examples. The examples described in the present invention are only used to illustrate the present invention and do not limit the scope of the present invention.

[0037] [Preparation Example 1] Preparation of modified polyisobutylene a

[0038] The modified polyisobutylene is prepared by the following method: 1.3 parts of polyisobutylene (composed of low molecular weight polyisobutylene and high molecular weight polyisobutylene in a weight ratio of 0.6:1.5) are dissolved in about 5.5 parts of xylene solvent, 0.25 parts of melamine and 0.03 parts of benzoyl peroxide are added as initiators, and stirred evenly. The reaction mixture is reacted at about 85° C. for 1.5 hours. After the reaction is completed, the product is separated from the solvent to obtain modified polyisobutylene a with nitrogen functional groups grafted onto the polyisobutylene molecules.

[0039] [Preparation Example 2] Preparation of modified polyisobutylene b

[0040] The modified polyisobutylene is prepared by the following method: 1.25 parts of polyisobutylene (composed of low molecular weight polyisobutylene and high molecular weight polyisobutylene in a weight ratio of 0.6:1.8) are dissolved in about 6 parts of xylene solvent, 0.28 parts of melamine and 0.035 parts of benzoyl peroxide are added as initiators, and stirred evenly. The reaction mixture is reacted at about 85° C. for 2 hours. After the reaction is completed, the product is separated from the solvent to obtain modified polyisobutylene b with nitrogen functional groups grafted onto the polyisobutylene molecules.

[0041] [Preparation Example 3] Preparation of modified polyisobutylene c

[0042] The modified polyisobutylene is prepared by the following method: 1.45 parts of polyisobutylene (composed of low molecular weight polyisobutylene and high molecular weight polyisobutylene in a weight ratio of 0.5:1.7) are dissolved in about 5.8 parts of xylene solvent, 0.3 parts of melamine and 0.04 parts of benzoyl peroxide are added as initiators, and stirred evenly. The reaction mixture is reacted at about 85° C. for 2 hours. After the reaction is completed, the product is separated from the solvent to obtain modified polyisobutylene c with nitrogen functional groups grafted onto the polyisobutylene molecules.

[0043] [Preparation Example 4] Preparation of flame-retardant acrylic polymer a

[0044] The preparation steps of flame retardant acrylic polymer are as follows:

[0045] (1) Preparing a phosphorus-containing monomer prepolymer: First, 5.6 parts of melamine polyphosphate and 16.8 parts of dichloromethane were added to a reaction kettle by weight, and 4.8 parts of hydroxyethyl acrylate and 5.4 parts of triethylamine were added dropwise at 0° C. After the addition was complete, the mixture was reacted for 2.5 hours, and then 2.5 parts of triethylamine was added and kept for 2 hours to obtain a light yellow transparent liquid phosphorus-containing monomer prepolymer;

[0046] (2) adding 35 parts of water and 2.2 parts of sodium dodecylbenzene sulfonate by weight into a reaction kettle, stirring and heating to 85° C. to obtain a bottom liquid;

[0047] (3) adding 42 parts of water and 3.1 parts of sodium succinate sulfonate by weight into an emulsification tank and stirring, then adding 3.5 parts of hard monomer styrene, 37 parts of soft monomer butyl acrylate, 2.59 parts of phosphorus-containing monomer prepolymer obtained in step (1), 1.36 parts of glycidyl methacrylate, and 0.95 parts of acrylic acid, and stirring uniformly to obtain a pre-emulsion;

[0048] (4) adding 4.5 wt% of the pre-emulsion to a reactor, adding 0.3 parts of sodium persulfate, and carrying out polymerization for 10 minutes;

[0049] (5) The remaining pre-emulsion and an aqueous solution of ammonium persulfate (0.35 parts of ammonium persulfate dissolved in 3 parts of water) were simultaneously added dropwise to the reaction kettle within 3.5 hours. After the addition was completed, the mixture was kept warm for 30 minutes to obtain a flame-retardant acrylic polymer a.

[0050] [Preparation Example 5] Preparation of flame-retardant acrylic polymer b

[0051] The preparation steps of flame retardant acrylic polymer are as follows:

[0052] (1) Preparing a phosphorus-containing monomer prepolymer: First, 5.6 parts of melamine polyphosphate and 15 parts of dichloromethane were added to a reaction kettle by weight, and 4.8 parts of hydroxyethyl acrylate and 5.4 parts of triethylamine were added dropwise at 0° C. After the addition was complete, the mixture was reacted for 2 hours, and then 2 parts of triethylamine was added and kept for 2 hours to obtain a light yellow transparent liquid phosphorus-containing monomer prepolymer;

[0053] (2) adding 32 parts of water and 2.2 parts of sodium dodecylbenzene sulfonate by weight into a reaction kettle, stirring and heating to 85° C. to obtain a bottom liquid;

[0054] (3) adding 31 parts of water and 3.1 parts of sodium succinate sulfonate by weight into an emulsification tank and stirring, then adding 3.5 parts of hard monomer styrene, 37 parts of soft monomer butyl acrylate, 2.59 parts of phosphorus-containing monomer prepolymer obtained in step (1), 1.36 parts of glycidyl methacrylate, and 0.95 parts of acrylic acid, and stirring uniformly to obtain a pre-emulsion;

[0055] (4) adding 4 wt% of the pre-emulsion to a reactor, adding 0.3 parts of sodium persulfate, and carrying out polymerization reaction for 10 minutes;

[0056] (5) The remaining pre-emulsion and an aqueous solution of ammonium persulfate (0.35 parts of ammonium persulfate dissolved in 3 parts of water) were simultaneously added dropwise to the reaction kettle within 3 hours. After the addition was completed, the mixture was kept warm for 30 minutes to obtain a flame-retardant acrylic polymer b.

[0057] [Preparation Example 6] Preparation of flame-retardant acrylic polymer c

[0058] The preparation steps of flame retardant acrylic polymer are as follows:

[0059] (1) Preparing a phosphorus-containing monomer prepolymer: First, 5.6 parts of melamine polyphosphate and 18 parts of dichloromethane were added to a reaction kettle by weight, and 4.8 parts of hydroxyethyl acrylate and 5.4 parts of triethylamine were added dropwise at 0° C. After the addition was complete, the mixture was reacted for 3 hours, and then 3 parts of triethylamine was added and kept for 2 hours to obtain a light yellow transparent liquid phosphorus-containing monomer prepolymer;

[0060] (2) adding 36 parts of water and 2.2 parts of sodium dodecylbenzene sulfonate by weight into a reaction kettle, stirring and heating to 85° C. to obtain a bottom liquid;

[0061] (3) adding 43 parts of water and 3.1 parts of sodium succinate sulfonate by weight into an emulsification tank and stirring, then adding 3.5 parts of hard monomer styrene, 37 parts of soft monomer butyl acrylate, 2.59 parts of phosphorus-containing monomer prepolymer obtained in step (1), 1.36 parts of glycidyl methacrylate, and 0.95 parts of acrylic acid, and stirring uniformly to obtain a pre-emulsion;

[0062] (4) adding 5 wt% of the total amount of the pre-emulsion into a reactor, adding 0.3 parts of sodium persulfate, and carrying out polymerization reaction for 10 minutes;

[0063] (5) The remaining pre-emulsion and an aqueous solution of ammonium persulfate (0.35 parts of ammonium persulfate dissolved in 3 parts of water) were simultaneously added dropwise to the reaction kettle within 3 hours. After the addition was completed, the mixture was kept warm for 45 minutes to obtain a flame-retardant acrylic polymer c.

[0064] [Preparation Example 7] Preparation of Acrylate Polymer a1

[0065] Compared with the flame retardant acrylate polymer a, no phosphorus-containing monomer prepolymer is added, and the preparation steps are as follows:

[0066] (1) adding 35 parts of water and 2.2 parts of sodium dodecylbenzene sulfonate by weight into a reaction kettle, stirring and heating to 85° C. to obtain a bottom liquid;

[0067] (2) adding 42 parts of water and 3.1 parts of sodium succinate sulfonate by weight into an emulsification tank and stirring, then adding 3.5 parts of hard monomer styrene, 37 parts of soft monomer butyl acrylate, 1.36 parts of glycidyl methacrylate, and 0.95 parts of acrylic acid, and stirring evenly to prepare a pre-emulsion;

[0068] (3) adding 4.5 wt% of the pre-emulsion to a reactor, adding 0.3 parts of sodium persulfate, and carrying out polymerization for 10 minutes;

[0069] (4) The remaining pre-emulsion and an aqueous solution of ammonium persulfate (0.35 parts of ammonium persulfate dissolved in 3 parts of water) were simultaneously added dropwise to the reaction kettle over a period of 3.5 hours. After the addition was completed, the mixture was kept warm for 30 minutes to obtain an acrylate polymer a1.

[0070] [Preparation Example 8] Preparation of flame-retardant acrylic polymer a2

[0071] Compared with the flame-retardant acrylate polymer a, the monomer glycidyl methacrylate is not added, and the rest is the same as that of Preparation Example 4.

[0072] The specific information of each raw material in the above preparation example is as follows:

[0073] Sodium dodecylbenzenesulfonate, CAS number: 25155-30-0;

[0074] Sodium octyl succinate sulfonate, CAS number: 577-11-7;

[0075] Butyl acrylate, CAS number: 141-32-2;

[0076] Glycidyl methacrylate, CAS No.: 106-91-2;

[0077] Acrylic acid, CAS No.: 90598-46-2;

[0078] Sodium persulfate, CAS number: 7775-27-1;

[0079] Ammonium persulfate, CAS number: 7727-54-0;

[0080] Styrene, CAS No.: 100-42-5;

[0081] Melamine polyphosphate, CAS No.: 15541-60-3;

[0082] Dichloromethane, CAS number: 75-09-2;

[0083] Hydroxyethyl acrylate, CAS No.: 818-61-1;

[0084] Triethylamine, CAS number: 121-44-8;

[0085] Low molecular weight polyisobutylene, using PB1300 from Daelim of South Korea;

[0086] High molecular weight polyisobutylene, Oppanol B 200 from BASF;

[0087] Xylene, CAS No.: 1330-20-7;

[0088] Melamine, CAS number: 108-78-1;

[0089] Benzoyl peroxide, CAS number: 94-36-0;

[0090] The water mentioned above is all deionized water, and other raw materials or reagents, unless otherwise specified, can be purchased from commercial sources.

[0091] [Example 1]

[0092] The heat-resistant and flame-retardant double-sided butyl adhesive material is prepared according to the following method:

[0093] (1) Preparation of flame-retardant butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 1 for specific components): 100 parts of butyl rubber matrix, 166 parts of modified polyisobutylene, 38 parts of flame-retardant acrylate polymer, 39 parts of tackifier, 20 parts of vulcanizer, 65 parts of nano flame-retardant fiber material, and 7 parts of additives. Add all the raw materials into a rubber mixer and mix them evenly. Mix them under a vacuum condition of about -0.1 MPa and a temperature of 80°C for 2 hours, and naturally cool to room temperature to obtain a flame-retardant butyl adhesive layer.

[0094] (2) uniformly extruding the flame retardant butyl adhesive layer through an extruder and coating it on the isolation layer at the mouth of the molding die, wherein the thickness of the flame retardant butyl adhesive layer is 0.3 mm;

[0095] (3) The release paper of the isolation layer is attached to the surface of the flame-retardant butyl adhesive layer, and the flame-retardant double-sided butyl adhesive material is obtained by pressing and laminating with a double-roller machine, automatically rolling up after cooling, and slitting into shape (see Figure 1 ).

[0096] [Example 2]

[0097] The heat-resistant and flame-retardant double-sided butyl adhesive material is prepared according to the following method:

[0098] (1) Preparation of flame-retardant butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 1 for specific components): 100 parts of butyl rubber matrix, 154 parts of modified polyisobutylene, 36 parts of flame-retardant acrylate polymer, 35 parts of tackifier, 15 parts of vulcanizer, 55 parts of nano flame-retardant fiber material, and 5 parts of additives. Add all the raw materials into a rubber mixer and mix them evenly. Mix them under a vacuum condition of about -0.1 MPa and a temperature of 80°C for 2 hours, and naturally cool to room temperature to obtain a flame-retardant butyl adhesive layer.

[0099] (2) uniformly extruding the flame retardant butyl adhesive layer through an extruder and coating it on the isolation layer at the mouth of the molding die, wherein the thickness of the flame retardant butyl adhesive layer is 0.3 mm;

[0100] (3) The isolation layer release paper is laminated on the surface of the flame-retardant butyl adhesive layer, and the laminate is pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a flame-retardant double-sided butyl adhesive material.

[0101] [Example 3]

[0102] The heat-resistant and flame-retardant double-sided butyl adhesive material is prepared according to the following method:

[0103] (1) Preparation of flame-retardant butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 1 for specific components): 100 parts of butyl rubber matrix, 176 parts of modified polyisobutylene, 42 parts of flame-retardant acrylate polymer, 40 parts of tackifier, 25 parts of vulcanizer, 75 parts of nano flame-retardant fiber material, and 8 parts of additives. Add all the raw materials into a rubber mixer and mix them evenly. Mix them under a vacuum condition of about -0.1 MPa and a temperature of 80°C for 2 hours, and naturally cool to room temperature to obtain a flame-retardant butyl adhesive layer.

[0104] (2) uniformly extruding the flame retardant butyl adhesive layer through an extruder and coating it on the isolation layer at the mouth of the molding die, wherein the thickness of the flame retardant butyl adhesive layer is 0.3 mm;

[0105] (3) The isolation layer release paper is laminated on the surface of the flame-retardant butyl adhesive layer, and the laminate is pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a flame-retardant double-sided butyl adhesive material.

[0106] [Example 4]

[0107] The heat-resistant and flame-retardant double-sided butyl adhesive material is prepared according to the following method:

[0108] (1) Preparation of flame-retardant butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 1 for specific components): 100 parts of butyl rubber matrix, 169 parts of modified polyisobutylene, 40 parts of flame-retardant acrylate polymer, 37 parts of tackifier, 22 parts of vulcanizer, 71 parts of nano flame-retardant fiber material, and 6 parts of additives. Add all the raw materials into a rubber mixer and mix them evenly. Mix them under a vacuum condition of about -0.1 MPa and a temperature of 80°C for 2 hours, and naturally cool to room temperature to obtain a flame-retardant butyl adhesive layer.

[0109] (2) uniformly extruding the flame retardant butyl adhesive layer through an extruder and coating it on the isolation layer at the mouth of the molding die, wherein the thickness of the flame retardant butyl adhesive layer is 0.3 mm;

[0110] (3) The isolation layer release paper is laminated on the surface of the flame-retardant butyl adhesive layer, and the laminate is pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a flame-retardant double-sided butyl adhesive material.

[0111] [Example 5]

[0112] The heat-resistant and flame-retardant double-sided butyl adhesive material is prepared according to the following method:

[0113] (1) Preparation of flame-retardant butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 1 for specific components): 100 parts of butyl rubber matrix, 170 parts of modified polyisobutylene, 38 parts of flame-retardant acrylate polymer, 38 parts of tackifier, 19 parts of vulcanizer, 68 parts of nano flame-retardant fiber material, and 6.5 parts of additives. Add all the raw materials into a rubber mixer and mix them evenly. Mix them under a vacuum condition of about -0.1 MPa and a temperature of 80°C for 2 hours, and naturally cool to room temperature to obtain a flame-retardant butyl adhesive layer.

[0114] (2) uniformly extruding the flame retardant butyl adhesive layer through an extruder and coating it on the isolation layer at the mouth of the molding die, wherein the thickness of the flame retardant butyl adhesive layer is 0.3 mm;

[0115] (3) The isolation layer release paper is laminated on the surface of the flame-retardant butyl adhesive layer, and the laminate is pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a flame-retardant double-sided butyl adhesive material.

[0116] Table 1

[0117]

[0118] [Comparative Example 1]

[0119] Compared with Example 1, unmodified polyisobutylene was used.

[0120] The heat-resistant and flame-retardant double-sided butyl adhesive material is prepared specifically according to the following method:

[0121] (1) Preparation of flame-retardant butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 2 for specific components): 100 parts of butyl rubber matrix, 166 parts of polyisobutylene (composed of low molecular weight polyisobutylene and high molecular weight polyisobutylene in a weight ratio of 0.6:1.5), 38 parts of flame-retardant acrylate polymer, 39 parts of tackifier, 20 parts of vulcanizer, 65 parts of nano flame-retardant fiber material, and 7 parts of additives. Add all the raw materials into a rubber mixer and mix them evenly. Mix them under a vacuum condition of about -0.1 MPa and a temperature of 80°C for 2 hours, and naturally cool them to room temperature to obtain a flame-retardant butyl adhesive layer.

[0122] (2) uniformly extruding the flame retardant butyl adhesive layer through an extruder and coating it on the isolation layer at the mouth of the molding die, wherein the thickness of the flame retardant butyl adhesive layer is 0.3 mm;

[0123] (3) The isolation layer release paper is laminated on the surface of the flame-retardant butyl adhesive layer, and the laminate is pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a flame-retardant double-sided butyl adhesive material.

[0124] [Comparative Example 2]

[0125] Compared to Example 1, no acrylate polymer was added.

[0126] The heat-resistant and flame-retardant double-sided butyl adhesive material is prepared specifically according to the following method:

[0127] (1) Preparation of flame-retardant butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 2 for specific components): 100 parts of butyl rubber matrix, 166 parts of modified polyisobutylene, 39 parts of tackifier, 20 parts of vulcanizer, 65 parts of nano flame-retardant fiber material, and 7 parts of additives. Add all the raw materials into a rubber mixer and mix them evenly. Mix them at a temperature of 80°C under a vacuum condition of about -0.1 MPa for 2 hours, and naturally cool to room temperature to obtain a flame-retardant butyl adhesive layer.

[0128] (2) uniformly extruding the flame retardant butyl adhesive layer through an extruder and coating it on the isolation layer at the mouth of the molding die, wherein the thickness of the flame retardant butyl adhesive layer is 0.3 mm;

[0129] (3) The isolation layer release paper is laminated on the surface of the flame-retardant butyl adhesive layer, and the laminate is pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a flame-retardant double-sided butyl adhesive material.

[0130] [Comparative Example 3]

[0131] Compared with Example 1, the flame-retardant acrylate polymer a is replaced by acrylate polymer a1.

[0132] The heat-resistant and flame-retardant double-sided butyl adhesive material is prepared specifically according to the following method:

[0133] (1) Preparation of flame-retardant butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 2 for specific components): 100 parts of butyl rubber matrix, 166 parts of modified polyisobutylene, 38 parts of flame-retardant acrylate polymer, 39 parts of tackifier, 20 parts of vulcanizer, 65 parts of nano flame-retardant fiber material, and 7 parts of additives. Add all the raw materials into a rubber mixer and mix them evenly. Mix them under a vacuum condition of about -0.1 MPa and a temperature of 80°C for 2 hours, and naturally cool to room temperature to obtain a flame-retardant butyl adhesive layer.

[0134] (2) uniformly extruding the flame retardant butyl adhesive layer through an extruder and coating it on the isolation layer at the mouth of the molding die, wherein the thickness of the flame retardant butyl adhesive layer is 0.3 mm;

[0135] (3) The isolation layer release paper is laminated on the surface of the flame-retardant butyl adhesive layer, and the laminate is pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a flame-retardant double-sided butyl adhesive material.

[0136] [Comparative Example 4]

[0137] Compared with Example 1, the flame retardant acrylate polymer a is replaced by the flame retardant acrylate polymer a2.

[0138] The heat-resistant and flame-retardant double-sided butyl adhesive material is prepared specifically according to the following method:

[0139] (1) Preparation of flame-retardant butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 2 for specific components): 100 parts of butyl rubber matrix, 166 parts of modified polyisobutylene, 38 parts of flame-retardant acrylate polymer, 39 parts of tackifier, 20 parts of vulcanizer, 65 parts of nano flame-retardant fiber material, and 7 parts of additives. Add all the raw materials into a rubber mixer and mix them evenly. Mix them under a vacuum condition of about -0.1 MPa and a temperature of 80°C for 2 hours, and naturally cool to room temperature to obtain a flame-retardant butyl adhesive layer.

[0140] (2) uniformly extruding the flame retardant butyl adhesive layer through an extruder and coating it on the isolation layer at the mouth of the molding die, wherein the thickness of the flame retardant butyl adhesive layer is 0.3 mm;

[0141] (3) The isolation layer release paper is laminated on the surface of the flame-retardant butyl adhesive layer, and the laminate is pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a flame-retardant double-sided butyl adhesive material.

[0142] [Comparative Example 5]

[0143] Compared with Example 1, no nano flame retardant fiber material is added.

[0144] The heat-resistant and flame-retardant double-sided butyl adhesive material is prepared specifically according to the following method:

[0145] (1) Preparation of flame-retardant butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 2 for specific components): 100 parts of butyl rubber matrix, 166 parts of modified polyisobutylene, 38 parts of flame-retardant acrylate polymer, 39 parts of tackifier, 20 parts of vulcanizer, and 7 parts of additives. Add all the raw materials into a rubber mixer and mix them evenly. Mix them at 80°C under a vacuum condition of about -0.1 MPa for 2 hours, and naturally cool to room temperature to obtain a flame-retardant butyl adhesive layer.

[0146] (2) uniformly extruding the flame retardant butyl adhesive layer through an extruder and coating it on the isolation layer at the mouth of the molding die, wherein the thickness of the flame retardant butyl adhesive layer is 0.3 mm;

[0147] (3) The isolation layer release paper is laminated on the surface of the flame-retardant butyl adhesive layer, and the laminate is pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a flame-retardant double-sided butyl adhesive material.

[0148] Table 2

[0149]

[0150] The specific information of each component in the above embodiments and comparative examples is as follows:

[0151] Chlorobutyl rubber, CAS number: 75214-07-2;

[0152] Terpene resin, CAS number: 9003-74-1;

[0153] C5 petroleum resin, CAS number: 64742-16-1;

[0154] Rosin, CAS No.: 8050-09-7;

[0155] Nano zinc oxide, CAS number: 1314-13-2;

[0156] Antioxidant 1010, CAS No.: 6683-19-8;

[0157] Aramid fiber, CAS number: 308069-56-9;

[0158] Polybenzimidazole, CAS No.: 25928-81-8;

[0159] Release paper, customized by Jiangsu Shengwei New Materials Co., Ltd., with a thickness of 0.1mm.

[0160] Other raw materials or reagents, unless otherwise specified, can be purchased from commercial sources.

[0161]

Performance test

[0162] The relevant properties of the products in the embodiments and comparative examples were tested with reference to the standard JC / T 942-2016.

[0163] 1. Stickiness: record the measured value (min), the standard requirement is ≥20 to pass;

[0164] 2. Heat resistance: record the holding time (h), the time to maintain no flow, cracking, or deformation at 80°C, the standard requirement is ≥2 to pass;

[0165] 3. Low temperature flexibility: record the lowest temperature (℃) at which cracks appear. The standard requires that the product be qualified if there is no crack at -40℃.

[0166] 4. Peel strength: record the measured value (N / mm), the standard requirement is ≥0.4;

[0167] 5. Peel strength retention rate after heat treatment, alkali treatment and water immersion treatment (%): The standard requires ≥80 to be qualified.

[0168] 6. Flammability test: vertical combustion test is carried out according to UL94-2022 test standard, and the RH-6033B horizontal vertical combustion tester is used for testing.

[0169] The experimental test results are detailed in Table 3.

[0170] Table 3

[0171]

[0172] As can be seen from Table 3, the products obtained in Examples 1 to 5 all reached the V-0 flame retardant grade, and at the same time had excellent adhesion, heat resistance, low-temperature flexibility and peel strength. The peel strength retention rate after heat treatment was not less than 90%, and had excellent comprehensive mechanical properties, especially Example 1, which had the best comprehensive performance.

[0173] Comparative Example 1 uses unmodified polyisobutylene, and its comprehensive mechanical properties are better than those of Example 1, but the flame retardant properties of the adhesive material are poor, and the flame retardant grade is reduced to V-3, indicating that the use of flame retardant modified polyisobutylene has a significant effect on improving the flame retardancy of the adhesive material. At the same time, other mechanical properties of the adhesive material are not significantly reduced. The method of grafting nitrogen functional groups on polyisobutylene molecules can effectively avoid the adverse effects of directly adding flame retardants on the mechanical properties of adhesive materials.

[0174] In Comparative Example 2, no acrylic polymer was added, and the mechanical properties were significantly reduced, indicating that the addition of acrylic pressure-sensitive adhesive has a significant improvement effect on the bonding properties, weather resistance, heat resistance, water resistance and other properties of the adhesive material, but the flame retardancy does not change much.

[0175] The acrylate polymer added in Comparative Example 3 does not contain a phosphorus monomer prepolymer, and its comprehensive mechanical properties are equivalent to those of Example 1, but its flame retardancy level is reduced to V-2, indicating that the use of an acrylate polymer containing a phosphorus monomer prepolymer improves the flame retardancy of the adhesive material without significantly reducing the mechanical properties of the adhesive material.

[0176] The acrylic polymer added in Comparative Example 4 does not contain glycidyl methacrylate, and the peel strength retention rate after heat treatment and water immersion treatment is significantly reduced, indicating that glycidyl methacrylate has a promoting effect on improving the moisture and heat resistance of the adhesive material.

[0177] In Comparative Example 5, no nano flame retardant fiber material was added, and the flame retardant grade dropped to V-1, and the adhesive material's adhesion, heat resistance, peel strength, etc. were significantly reduced.

[0178] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A heat-resistant and flame-retardant double-sided butyl adhesive material, comprising a flame-retardant butyl adhesive layer and an isolation layer, characterized in that: The flame retardant butyl adhesive layer comprises the following components in parts by weight: 100 parts of butyl rubber matrix, 154-176 parts of modified polyisobutylene, 36-42 parts of flame retardant acrylate polymer, 35-40 parts of tackifier, 15-25 parts of vulcanizer, 55-75 parts of nano flame retardant fiber material, and 5-8 parts of auxiliary agent; The modified polyisobutylene is a mixture of low molecular weight polyisobutylene grafted with nitrogen functional groups and high molecular weight polyisobutylene, wherein the weight ratio of the low molecular weight polyisobutylene to the high molecular weight polyisobutylene is 0.5-0.8:1-2; The low molecular weight polyisobutylene is low molecular weight polyisobutylene PB1300 produced by Daelim of South Korea; The high molecular weight polyisobutylene is Oppanol B 200 from BASF; The modified polyisobutylene is prepared by the following method: dissolving 1 to 1.5 parts of polyisobutylene in 5 to 6 parts of xylene solvent by weight, adding 0.2 to 0.3 parts of melamine and 0.01 to 0.05 parts of benzoyl peroxide as initiators, stirring evenly, reacting the reaction mixture at 82 to 86° C. for 1 to 2 hours, and separating the product from the solvent after the reaction is completed, namely the modified polyisobutylene; The flame-retardant acrylate polymer is a water-based acrylic pressure-sensitive adhesive containing a phosphorus-based flame retardant, and is prepared by the following method: (1) Add 32-36 parts of water and 2.2 parts of sodium dodecylbenzene sulfonate by weight into a reaction kettle, stir and heat to 85°C to obtain a bottom liquid; (2) Add 31-43 parts of water and 3.1 parts of sodium succinate sulfonate by weight into an emulsification tank and stir, then add 3.5 parts of hard monomer, 37 parts of soft monomer, 2.59 parts of phosphorus-containing monomer prepolymer, 1.36 parts of glycidyl methacrylate and 0.95 parts of acrylic acid, and stir to obtain a pre-emulsion; (3) 4-5 wt% of the total pre-emulsion was added to the reactor, and 0.3 parts of sodium persulfate was added, and the polymerization reaction was carried out for 10-12 minutes; (4) Add the remaining pre-emulsion and 0.35 parts of ammonium persulfate to the reactor simultaneously within 3 to 4 hours, and keep warm for 30 to 45 minutes after the addition is completed to obtain a flame-retardant acrylate polymer; The phosphorus-containing monomer prepolymer is prepared by the following method: first, by weight, 5.6 parts of melamine polyphosphate and 15-18 parts of dichloromethane are added into a reaction kettle, 4.8 parts of hydroxyethyl acrylate and 5.4 parts of triethylamine are added dropwise at 0-4°C, reacted for 2-3 hours after the addition, and then 2-3 parts of triethylamine are added and kept for 1-2 hours to obtain a phosphorus-containing monomer prepolymer.

2. The heat-resistant and flame-retardant double-sided butyl adhesive material according to claim 1, characterized in that: The butyl rubber matrix is ​​selected from one or more of butyl rubber, brominated butyl rubber and chlorinated butyl rubber.

3. The heat-resistant and flame-retardant double-sided butyl adhesive material according to claim 2, characterized in that: The butyl rubber matrix is ​​made of chlorinated butyl rubber.

4. The heat-resistant and flame-retardant double-sided butyl adhesive material according to claim 1, characterized in that: The hard monomer is selected from one or more of styrene, methyl methacrylate, methyl acrylate, and vinyl acetate; The soft monomer is selected from one or more of butyl acrylate, isooctyl acrylate and ethyl acrylate.

5. The heat-resistant and flame-retardant double-sided butyl adhesive material according to claim 4, characterized in that: The hard monomer is styrene; the soft monomer is butyl acrylate.

6. The heat-resistant and flame-retardant double-sided butyl adhesive material according to claim 1, characterized in that: The tackifier is selected from one or more of terpene resin, rosin, and C5 petroleum resin; And / or, the vulcanizing agent is nano zinc oxide.

7. The heat-resistant and flame-retardant double-sided butyl adhesive material according to claim 1, characterized in that: The nano flame retardant fiber material is selected from one or more of aramid fiber, polybenzimidazole fiber, polyimide fiber, phenolic fiber, and polyacrylonitrile pre-oxidized fiber; And / or, the auxiliary agent includes an antioxidant, and the antioxidant is antioxidant 1010.

8. The heat-resistant and flame-retardant double-sided butyl adhesive material according to any one of claims 1 to 7, characterized in that: The flame retardant butyl adhesive layer is prepared by the following method: butyl rubber matrix, polyisobutylene, flame retardant acrylate polymer, tackifier, vulcanizer, modified nano flame retardant fiber material, and additives are added into a rubber mixer and mixed evenly, mixed for 1 to 3 hours under a vacuum condition of -0.06 to -0.1 MPa and a temperature of 60 to 85° C., and naturally cooled to room temperature to obtain the flame retardant butyl adhesive layer.

9. The method for preparing a moisture-heat-resistant and flame-retardant double-sided butyl adhesive material according to claim 1, characterized in that: The following steps are involved: The flame retardant butyl adhesive layer is uniformly extruded through an extruder and coated on the isolation layer at the mouth of a molding die with a thickness of 0.1 to 0.6 mm; the isolation layer is attached to the surface of the flame retardant butyl adhesive layer; the double-roller machine is used for pressing and laminating, automatically rewinding after cooling, and slitting and molding to obtain a moisture-heat resistant flame retardant double-sided butyl adhesive material; The isolation layer comprises release paper with a thickness of 0.05-0.5 mm.

10. The use of a moisture-heat-resistant and flame-retardant double-sided butyl adhesive material as claimed in claim 1, characterized in that: This double-sided butyl adhesive material is used for automotive interior fixing, line interior installation, screen cable fixing, wire and cable fixing, and new energy battery installation.

Images