A pressure-resistant adhesive waterproof sealing material and its preparation method and application

Abstract

The present invention relates to a pressure-resistant adhesive waterproof sealing material and a preparation method and application thereof. The waterproof sealing material comprises a substrate layer, a butyl adhesive layer, and a release film. The butyl adhesive layer comprises the following components in parts by weight: 100 parts of a butyl rubber matrix, 180 to 220 parts of polyisobutylene, 20 to 30 parts of an acrylate polymer, 40 to 45 parts of a tackifier, 15 to 25 parts of a vulcanizing agent, 50 to 80 parts of a modified nano-reinforced filler, and 5 to 8 parts of an auxiliary agent. The present invention improves the high and low temperature resistance, acid and alkali resistance, and wet surface adhesion properties of butyl rubber. The prepared pressure-resistant adhesive waterproof sealing material can be used in ultra-low temperature and high temperature environments through a layer of adhesive layer, and has strong wet adhesion under high water pressure.

Description

Technical Field

[0001] The invention relates to the field of new materials, and in particular to a pressure-resistant adhesive waterproof sealing material and a preparation method and application thereof. Background Art

[0002] Waterproof materials have a wide range of uses, among which butyl rubber waterproof sealing materials have excellent water and air tightness and are suitable for overlapping and sealing of polymer waterproof membranes. They can be used not only for waterproof and airtight joints in color steel plates and construction projects, as well as for sealing seams in subway tunnel structures, but also for waterproof and airtight treatment in the solar energy, lithium battery, and hydrogen power industries. The main body of butyl rubber waterproof sealing materials is usually made of butyl rubber mixed with thermoplastic elastomers and tackifying resins. After heating and mixing, they are made into rollable sheet waterproof materials through processing techniques such as extrusion or calendering. However, butyl rubber has low cohesion, poor heat resistance, poor aging resistance, poor initial adhesion, and low peel strength, and cannot be used in high temperature environments to achieve good waterproof effects. In addition, as a waterproof membrane, it needs to have good water resistance, viscosity (meet the requirements of adhesion under a certain pressure), stability to temperature changes (no flowing, bubbling, or shaking at high temperatures, and no brittle cracking at low temperatures), certain mechanical strength, elongation and fracture resistance, certain flexibility and aging resistance, etc. For example, for use in scenes such as private yachts and private swimming pools, this puts higher requirements on the performance of butyl rubber waterproof sealing tape.

[0003] Patent CN 116515410 B discloses a butyl rubber waterproof sealing adhesive tape, which is used for marine anti-corrosion projects such as pipelines. It prepares a butyl rubber waterproof sealing adhesive layer and an active surface layer, and places a corrosion inhibitor and a rust converter on the active surface layer instead of a butyl rubber waterproof sealing adhesive layer, thereby ensuring that the butyl rubber waterproof sealing adhesive tape has a high concentration of corrosion inhibitor and rust converter in the initial stage of contact with the metal surface, thereby improving the speed and effect of rust removal and corrosion inhibition, ensuring better adhesion between the butyl rubber waterproof sealing adhesive tape and the metal surface, enhancing waterproof sealing and improving adhesion. It is mainly used for metal anti-corrosion, and does not pay attention to performance such as stability of temperature changes and weather resistance. Patent CN 110397222 A discloses a composite roof waterproofing roll, whose self-adhesive layer includes a heat-resistant butyl adhesive layer and a high-viscosity butyl adhesive layer, and the polymer substrate layer, the heat-resistant butyl adhesive layer and the high-viscosity butyl adhesive layer are stacked in sequence. The waterproofing roll achieves heat resistance and high viscosity by respectively setting the heat-resistant butyl adhesive layer and the high-viscosity butyl adhesive layer, and cannot achieve the improvement of comprehensive performance through one adhesive layer, especially it is difficult to take into account the high temperature and high humidity and pressure-resistant adhesion performance. For waterproof materials, special attention should be paid to the sealing performance under certain pressure and high temperature, such as for the repair of leaks in inflatable yachts, kayaks, hovercraft or pipelines, which all have high pressure and are used outdoors. After the waterproof repair material is used, if the adhesion is poor under pressure shock, it is very easy to fall off or leak, and the repair effect cannot be achieved. Summary of the invention

[0004] The purpose of the present invention is to provide a pressure-resistant adhesive waterproof sealing 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 pressure-resistant adhesive waterproof sealing material comprises a substrate layer, a butyl adhesive layer and a release film, wherein the butyl adhesive layer comprises the following components in parts by weight: 100 parts of a butyl rubber matrix, 180-220 parts of polyisobutylene, 20-30 parts of an acrylate polymer, 40-45 parts of a tackifier, 15-25 parts of a vulcanizer, 50-80 parts of a modified nano-reinforced filler and 5-8 parts of an auxiliary agent.

[0007] 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.

[0008] As a preferred embodiment of the present invention, the butyl rubber matrix is ​​made of butyl rubber.

[0009] As a preferred technical solution of the present invention, the polyisobutylene is composed of low molecular weight polyisobutylene, medium molecular weight polyisobutylene and high molecular weight polyisobutylene in a weight ratio of 0.5-0.8:1-2:0.5-0.8.

[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 average number average molecular weight of the medium molecular weight polyisobutylene is 40000 to 95000 g / mol. As a preferred embodiment, BASF's Oppanol B 15N is preferably used;

[0012] 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.

[0013] The invention adopts low, medium and high molecular weight polyisobutylene in a specific ratio, and the prepared sealing adhesive has more excellent comprehensive mechanical properties than single polyisobutylene. Among them, low molecular weight polyisobutylene has good heat resistance, oxygen resistance, acid and alkali resistance and other properties, good compatibility with polymer materials, good compatibility with general non-polar substances, and low temperature dispersibility; medium molecular weight polyisobutylene has acid, alkali, salt resistance, water resistance, ozone resistance and aging resistance, as well as excellent air tightness, and has good compatibility with polyethylene; high molecular weight polyisobutylene is a typical saturated linear polymer, with good heat resistance, light resistance, aging resistance, ideal chemical stability, and still has excellent waterproofness and air tightness at higher temperatures.

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

[0015] (1) adding 30-35 parts of water and 2 parts of sodium dodecylbenzene sulfonate by weight into a reaction kettle, stirring and heating to 85° C. to obtain a bottom liquid;

[0016] (2) adding 30-45 parts of water and 3 parts of sodium succinate sulfonate by weight into an emulsification tank and stirring, then adding 3 parts of hard monomer, 35 parts of soft monomer, 0.55 parts of fluorine-containing monomer, 1.68 parts of glycidyl methacrylate, and 0.76 parts of acrylic acid, and stirring uniformly to prepare a pre-emulsion;

[0017] (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;

[0018] (4) Add the remaining pre-emulsion and 0.35 parts of ammonium persulfate to the reaction kettle simultaneously over 3 to 4 hours, and keep warm for 30 to 45 minutes after the addition is completed to obtain an acrylate polymer.

[0019] 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;

[0020] The soft monomer is selected from one or more of butyl acrylate, isooctyl acrylate, and ethyl acrylate;

[0021] The fluorine-containing monomer is selected from one or more of hexafluorobutyl acrylate, hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate, and octafluoropentyl methacrylate.

[0022] The present invention improves the performance of pressure-resistant adhesive waterproof sealing materials by adding water-based acrylic pressure-sensitive adhesive containing epoxy groups into the butyl adhesive layer, and utilizing the characteristics of acrylic pressure-sensitive adhesive having excellent bonding performance and good interfacial stress dispersion ability to various substrates, as well as weather resistance, heat resistance, no phase separation and migration phenomenon. In the acrylic pressure-sensitive adhesive, the presence of epoxy groups in glycidyl methacrylate opens the epoxy groups in a high temperature and high humidity environment to generate hydrophilic hydroxyl groups, which helps to fit the wet surface, can maintain stable performance in a high temperature environment, and improve the wet surface bonding performance. In the acrylic pressure-sensitive adhesive, the soft monomer is the main component, which provides soft film-forming properties, elongation and adhesion. The acrylic acid containing acryl functional groups reduces the glass transition temperature of the adhesive, increases flexibility, can better adapt to material deformation and expansion in a high temperature and high humidity environment, and remains non-cracking in a low temperature environment. The presence of acrylic acid and glycidyl methacrylate increases the contact area between the adhesive and the substrate, enhances adhesion, and has good bonding properties. In addition, water-based pressure-sensitive adhesives can cause poor wetting on low-surface-energy film materials, which can cause problems in the release film coating process. The present invention introduces a low-surface-energy structure into the main polymer chain segment by introducing a fluorinated monomer, thereby improving the wettability of the adhesive layer on the low-surface-energy surface and satisfying the dispersion and adhesion requirements on the low-surface-energy substrate (PE).

[0023] 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;

[0024] As a preferred technical solution of the present invention, the vulcanizing agent is nano zinc oxide.

[0025] As a preferred technical solution of the present invention, the modified nano-reinforcing filler is nano-calcium carbonate modified by long-chain alkyl alkoxysilane, which is prepared by the following method: adding 20 to 30 parts of nano-calcium carbonate to 100 parts by weight of ethanol, adding 5 to 6 parts by weight of long-chain alkyl alkoxysilane, heating to 40 to 45° C., stirring for 1 to 3 hours, centrifuging, washing, and drying to obtain the modified nano-reinforcing filler;

[0026] The long-chain alkyl alkoxysilane is methyl dodecyl dimethoxysilane;

[0027] The nano calcium carbonate is nano-scale ultrafine calcium carbonate, and the particle size is 1 to 100 nm.

[0028] Calcium carbonate as a reinforcing filler is difficult to disperse evenly when added directly into the glue, and has poor compatibility with polymer materials such as rubber, which can easily cause bulging problems. Long-chain alkyl alkoxysilane has a flexible long chain, which can reduce the surface energy of the filler. The polymer evenly penetrates the surface of the nano filler, and through the entanglement of the long chain and the polymer chain, the compatibility of nano calcium carbonate particles and the glue is improved, so that the nano material can better play the modification effect.

[0029] As a preferred technical solution of the present invention, the auxiliary agent includes an antioxidant and / or an ultraviolet absorber;

[0030] The antioxidant is antioxidant 1010;

[0031] The ultraviolet absorber is benzotriazole.

[0032] As a preferred technical solution of the present invention, the butyl adhesive layer is prepared by the following method: butyl rubber matrix, polyisobutylene, acrylate polymer, tackifier, vulcanizer, modified nano-reinforcement filler, and additives 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 butyl adhesive layer.

[0033] A method for preparing a pressure-resistant adhesive waterproof sealing material comprises the following steps: uniformly extruding a butyl adhesive layer through an extruder and coating it on a substrate layer at the mouth of a molding die, with a thickness of 0.3 to 0.8 mm, preferably 0.4 to 0.45 mm, and laminating an isolation layer on the surface of the butyl adhesive layer; using a double-roller machine to press and grind the composite, automatically rewind after cooling, and slitting and molding to obtain a pressure-resistant adhesive waterproof sealing material;

[0034] The substrate layer comprises a polyethylene film having a thickness of 0.05 to 0.5 mm;

[0035] The isolation layer comprises release paper with a thickness of 0.05 to 0.6 mm, preferably 0.09 to 0.1 mm;

[0036] The total thickness of the sealing adhesive tape is preferably 0.6 to 0.67 mm, for example, 0.6 mm.

[0037] The application of a pressure-resistant adhesive waterproof sealing material (refer to Figure 4 ), this waterproof sealing material is used to repair holes, cracks, gaps, and tears. It is particularly suitable for waterproof repairs with a certain pressure, including downpipes, pipes, ventilation, air-conditioning systems, boats, kayaks, canoes, PVC pipes, swimming pools, etc. When using, tear off the isolation layer and stick it directly.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] The present invention adopts low, medium and high molecular weight polyisobutylene of a specific ratio on the one hand, and combines the advantages of each molecular weight polyisobutylene to improve the low temperature resistance, heat resistance, acid and alkali resistance and other properties of butyl rubber. On the other hand, by adding a water-based acrylic pressure-sensitive adhesive containing an epoxy group, the acrylic pressure-sensitive adhesive has excellent bonding performance and good interfacial stress dispersion ability and heat resistance, no phase separation and migration phenomenon on the substrate, thereby improving the performance of the waterproof sealing material. In addition, the calcium carbonate used as a reinforcing filler has been modified with a long-chain alkyl alkoxysilane to improve the compatibility of nano calcium carbonate particles and the glue, so that the reinforcing filler can play a better role. Through the above improvements, the pressure-resistant adhesive waterproof sealing material prepared by the present invention can be used in ultra-low temperature and high temperature environments through an adhesive layer, has extremely strong wet viscosity, and can withstand strong adhesion of high water pressure. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 is a physical photo of the product related to the present invention;

[0041] Figure 2 and Figure 3 The photos of the test samples before and after the hydraulic test are shown respectively;

[0042] Figure 4 A photograph of the present invention used to repair a hole in a pipeline;

[0043] Figure 5 This is a photo of the hovercraft being repaired. DETAILED DESCRIPTION

[0044] 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.

[0045] [Preparation Example 1] Preparation of Acrylate Polymer a

[0046] The preparation steps of acrylate polymer are as follows:

[0047] (1) adding 33 parts of water and 2 parts of sodium dodecylbenzene sulfonate into a reaction kettle, stirring and heating to 85° C. to obtain a bottom liquid;

[0048] (2) adding 42 parts of water and 3 parts of sodium succinate sulfonate to an emulsifying tank and stirring, then adding 3 parts of methyl methacrylate, 35 parts of butyl acrylate, 0.55 parts of hexafluorobutyl acrylate, 1.68 parts of glycidyl methacrylate, and 0.76 parts of acrylic acid, and stirring uniformly to prepare a pre-emulsion;

[0049] (3) adding 4.2 wt% of the pre-emulsion to a reactor, adding 0.3 parts of sodium persulfate, and carrying out polymerization for about 10 minutes;

[0050] (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 about 3 hours. After the addition was completed, the mixture was kept warm for about 30 minutes to obtain an acrylate polymer a.

[0051] [Preparation Example 2] Preparation of Acrylate Polymer b

[0052] The preparation steps of acrylate polymer are as follows:

[0053] (1) adding 30 parts of water and 2 parts of sodium dodecylbenzene sulfonate into a reaction kettle, stirring and heating to 85° C. to obtain a bottom liquid;

[0054] (2) adding 30 parts of water and 3 parts of sodium succinate sulfonate to an emulsification tank and stirring, then adding 3 parts of styrene, 35 parts of isooctyl acrylate, 0.55 parts of hexafluoroisopropyl acrylate, 1.68 parts of glycidyl methacrylate, and 0.76 parts of acrylic acid, and stirring uniformly to prepare a pre-emulsion;

[0055] (3) adding 4.5 wt% of the pre-emulsion to a reactor, adding 0.3 parts of sodium persulfate, and carrying out polymerization for about 10 minutes;

[0056] (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 about 3.5 hours. After the addition was completed, the mixture was kept warm for about 30 minutes to obtain an acrylate polymer b.

[0057] [Preparation Example 3] Preparation of Acrylate Polymer c

[0058] The preparation steps of acrylate polymer are as follows:

[0059] (1) adding 35 parts of water and 2 parts of sodium dodecylbenzene sulfonate into a reaction kettle, stirring and heating to 85° C. to obtain a bottom liquid;

[0060] (2) adding 40 parts of water and 3 parts of sodium succinate sulfonate to an emulsifying tank and stirring, then adding 1 part of styrene, 2 parts of methyl methacrylate, 20 parts of butyl acrylate, 15 parts of isooctyl acrylate, 0.55 parts of hexafluoroisopropyl acrylate, 1.68 parts of glycidyl methacrylate, and 0.76 parts of acrylic acid, and stirring uniformly to obtain a pre-emulsion;

[0061] (3) 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 about 10 minutes;

[0062] (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 about 3.5 hours. After the addition was completed, the mixture was kept warm for about 30 minutes to obtain an acrylate polymer c.

[0063] [Preparation Example 4] Preparation of Acrylate Polymer d

[0064] The preparation steps of acrylate polymer are as follows:

[0065] (1) adding 33 parts of water and 2 parts of sodium dodecylbenzene sulfonate into a reaction kettle, stirring and heating to 85° C. to obtain a bottom liquid;

[0066] (2) adding 38 parts of water and 3 parts of sodium succinate sulfonate to an emulsification tank and stirring, then adding 3 parts of styrene, 35 parts of butyl acrylate, 0.55 parts of hexafluoroisopropyl acrylate, 1.68 parts of glycidyl methacrylate, and 0.76 parts of acrylic acid, and stirring uniformly to obtain a pre-emulsion;

[0067] (3) adding 4 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 about 10 minutes;

[0068] (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 about 4 hours. The mixture was kept warm for about 45 minutes after the addition was completed to obtain an acrylate polymer d.

[0069] [Preparation Example 5] Preparation of modified nano-reinforced filler a

[0070] The modified nano-reinforcing filler is prepared by the following method: 25 parts of nano-calcium carbonate are added to 100 parts by weight of ethanol, 5 parts by weight of methyl dodecyl dimethoxy silane are added, the mixture is heated to about 40°C, stirred for 2 hours, centrifuged, washed with ethanol, and dried to obtain the modified nano-reinforcing filler a.

[0071] [Preparation Example 6] Preparation of modified nano-reinforced filler b

[0072] The modified nano-reinforced filler was prepared by the following method: 28 parts of nano-calcium carbonate were added to 100 parts by weight of ethanol, 6 parts by weight of methyl dodecyl dimethoxy silane were added, the mixture was heated to about 45°C, stirred for 3 hours, centrifuged, washed with ethanol, and dried to obtain the modified nano-reinforced filler b.

[0073] [Preparation Example 7] Preparation of Acrylate Polymer c1

[0074] Compared with acrylate polymer c, the monomer in step (2) does not contain glycidyl methacrylate, and the rest is the same as that in preparation example 3.

[0075] [Preparation Example 8] Preparation of Acrylate Polymer c2

[0076] Compared with acrylate polymer c, the monomer in step (2) does not contain hexafluoroisopropyl acrylate, and the rest is the same as that in preparation example 3.

[0077] The specific raw material information in the above preparation example is:

[0078] Sodium dodecylbenzenesulfonate, CAS number: 25155-30-0;

[0079] Sodium octyl succinate sulfonate, CAS number: 577-11-7;

[0080] Methyl methacrylate, CAS number: 80-62-6;

[0081] Butyl acrylate, CAS number: 141-32-2;

[0082] Hexafluorobutyl acrylate, CAS No.: 54052-90-3;

[0083] Glycidyl methacrylate, CAS No.: 106-91-2;

[0084] Acrylic acid, CAS No.: 90598-46-2;

[0085] Sodium persulfate, CAS number: 7775-27-1;

[0086] Ammonium persulfate, CAS number: 7727-54-0;

[0087] Styrene, CAS No.: 100-42-5;

[0088] 2-Ethylhexyl acrylate, CAS No.: 29590-42-9;

[0089] Hexafluoroisopropyl acrylate, CAS No.: 2160-89-6;

[0090] Nano calcium carbonate, CAS number: 471-34-1;

[0091] Ethanol, CAS No.: 64-17-5;

[0092] Methyldodecyldimethoxysilane, CAS No.: 66604-31-7;

[0093] The water mentioned above is all deionized water, and other raw materials or reagents, unless otherwise specified, can be purchased from commercial sources.

[0094] [Example 1]

[0095] The pressure-resistant adhesive waterproof sealing material is prepared as follows:

[0096] (1) Preparation of butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 1 for specific components): 100 parts of butyl rubber matrix, 200 parts of polyisobutylene (composed of low molecular weight polyisobutylene, medium molecular weight polyisobutylene and high molecular weight polyisobutylene in a weight ratio of 0.5:1:0.5), 25 parts of acrylate polymer, 42 parts of tackifier, 20 parts of vulcanizer, 60 parts of modified nano-reinforced filler, 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 h, and naturally cool to room temperature to obtain a butyl adhesive layer.

[0097] (2) uniformly extruding the butyl adhesive layer through an extruder and coating it on the polyethylene film substrate layer at the mouth of a molding die, wherein the polyethylene film has a thickness of 0.1 mm and the butyl adhesive layer has a thickness of 0.4 mm;

[0098] (3) The isolation layer release paper is attached to the surface of the butyl adhesive layer, and the two rollers are passed through a double roller machine for pressing and laminating, and the two rollers are automatically rolled up after cooling, and the two rollers are cut into pieces to obtain a pressure-resistant adhesive waterproof sealing material (refer to Figure 1 ).

[0099] [Example 2]

[0100] The pressure-resistant adhesive waterproof sealing material is prepared as follows:

[0101] (1) Preparation of butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 1 for specific components): 100 parts of butyl rubber matrix, 180 parts of polyisobutylene (composed of low molecular weight polyisobutylene, medium molecular weight polyisobutylene and high molecular weight polyisobutylene in a weight ratio of 0.5:2:0.5), 20 parts of acrylate polymer, 40 parts of tackifier, 15 parts of vulcanizer, 50 parts of modified nano-reinforced filler, 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 h, and naturally cool to room temperature to obtain a butyl adhesive layer.

[0102] (2) uniformly extruding the butyl adhesive layer through an extruder and coating it on the polyethylene film substrate layer at the mouth of a molding die, wherein the polyethylene film has a thickness of 0.1 mm and the butyl adhesive layer has a thickness of 0.4 mm;

[0103] (3) The isolation layer release paper is attached to the surface of the butyl adhesive layer, and the two layers are pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a pressure-resistant adhesive waterproof sealing material.

[0104] [Example 3]

[0105] The pressure-resistant adhesive waterproof sealing material is prepared as follows:

[0106] (1) Preparation of butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 1 for specific components): 100 parts of butyl rubber matrix, 220 parts of polyisobutylene (composed of low molecular weight polyisobutylene, medium molecular weight polyisobutylene and high molecular weight polyisobutylene in a weight ratio of 0.6:1.5:0.6), 30 parts of acrylate polymer, 45 parts of tackifier, 25 parts of vulcanizer, 80 parts of modified nano-reinforced filler, 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 h, and naturally cool to room temperature to obtain a butyl adhesive layer.

[0107] (2) uniformly extruding the butyl adhesive layer through an extruder and coating it on the polyethylene film substrate layer at the mouth of a molding die, wherein the polyethylene film has a thickness of 0.1 mm and the butyl adhesive layer has a thickness of 0.4 mm;

[0108] (3) The isolation layer release paper is attached to the surface of the butyl adhesive layer, and the two layers are pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a pressure-resistant adhesive waterproof sealing material.

[0109] [Example 4]

[0110] The pressure-resistant adhesive waterproof sealing material is prepared as follows:

[0111] (1) Preparation of butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 1 for specific components): 100 parts of butyl rubber matrix, 210 parts of polyisobutylene (composed of low molecular weight polyisobutylene, medium molecular weight polyisobutylene and high molecular weight polyisobutylene in a weight ratio of 0.6:1.7:0.7), 26 parts of acrylate polymer, 41 parts of tackifier, 18 parts of vulcanizer, 55 parts of modified nano-reinforced filler, 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 h, and naturally cool to room temperature to obtain a butyl adhesive layer.

[0112] (2) uniformly extruding the butyl adhesive layer through an extruder and coating it on the polyethylene film substrate layer at the mouth of a molding die, wherein the polyethylene film has a thickness of 0.1 mm and the butyl adhesive layer has a thickness of 0.4 mm;

[0113] (3) The isolation layer release paper is attached to the surface of the butyl adhesive layer, and the two layers are pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a pressure-resistant adhesive waterproof sealing material.

[0114] [Example 5]

[0115] The pressure-resistant adhesive waterproof sealing material is prepared as follows:

[0116] (1) Preparation of butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 1 for specific components): 100 parts of butyl rubber matrix, 215 parts of polyisobutylene (composed of low molecular weight polyisobutylene, medium molecular weight polyisobutylene and high molecular weight polyisobutylene in a weight ratio of 0.7:2:0.8), 27 parts of acrylate polymer, 43 parts of tackifier, 23 parts of vulcanizer, 65 parts of modified nano-reinforced filler, 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 h, and naturally cool to room temperature to obtain a butyl adhesive layer.

[0117] (2) uniformly extruding the butyl adhesive layer through an extruder and coating it on the polyethylene film substrate layer at the mouth of a molding die, wherein the polyethylene film has a thickness of 0.1 mm and the butyl adhesive layer has a thickness of 0.4 mm;

[0118] (3) The isolation layer release paper is attached to the surface of the butyl adhesive layer, and the two layers are pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a pressure-resistant adhesive waterproof sealing material.

[0119] [Example 6]

[0120] The pressure-resistant adhesive waterproof sealing material is prepared as follows:

[0121] (1) Preparation of butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 1 for specific components): 100 parts of butyl rubber matrix, 195 parts of polyisobutylene (composed of low molecular weight polyisobutylene, medium molecular weight polyisobutylene and high molecular weight polyisobutylene in a weight ratio of 0.8:1:0.8), 28 parts of acrylate polymer, 44 parts of tackifier, 24 parts of vulcanizer, 66 parts of modified nano-reinforced filler, 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 h, and naturally cool to room temperature to obtain a butyl adhesive layer.

[0122] (2) uniformly extruding the butyl adhesive layer through an extruder and coating it on the polyethylene film substrate layer at the mouth of a molding die, wherein the polyethylene film has a thickness of 0.1 mm and the butyl adhesive layer has a thickness of 0.4 mm;

[0123] (3) The isolation layer release paper is attached to the surface of the butyl adhesive layer, and the two layers are pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a pressure-resistant adhesive waterproof sealing material.

[0124] Table 1

[0125]

[0126]

[0127] [Comparative Example 1]

[0128] Compared to Example 3, a single source of polyisobutylene was used.

[0129] The pressure-resistant adhesive waterproof sealing material is prepared specifically according to the following method:

[0130] (1) Preparation of butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 2 for specific components): 100 parts of butyl rubber matrix, 220 parts of polyisobutylene, 30 parts of acrylate polymer, 45 parts of tackifier, 25 parts of vulcanizer, 80 parts of modified nano-reinforced filler, 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 h, and naturally cool to room temperature to obtain a butyl adhesive layer.

[0131] (2) uniformly extruding the butyl adhesive layer through an extruder and coating it on the polyethylene film substrate layer at the mouth of a molding die, wherein the polyethylene film has a thickness of 0.1 mm and the butyl adhesive layer has a thickness of 0.4 mm;

[0132] (3) The isolation layer release paper is attached to the surface of the butyl adhesive layer, and the two layers are pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a pressure-resistant adhesive waterproof sealing material.

[0133] [Comparative Example 2]

[0134] Compared to Example 3, no acrylate polymer was added.

[0135] The pressure-resistant adhesive waterproof sealing material is prepared specifically according to the following method:

[0136] (1) Preparation of butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 2 for specific components): 100 parts of butyl rubber matrix, 220 parts of polyisobutylene (composed of low molecular weight polyisobutylene, medium molecular weight polyisobutylene and high molecular weight polyisobutylene in a weight ratio of 0.6:1.5:0.6), 45 parts of tackifier, 25 parts of vulcanizer, 80 parts of modified nano-reinforced filler, 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 h, and naturally cool to room temperature to obtain a butyl adhesive layer.

[0137] (2) uniformly extruding the butyl adhesive layer through an extruder and coating it on the polyethylene film substrate layer at the mouth of a molding die, wherein the polyethylene film has a thickness of 0.1 mm and the butyl adhesive layer has a thickness of 0.4 mm;

[0138] (3) The isolation layer release paper is attached to the surface of the butyl adhesive layer, and the two layers are pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a pressure-resistant adhesive waterproof sealing material.

[0139] [Comparative Example 3]

[0140] Compared with Example 3, the acrylate polymer c is replaced by the acrylate polymer c1.

[0141] The pressure-resistant adhesive waterproof sealing material is prepared specifically according to the following method:

[0142] (1) Preparation of butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 2 for specific components): 100 parts of butyl rubber matrix, 220 parts of polyisobutylene (composed of low molecular weight polyisobutylene, medium molecular weight polyisobutylene and high molecular weight polyisobutylene in a weight ratio of 0.6:1.5:0.6), 30 parts of acrylate polymer, 45 parts of tackifier, 25 parts of vulcanizer, 80 parts of modified nano-reinforced filler, 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 h, and naturally cool to room temperature to obtain a butyl adhesive layer.

[0143] (2) uniformly extruding the butyl adhesive layer through an extruder and coating it on the polyethylene film substrate layer at the mouth of a molding die, wherein the polyethylene film has a thickness of 0.1 mm and the butyl adhesive layer has a thickness of 0.4 mm;

[0144] (3) The isolation layer release paper is attached to the surface of the butyl adhesive layer, and the two layers are pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a pressure-resistant adhesive waterproof sealing material.

[0145] [Comparative Example 4]

[0146] Compared with Example 3, the acrylate polymer c is replaced by the acrylate polymer c2.

[0147] The pressure-resistant adhesive waterproof sealing material is prepared specifically according to the following method:

[0148] (1) Preparation of butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 2 for specific components): 100 parts of butyl rubber matrix, 220 parts of polyisobutylene (composed of low molecular weight polyisobutylene, medium molecular weight polyisobutylene and high molecular weight polyisobutylene in a weight ratio of 0.6:1.5:0.6), 30 parts of acrylate polymer, 45 parts of tackifier, 25 parts of vulcanizer, 80 parts of modified nano-reinforced filler, 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 h, and naturally cool to room temperature to obtain a butyl adhesive layer.

[0149] (2) uniformly extruding the butyl adhesive layer through an extruder and coating it on the polyethylene film substrate layer at the mouth of a molding die, wherein the polyethylene film has a thickness of 0.1 mm and the butyl adhesive layer has a thickness of 0.4 mm;

[0150] (3) The isolation layer release paper is attached to the surface of the butyl adhesive layer, and the two layers are pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a pressure-resistant adhesive waterproof sealing material.

[0151] [Comparative Example 5]

[0152] Compared with Example 3, no nano reinforcing filler is added.

[0153] The pressure-resistant adhesive waterproof sealing material is prepared specifically according to the following method:

[0154] (1) Preparation of butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 2 for specific components): 100 parts of butyl rubber matrix, 220 parts of polyisobutylene (composed of low molecular weight polyisobutylene, medium molecular weight polyisobutylene and high molecular weight polyisobutylene in a weight ratio of 0.6:1.5:0.6), 30 parts of acrylate polymer, 45 parts of tackifier, 25 parts of vulcanizer, and 8 parts of additive. 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 h, and naturally cool to room temperature to obtain a butyl adhesive layer.

[0155] (2) uniformly extruding the butyl adhesive layer through an extruder and coating it on the polyethylene film substrate layer at the mouth of a molding die, wherein the polyethylene film has a thickness of 0.1 mm and the butyl adhesive layer has a thickness of 0.4 mm;

[0156] (3) The isolation layer release paper is attached to the surface of the butyl adhesive layer, and the two layers are pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a pressure-resistant adhesive waterproof sealing material.

[0157] [Comparative Example 6]

[0158] Compared with Example 3, 80 parts of the modified nano reinforcing filler are replaced by unmodified common nano calcium carbonate.

[0159] The pressure-resistant adhesive waterproof sealing material is prepared specifically according to the following method:

[0160] (1) Preparation of butyl adhesive layer. Prepare the raw materials according to the following formula (see Table 2 for specific components): 100 parts of butyl rubber matrix, 220 parts of polyisobutylene (composed of low molecular weight polyisobutylene, medium molecular weight polyisobutylene and high molecular weight polyisobutylene in a weight ratio of 0.6:1.5:0.6), 30 parts of acrylate polymer, 45 parts of tackifier, 25 parts of vulcanizer, 80 parts of nano-reinforcement filler, 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 h, and naturally cool to room temperature to obtain a butyl adhesive layer.

[0161] (2) uniformly extruding the butyl adhesive layer through an extruder and coating it on the polyethylene film substrate layer at the mouth of a molding die, wherein the polyethylene film has a thickness of 0.1 mm and the butyl adhesive layer has a thickness of 0.4 mm;

[0162] (3) The isolation layer release paper is attached to the surface of the butyl adhesive layer, and the two layers are pressed and laminated by a double-roller machine, and automatically rolled up after cooling, and cut into pieces to obtain a pressure-resistant adhesive waterproof sealing material.

[0163] Table 2

[0164]

[0165]

[0166] The specific information of each component in the above embodiments and comparative examples is as follows:

[0167] Butyl rubber, copolymer of isoprene and isobutyl, CAS number: 9010-85-9;

[0168] Low molecular weight polyisobutylene, using PB1300 from Daelim of South Korea;

[0169] Medium molecular weight polyisobutylene, Oppanol B 15N from BASF;

[0170] High molecular weight polyisobutylene, Oppanol B 200 from BASF;

[0171] Terpene resin, CAS number: 9003-74-1;

[0172] C5 petroleum resin, CAS number: 64742-16-1;

[0173] Rosin, CAS No.: 8050-09-7;

[0174] Nano zinc oxide, CAS number: 1314-13-2;

[0175] Antioxidant 1010, CAS No.: 6683-19-8;

[0176] Benzotriazole, CAS number: 27556-51-0;

[0177] Polyethylene film, customized by Guangdong Changtuniu Film Technology Co., Ltd., thickness 0.1mm.

[0178] Release paper, customized by Jiangsu Shengwei New Materials Co., Ltd., with a thickness of 0.1mm.

[0179] Other raw materials or reagents, unless otherwise specified, can be purchased from commercial sources.

[0180]

Performance test

[0181] The relevant properties of the products in the examples and comparative examples were tested with reference to JC / T 942-2016 "Butyl Rubber Waterproof Sealing Adhesive Tape".

[0182] 1. Stickiness: record the measured value (min), the standard requirement is ≥20 to pass;

[0183] 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;

[0184] 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℃.

[0185] 4. Peel strength: record the measured value (N / mm), the standard requirement is ≥0.4;

[0186] 5. Peel strength retention rate after heat treatment, alkali treatment and water immersion treatment (%): The standard requires ≥80 to be qualified.

[0187] 6. According to GB / T 15560-1995, use the pipeline hydraulic resistance tester to conduct a short-time hydraulic test (refer to Figure 2 , Figure 3 ), the hydraulic pressure is 0.494MPa, and the hydraulic failure time (s) is recorded. ≥3s is qualified.

[0188] The experimental test results are detailed in Table 3.

[0189] Table 3

[0190]

[0191] As can be seen from Table 1, the products obtained in Examples 1 to 6 have excellent comprehensive mechanical properties, especially Example 3, which has the best performance.

[0192] Comparative Example 1 uses only medium molecular weight polyisobutylene, and the heat resistance, low temperature flexibility, peel strength are significantly reduced, and the heat resistance and alkali resistance are reduced, indicating that the addition of low molecular weight polyisobutylene and high molecular weight polyisobutylene has a great influence on improving the performance of butyl tape.

[0193] In Comparative Example 2, no acrylic polymer was added, and the properties decreased significantly, indicating that the addition of acrylic pressure-sensitive adhesive has a significant improvement effect on the bonding performance, weather resistance, heat resistance, water resistance and other properties of the butyl tape.

[0194] In comparative example 3, acrylate polymer c is replaced by acrylate polymer c1 which does not contain glycidyl methacrylate raw material. The peel strength retention rate after heat treatment and water immersion treatment is significantly reduced, and the pressure resistance is reduced, indicating that glycidyl methacrylate can improve the high temperature and wet surface bonding performance of butyl tape.

[0195] In comparative example 4, acrylate polymer c is replaced with acrylate polymer c2 which does not contain hexafluoroisopropyl acrylate as raw material. The adhesion and peel strength decrease, and the pressure resistance decreases significantly, indicating that hexafluoroisopropyl acrylate can improve the adhesion and peel strength of butyl tape.

[0196] In Comparative Example 5, no nano-reinforcing filler is added, and the adhesion, heat resistance, peel strength and pressure resistance of the butyl tape are significantly reduced, and the heat resistance does not meet the requirements, indicating that filling with reinforcing fillers is necessary for the butyl tape.

[0197] In Comparative Example 6, unmodified common nano-reinforcing filler was added. Compared with Example 3, the adhesion, peel strength, and pressure resistance of the butyl tape were all reduced, indicating that the modified nano-calcium carbonate significantly improved the performance of the butyl tape.

[0198] 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 pressure-resistant adhesive waterproof sealing material, comprising a substrate layer, a butyl adhesive layer, and a release film, characterized in that: The butyl adhesive layer comprises the following components in parts by weight: 100 parts of butyl rubber matrix, 180-220 parts of polyisobutylene, 20-30 parts of acrylate polymer, 40-45 parts of tackifier, 15-25 parts of vulcanizer, 50-80 parts of modified nano-reinforced filler, and 5-8 parts of auxiliary agent; The polyisobutylene is composed of low molecular weight polyisobutylene, medium molecular weight polyisobutylene and high molecular weight polyisobutylene in a weight ratio of 0.5-0.8:1-2:0.5-0.8; The acrylate polymer is a water-based acrylate pressure-sensitive adhesive containing epoxy groups, which is prepared by the following method: (1) adding 30-35 parts of water and 2 parts of sodium dodecylbenzene sulfonate by weight into a reaction kettle, stirring and heating to 85° C. to obtain a bottom liquid; (2) adding 30-45 parts of water and 3 parts of sodium succinate sulfonate by weight into an emulsification tank and stirring, then adding 3 parts of hard monomer, 35 parts of soft monomer, 0.55 parts of fluorine-containing monomer, 1.68 parts of glycidyl methacrylate, and 0.76 parts of acrylic acid, and stirring uniformly to prepare a pre-emulsion; (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; (4) adding the remaining pre-emulsion and 0.35 parts of ammonium persulfate to the reaction kettle simultaneously within 3 to 4 hours, and keeping warm for 30 to 45 minutes after the addition is completed, thereby obtaining an acrylate polymer; In the step (2), 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; and the fluorine-containing monomer is selected from one or more of hexafluorobutyl acrylate, hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate, and octafluoropentyl methacrylate.

2. A pressure-resistant adhesive waterproof sealing 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. A pressure-resistant adhesive waterproof sealing 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.

4. A pressure-resistant adhesive waterproof sealing material according to claim 1, characterized in that: The modified nano reinforcing filler is nano calcium carbonate modified by long-chain alkyl alkoxysilane, which is prepared by the following method: adding 20 to 30 parts of nano calcium carbonate to 100 parts by weight of ethanol, adding 5 to 6 parts by weight of long-chain alkyl alkoxysilane, heating to 40 to 45° C., stirring for 1 to 3 hours, centrifuging, washing, and drying to obtain the modified nano reinforcing filler; The long-chain alkyl alkoxysilane is methyl dodecyl dimethoxysilane; The nano calcium carbonate is nano-scale ultrafine calcium carbonate, and the particle size is 1 to 100 nm.

5. The pressure-resistant adhesive waterproof sealing material according to claim 1, characterized in that: The auxiliary agent includes an antioxidant and / or an ultraviolet absorber, The antioxidant is antioxidant 1010; The ultraviolet absorber is benzotriazole.

6. A pressure-resistant adhesive waterproof sealing material according to any one of claims 1 to 5, characterized in that: The butyl adhesive layer is prepared by the following method: butyl rubber matrix, polyisobutylene, acrylate polymer, tackifier, vulcanizer, modified nano-reinforced filler 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 butyl adhesive layer.

7. The method for preparing a pressure-resistant adhesive waterproof sealing material according to claim 1, characterized in that: The following steps are involved: The butyl adhesive layer is uniformly extruded through an extruder and coated on the substrate layer at the mouth of a molding die with a thickness of 0.3 to 0.8 mm; a release film is attached to the surface of the butyl adhesive layer; a double-roller machine is used for pressing and laminating, automatically winding after cooling, and slitting to obtain a pressure-resistant adhesive waterproof sealing material; The substrate layer comprises a polyethylene film having a thickness of 0.05 to 0.5 mm; The release film comprises release paper and has a thickness of 0.05 to 0.6 mm.

8. The use of a pressure-resistant adhesive waterproof sealing material as claimed in claim 1, characterized in that: This waterproof sealant is used to repair holes, cracks, gaps, and tears.

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