Method for preparing acrylic ester pressure-sensitive adhesive modified by functionalized mesoporous material and application thereof

Abstract

The application relates to the technical field of acrylate pressure-sensitive adhesive, and discloses a functionalized mesoporous material modified acrylate pressure-sensitive adhesive, which takes phosphate-isocyanuric ester functionalized mesoporous SiO2 as a composite flame retardant, the phosphate-isocyanuric ester functional group is used as a nitrogen-phosphorus synergistic flame retardant component, under the synergistic action of the mesoporous nano SiO2, the acrylate pressure-sensitive adhesive is endowed with excellent flame retardant performance, and the mesoporous nano SiO2 is used as inorganic nano filler and is uniformly dispersed in the acrylate pressure-sensitive adhesive matrix to form stable physical crosslinking sites, the crosslinking degree and the cohesive strength of molecular chains are improved, the movement of acrylate molecular chains is limited, and the addition of proper mesoporous nano SiO2 can effectively improve the thermal decomposition temperature and the thermal stability of the acrylate pressure-sensitive adhesive, and will not cause influences on the adhesion and the peeling strength of the pressure-sensitive adhesive.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of acrylate pressure sensitive adhesive, in particular to a preparation method and application of a functionalized mesoporous material modified acrylate pressure sensitive adhesive. BACKGROUND

[0002] Acrylate pressure sensitive adhesive is very sensitive to pressure and has excellent bonding performance, and only slight pressure is needed to achieve good adhesion. In addition, acrylate pressure sensitive adhesive has excellent aging resistance and corrosion resistance, and plays an important role in packaging materials, building materials, electronics, transportation and other fields. However, general acrylate pressure sensitive adhesive has poor heat resistance and flame retardance, is prone to burning, and can produce a large amount of toxic smoke, which limits its practical application. Therefore, it is necessary to modify the flame retardance of acrylate pressure sensitive adhesive to improve its flame retardance.

[0003] At present, adding a flame retardant to acrylate pressure sensitive adhesive is an effective method to improve flame retardance. Traditional flame retardants mainly include magnesium hydroxide, halogen-containing flame retardants, silicon-based flame retardants, etc. Nitrogen and phosphorus flame retardants are a class of highly efficient flame retardants, widely used in high molecular materials. In the process of high temperature combustion, or thermal decomposition, oxygen-containing phosphoric acid derivatives, and a large amount of non-combustible gases such as nitrogen and ammonia are produced, which have the effects of promoting carbonization, heat dissipation, and inhibiting combustion. In recent years, mesoporous SiO2 has been found to have broad research prospects in the field of flame retardance due to its high specific surface area and rich pore structure. Therefore, nitrogen and phosphorus flame retardants can be grafted onto the surface of mesoporous SiO2 to obtain functionalized mesoporous SiO2 composite flame retardant, which can be applied to acrylate pressure sensitive adhesive to improve the flame retardance of the pressure sensitive adhesive.

[0004] (I) Technical problems solved

[0005] In view of the deficiencies of the prior art, the present application provides a preparation method and application of a functionalized mesoporous material modified acrylate pressure sensitive adhesive, which has better thermal stability and flame retardance.

[0006] (II) Technical solutions

[0007] To achieve the above-mentioned purpose, the present application provides the following technical solutions: a functionalized mesoporous SiO2 modified acrylate pressure sensitive adhesive, and a preparation method of the functionalized mesoporous SiO2 modified acrylate pressure sensitive adhesive as follows:

[0008] (1) Using hexadecyl trimethyl ammonium bromide as a template agent, mesoporous nano-SiO2 is prepared by alcoholysis-hydrolysis treatment of tetraethyl orthosilicate.

[0009] (2) Add toluene solvent into the reaction flask and purge nitrogen to remove air, add mesoporous nano-SiO2 and isophorone diisocyanate, after uniform dispersion, isocyanate functionalization treatment is carried out, centrifugal separation is used to remove the solvent, the solid product is washed with toluene and acetone respectively, and isocyanate functionalized mesoporous SiO2 is prepared.

[0010] (3) Add methyl ethyl ketone solvent into the reaction flask, after purging nitrogen, add isocyanate functionalized mesoporous SiO2 and tris (2-hydroxyethyl) isocyanurate, after uniform dispersion, add catalyst dibutyl tin dilaurate, isocyanurate functionalization treatment is carried out, centrifugal separation is used to remove the solvent, the solid product is washed with tetrahydrofuran and acetone respectively, and isocyanurate functionalized mesoporous SiO2 is prepared.

[0011] (4) Add pyridine solvent, diphenyloxy phosphoryl chloride and isocyanurate functionalized mesoporous SiO2 into the reaction flask, after uniform dispersion, add catalyst 4-dimethylamino pyridine and promoter triethylamine, phosphate functionalization treatment is carried out, filter the solvent, the solid product is washed with tetrahydrofuran and acetone respectively, and phosphate-isocyanurate functionalized mesoporous SiO2 is prepared.

[0012] (5) Add toluene solvent into the reaction flask, after purging nitrogen, add acrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate and phosphate-isocyanurate functionalized mesoporous SiO2, after uniform dispersion, drop initiator azobisisobutyronitrile, polymerization process is carried out, then add mineral oil defoaming agent and aziridine crosslinking agent, after high speed emulsification, functionalized mesoporous SiO2 modified acrylate pressure sensitive adhesive is obtained.

[0013] Preferably, the mass ratio of mesoporous nano-SiO2 and isophorone diisocyanate in step (2) is 100:120-180.

[0014] Preferably, the temperature of isocyanate functionalization treatment in step (2) is 80-100℃, and the treatment time is 5-10h.

[0015] Preferably, the mass ratio of isocyanate functionalized mesoporous SiO2, tris (2-hydroxyethyl) isocyanurate and dibutyl tin dilaurate in step (3) is 100:85-130:0.2-0.4.

[0016] Preferably, the temperature of isocyanurate functionalization treatment in step (3) is 75-90℃, and the treatment time is 10-20h.

[0017] Preferably, the mass ratio of diphenyloxy phosphoryl chloride, isocyanurate functionalized mesoporous SiO2, 4-dimethylamino pyridine and triethylamine in step (4) is 50-80:100:0.65-1:20-32.

[0018] Preferably, the temperature of the phosphate functionalization treatment in step (4) is 40-60℃, and the treatment time is 24-48h.

[0019] Preferably, the mass ratio of the acrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, phosphate-isocyanurate functionalized mesoporous SiO2, mineral oil defoamer and aziridine crosslinking agent in step (4) is 10-14:25-30:100:30-40:1-4:0.2-0.5:1-3.5.

[0020] Preferably, the temperature of the polymerization process in step (4) is 75-85℃, and the polymerization time is 4-8h.

[0021] (III) Beneficial technical effects

[0022] Compared with the prior art, the present application has the following beneficial technical effects:

[0023] The isocyanate group of the isophorone diisocyanate reacts with the hydroxyl group on the surface of the mesoporous nano-SiO2 to obtain isocyanate functionalized mesoporous SiO2, then under the catalysis of dibutyltin dilaurate, the hydroxyethyl group of tris(2-hydroxyethyl) isocyanurate reacts with the isocyanate group on the surface of the mesoporous SiO2 to obtain isocyanurate functionalized mesoporous SiO2, and finally under the catalysis of 4-dimethylaminopyridine and triethylamine, the hydroxyethyl group of the modified isocyanurate reacts with phosphorus oxychloride to obtain phosphate-isocyanurate functionalized mesoporous SiO2, so that the phosphate and isocyanurate functional groups are covalently bonded to the surface of the mesoporous nano-SiO2, realizing the functionalization modification of the nano-SiO2.

[0024] The functionalized mesoporous SiO2 modified acrylate pressure-sensitive adhesive uses phosphate-isocyanurate functionalized mesoporous SiO2 as a composite flame retardant, and the phosphate-isocyanurate functional group as a nitrogen-phosphorus synergistic flame retardant component, and under the synergistic effect of the mesoporous nano-SiO2, the acrylate pressure-sensitive adhesive is endowed with excellent flame retardant performance, and the mesoporous nano-SiO2 as an inorganic nano-filler is uniformly dispersed in the acrylate pressure-sensitive adhesive matrix to form stable physical crosslinking sites, improve the crosslinking degree and cohesive strength of the molecular chain, and limit the movement of the acrylate molecular chain. The addition of an appropriate amount of mesoporous nano-SiO2 can effectively improve the thermal decomposition temperature and thermal stability of the acrylate pressure-sensitive adhesive, and will not affect the adhesion and peel strength of the pressure-sensitive adhesive. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1is a reaction diagram of isocyanate functionalized mesoporous SiO2 and tri(2-hydroxyethyl) isocyanurate;

[0026] Figure 2 is a reaction diagram of diphenyloxy phosphoryl chloride and isocyanurate functionalized mesoporous SiO2. DETAILED DESCRIPTION

[0027] To achieve the above-mentioned purpose, the present application provides the following specific embodiments and examples: a method for preparing a functionalized mesoporous SiO2 modified acrylate pressure-sensitive adhesive is as follows:

[0028] (1) mesoporous nano-SiO2 is prepared by using hexadecyl trimethyl ammonium bromide as a template agent and tetraethyl orthosilicate through alcoholysis-hydrolysis treatment.

[0029] (2) toluene solvent is added to a reaction flask and nitrogen is introduced to remove air, mesoporous nano-SiO2 and isophorone diisocyanate with a mass ratio of 100:120-180 are added, and after being uniformly dispersed, isocyanate functionalization treatment is carried out at 80-100℃ for 5-10h, the solvent is removed by centrifugal separation, and the solid product is washed with toluene and acetone respectively to prepare isocyanate functionalized mesoporous SiO2.

[0030] (3) methyl ethyl ketone solvent is added to a reaction flask, and after nitrogen is introduced, isocyanate functionalized mesoporous SiO2 and tri(2-hydroxyethyl) isocyanurate are added, and after being uniformly dispersed, a catalyst dibutyl tin dilaurate is added, and the three have a mass ratio of 100:85-130:0.2-0.4, isocyanurate functionalization treatment is carried out at 75-90℃ for 10-20h, the solvent is removed by centrifugal separation, and the solid product is washed with tetrahydrofuran and acetone respectively to prepare isocyanurate functionalized mesoporous SiO2.

[0031] (4) pyridine solvent, diphenyloxy phosphoryl chloride and isocyanurate functionalized mesoporous SiO2 are added to a reaction flask, and after being uniformly dispersed, a catalyst 4-dimethylamino pyridine and a promoter triethylamine are added, and the four have a mass ratio of 50-80:100:0.65-1:20-32, phosphate functionalization treatment is carried out at 40-60℃ for 24-48h, the solvent is filtered, and the solid product is washed with tetrahydrofuran and acetone respectively to prepare phosphate-isocyanurate functionalized mesoporous SiO2.

[0032] (5) Into the reaction flask, toluene solvent was added, and nitrogen was bubbled to remove air. Then, acrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, and phosphate-isocyanurate functionalized mesoporous SiO2 were added. After being uniformly dispersed, initiator azobisisobutyronitrile was added dropwise. The polymerization process was carried out at 75-85°C for 4-8h. Then, mineral oil defoaming agent and aziridine crosslinking agent were added. The mass ratio of acrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, phosphate-isocyanurate functionalized mesoporous SiO2, mineral oil defoaming agent, and aziridine crosslinking agent was 10-14:25-30:100:30-40:1-4:0.2-0.5:1-3.5. After high-speed emulsification, functionalized mesoporous SiO2 modified acrylate pressure-sensitive adhesive was obtained.

[0033] Example 1

[0034] (1) Mesoporous nano-SiO2 was prepared by using cetyltrimethylammonium bromide as a template and tetraethyl orthosilicate through alcoholysis-hydrolysis treatment.

[0035] (2) Into the reaction flask, toluene solvent was added, and nitrogen was bubbled to remove air. Then, mesoporous nano-SiO2 and isophorone diisocyanate were added at a mass ratio of 100:120. After being uniformly dispersed, isocyanate functionalization treatment was carried out at 80°C for 5h. The solvent was removed by centrifugal separation, and the solid product was washed with toluene and acetone, respectively, to obtain isocyanate functionalized mesoporous SiO2.

[0036] (3) Into the reaction flask, methyl ethyl ketone solvent was added, and nitrogen was bubbled to remove air. Then, isocyanate functionalized mesoporous SiO2 and tris(2-hydroxyethyl) isocyanurate were added. After being uniformly dispersed, catalyst dibutyltin dilaurate was added at a mass ratio of 100:85:0.2. Isocyanurate functionalization treatment was carried out at 75°C for 10h. The solvent was removed by centrifugal separation, and the solid product was washed with tetrahydrofuran and acetone, respectively, to obtain isocyanurate functionalized mesoporous SiO2.

[0037] (4) Into the reaction flask, pyridine solvent, diphenyloxyphosphoryl chloride, and isocyanurate functionalized mesoporous SiO2 were added. After being uniformly dispersed, catalyst 4-dimethylaminopyridine and promoter triethylamine were added at a mass ratio of 50:100:0.65:20. Phosphate functionalization treatment was carried out at 40°C for 24h. The solvent was filtered, and the solid product was washed with tetrahydrofuran and acetone, respectively, to obtain phosphate-isocyanurate functionalized mesoporous SiO2.

[0038] (5) Into the reaction flask, toluene solvent was added, and nitrogen was bubbled through to remove air. Acrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, and phosphate-isocyanurate functionalized mesoporous SiO2 were added, and dispersed uniformly. Initiator azobisisobutyronitrile was added dropwise, and polymerization was carried out at 75°C for 4h. Mineral oil defoaming agent and aziridine crosslinking agent were added, and the mass ratio of acrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, phosphate-isocyanurate functionalized mesoporous SiO2, mineral oil defoaming agent, and aziridine crosslinking agent was controlled to be 10:25:100:30:1:0.2:1. After high-speed emulsification, functionalized mesoporous SiO2 modified acrylate pressure-sensitive adhesive was obtained.

[0039] Example 2

[0040] (1) Mesoporous nano-SiO2 was prepared by alcoholysis-hydrolysis treatment of tetraethyl orthosilicate using cetyltrimethylammonium bromide as a template.

[0041] (2) Into the reaction flask, toluene solvent was added, and nitrogen was bubbled through to remove air. Mesoporous nano-SiO2 and isophorone diisocyanate were added at a mass ratio of 100:140, and dispersed uniformly. Isocyanate functionalization was carried out at 100°C for 8h. The solvent was removed by centrifugal separation, and the solid product was washed with toluene and acetone, respectively, to obtain isocyanate functionalized mesoporous SiO2.

[0042] (3) Into the reaction flask, methyl ethyl ketone solvent was added, and nitrogen was bubbled through to remove air. Isocyanate functionalized mesoporous SiO2 and tris(2-hydroxyethyl) isocyanurate were added, and dispersed uniformly. Catalyst dibutyltin dilaurate was added at a mass ratio of 100:100:0.25, and isocyanurate functionalization was carried out at 90°C for 10h. The solvent was removed by centrifugal separation, and the solid product was washed with tetrahydrofuran and acetone, respectively, to obtain isocyanurate functionalized mesoporous SiO2.

[0043] (4) Into the reaction flask, pyridine solvent, diphenyloxyphosphoryl chloride, and isocyanurate functionalized mesoporous SiO2 were added, and dispersed uniformly. Catalyst 4-dimethylaminopyridine and promoter triethylamine were added at a mass ratio of 60:100:0.75:24, and phosphate functionalization was carried out at 50°C for 48h. The solvent was filtered, and the solid product was washed with tetrahydrofuran and acetone, respectively, to obtain phosphate-isocyanurate functionalized mesoporous SiO2.

[0044] (5) Into the reaction flask, toluene solvent was added, and nitrogen was bubbled through to remove air. Acrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, and phosphate-isocyanurate functionalized mesoporous SiO2 were added, and dispersed uniformly. Initiator azobisisobutyronitrile was added dropwise, and polymerization was carried out at 85°C for 4h. Mineral oil defoaming agent and aziridine crosslinking agent were added, and the mass ratio of acrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, phosphate-isocyanurate functionalized mesoporous SiO2, mineral oil defoaming agent, and aziridine crosslinking agent was controlled to be 11:26:100:33:2:0.3:2. After high-speed emulsification, functionalized mesoporous SiO2 modified acrylate pressure-sensitive adhesive was obtained.

[0045] Example 3

[0046] (1) Mesoporous nano-SiO2 was prepared by alcoholysis-hydrolysis treatment of tetraethyl orthosilicate using cetyltrimethylammonium bromide as a template.

[0047] (2) Into the reaction flask, toluene solvent was added, and nitrogen was bubbled through to remove air. Mesoporous nano-SiO2 and isophorone diisocyanate were added at a mass ratio of 100:160, and dispersed uniformly. Isocyanate functionalization was carried out at 90°C for 8h. The solvent was removed by centrifugal separation, and the solid product was washed with toluene and acetone, respectively, to obtain isocyanate functionalized mesoporous SiO2.

[0048] (3) Into the reaction flask, methyl ethyl ketone solvent was added, and nitrogen was bubbled through to remove air. Isocyanate functionalized mesoporous SiO2 and tris(2-hydroxyethyl) isocyanurate were added, and dispersed uniformly. Catalyst dibutyltin dilaurate was added at a mass ratio of 100:115:0.32, and isocyanurate functionalization was carried out at 85°C for 12h. The solvent was removed by centrifugal separation, and the solid product was washed with tetrahydrofuran and acetone, respectively, to obtain isocyanurate functionalized mesoporous SiO2.

[0049] (4) Into the reaction flask, pyridine solvent, diphenyloxyphosphoryl chloride, and isocyanurate functionalized mesoporous SiO2 were added, and dispersed uniformly. Catalyst 4-dimethylaminopyridine and promoter triethylamine were added at a mass ratio of 70:100:0.85:28, and phosphate functionalization was carried out at 50°C for 36h. The solvent was filtered, and the solid product was washed with tetrahydrofuran and acetone, respectively, to obtain phosphate-isocyanurate functionalized mesoporous SiO2.

[0050] (5) Into the reaction flask, toluene solvent was added, and nitrogen was bubbled through to remove air. Acrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, and phosphate-isocyanurate functionalized mesoporous SiO2 were added, and dispersed uniformly. Initiator azobisisobutyronitrile was added dropwise, and polymerization was carried out at 80°C for 6h. Mineral oil defoaming agent and aziridine crosslinking agent were added, and the mass ratio of acrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, phosphate-isocyanurate functionalized mesoporous SiO2, mineral oil defoaming agent, and aziridine crosslinking agent was controlled to be 12.5:28:100:38:3:0.4:2.8. After high-speed emulsification, functionalized mesoporous SiO2 modified acrylate pressure-sensitive adhesive was obtained.

[0051] Example 4

[0052] (1) Mesoporous nano-SiO2 was prepared by alcoholysis-hydrolysis treatment of tetraethyl orthosilicate using cetyltrimethylammonium bromide as a template.

[0053] (2) Into the reaction flask, toluene solvent was added, and nitrogen was bubbled through to remove air. Mesoporous nano-SiO2 and isophorone diisocyanate were added in a mass ratio of 100:180, and dispersed uniformly. Isocyanate functionalization was carried out at 100°C for 10h. The solvent was removed by centrifugal separation, and the solid product was washed with toluene and acetone, respectively, to obtain isocyanate functionalized mesoporous SiO2.

[0054] (3) Into the reaction flask, methyl ethyl ketone solvent was added, and nitrogen was bubbled through to remove air. Isocyanate functionalized mesoporous SiO2 and tris(2-hydroxyethyl) isocyanurate were added, and dispersed uniformly. Catalyst dibutyltin dilaurate was added in a mass ratio of 100:130:0.4, and isocyanurate functionalization was carried out at 90°C for 20h. The solvent was removed by centrifugal separation, and the solid product was washed with tetrahydrofuran and acetone, respectively, to obtain isocyanurate functionalized mesoporous SiO2.

[0055] (4) Into the reaction flask, pyridine solvent, diphenyloxyphosphoryl chloride, and isocyanurate functionalized mesoporous SiO2 were added, and dispersed uniformly. Catalyst 4-dimethylaminopyridine and promoter triethylamine were added in a mass ratio of 80:100:1:32, and phosphate functionalization was carried out at 60°C for 48h. The solvent was filtered, and the solid product was washed with tetrahydrofuran and acetone, respectively, to obtain phosphate-isocyanurate functionalized mesoporous SiO2.

[0056] (5) Into the reaction flask, toluene solvent was added, and nitrogen was bubbled through to remove air. Acrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, and phosphate-isocyanurate functionalized mesoporous SiO2 were added, and then dispersed uniformly. Initiator azobisisobutyronitrile was added dropwise, and polymerization was carried out at 85°C for 8h. Mineral oil defoaming agent and aziridine crosslinking agent were then added, and the mass ratio of acrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, phosphate-isocyanurate functionalized mesoporous SiO2, mineral oil defoaming agent, and aziridine crosslinking agent was controlled to be 14:30:100:40:4:0.5:3.5. After high-speed emulsification, functionalized mesoporous SiO2 modified acrylate pressure-sensitive adhesive was obtained.

[0057] Comparative Example 1

[0058] (1) Mesoporous nano-SiO2 was prepared by alcoholysis-hydrolysis treatment of tetraethyl orthosilicate using hexadecyltrimethylammonium bromide as a template.

[0059] (2) Into the reaction flask, toluene solvent was added, and nitrogen was bubbled through to remove air. Mesoporous nano-SiO2 and isophorone diisocyanate were added in a mass ratio of 1:1, and then dispersed uniformly. Isocyanate functionalization was carried out at 100°C for 10h. The solvent was removed by centrifugal separation, and the solid product was washed with toluene and acetone, respectively, to obtain isocyanate functionalized mesoporous SiO2.

[0060] (3) Into the reaction flask, methyl ethyl ketone solvent was added, and nitrogen was bubbled through to remove air. Isocyanate functionalized mesoporous SiO2 and tris(2-hydroxyethyl) isocyanurate were added, and then dispersed uniformly. Catalyst dibutyltin dilaurate was added in a mass ratio of 100:65:0.16, and isocyanurate functionalization was carried out at 90°C for 12h. The solvent was removed by centrifugal separation, and the solid product was washed with tetrahydrofuran and acetone, respectively, to obtain isocyanurate functionalized mesoporous SiO2.

[0061] (4) Into the reaction flask, pyridine solvent, diphenyloxyphosphoryl chloride, and isocyanurate functionalized mesoporous SiO2 were added, and then dispersed uniformly. Catalyst 4-dimethylaminopyridine and promoter triethylamine were added in a mass ratio of 40:100:0.5:16, and phosphate functionalization was carried out at 50°C for 36h. The solvent was filtered, and the solid product was washed with tetrahydrofuran and acetone, respectively, to obtain phosphate-isocyanurate functionalized mesoporous SiO2.

[0062] (5) Into the reaction flask, toluene solvent was added, and nitrogen was bubbled through to remove air. Then, acrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, and phosphate-isocyanurate functionalized mesoporous SiO2 were added, and the mixture was uniformly dispersed. Then, initiator azobisisobutyronitrile was added dropwise, and the mixture was subjected to polymerization at 80°C for 6 h. Then, mineral oil defoaming agent and aziridine crosslinking agent were added, and the mass ratio of acrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, phosphate-isocyanurate functionalized mesoporous SiO2, mineral oil defoaming agent, and aziridine crosslinking agent was controlled to be 9:23:100:26:0.5:0.15:0.6. After high-speed emulsification, functionalized mesoporous SiO2 modified acrylate pressure-sensitive adhesive was obtained.

[0063] Comparative Example 2

[0064] (1) Mesoporous nano-SiO2 was prepared by alcoholysis-hydrolysis treatment of tetraethyl orthosilicate using hexadecyltrimethylammonium bromide as a template.

[0065] (2) Into the reaction flask, toluene solvent was added, and nitrogen was bubbled through to remove air. Then, mesoporous nano-SiO2 and isophorone diisocyanate were added at a mass ratio of 1:2, and the mixture was uniformly dispersed. Then, the mixture was subjected to isocyanate treatment at 90°C for 8 h. The solvent was removed by centrifugal separation, and the solid product was washed with toluene and acetone, respectively, to obtain isocyanate functionalized mesoporous SiO2.

[0066] (3) Into the reaction flask, methyl ethyl ketone solvent was added, and nitrogen was bubbled through to remove air. Then, isocyanate functionalized mesoporous SiO2 and tris(2-hydroxyethyl) isocyanurate were added, and the mixture was uniformly dispersed. Then, catalyst dibutyltin dilaurate was added at a mass ratio of 100:150:0.4, and the mixture was subjected to isocyanurate functionalization treatment at 80°C for 15 h. The solvent was removed by centrifugal separation, and the solid product was washed with tetrahydrofuran and acetone, respectively, to obtain isocyanurate functionalized mesoporous SiO2.

[0067] (4) Into the reaction flask, pyridine solvent, diphenyloxyphosphoryl chloride, and isocyanurate functionalized mesoporous SiO2 were added, and the mixture was uniformly dispersed. Then, catalyst 4-dimethylaminopyridine and promoter triethylamine were added at a mass ratio of 90:100:1.15:36, and the mixture was subjected to phosphate functionalization treatment at 60°C for 48 h. The solvent was filtered, and the solid product was washed with tetrahydrofuran and acetone, respectively, to obtain phosphate-isocyanurate functionalized mesoporous SiO2.

[0068] (5) Into the reaction flask, toluene solvent was added, nitrogen was passed, then acrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate and phosphate-isocyanurate functionalized mesoporous SiO2 were added, and after being uniformly dispersed, initiator azobisisobutyronitrile was added dropwise, and the polymerization process was carried out at 80°C for 6h, then mineral oil defoaming agent and aziridine crosslinking agent were added, and the mass ratio of acrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, phosphate-isocyanurate functionalized mesoporous SiO2, mineral oil defoaming agent and aziridine crosslinking agent was controlled to be 15.5:32:100:44:5:0.6:4.5, and after high-speed emulsification, functionalized mesoporous SiO2 modified acrylate pressure-sensitive adhesive was obtained.

[0069] The functionalized mesoporous SiO2 modified acrylate pressure-sensitive adhesive was poured into a mold, cured into an adhesive film, and then placed in an FL-8620A horizontal and vertical combustion tester to test the flame retardant performance, and the test standard was UL94 fireproof grade.

[0070]

[0071] The adhesive film was placed in a DSC214 thermal gravimetric analyzer to test the decomposition temperature and thermal stability of the adhesive film.

[0072]

[0073] The functionalized mesoporous SiO2 modified acrylate pressure-sensitive adhesive was coated on the surface of a PET substrate, and a BLD-CH electronic peeling tester was used to test the peeling strength.

[0074]

Claims

1. A functionalized mesoporous material modified acrylic pressure-sensitive adhesive, characterized in that: The preparation method of the functionalized mesoporous SiO2 modified acrylate pressure-sensitive adhesive is as follows: (1) Mesoporous nano-SiO2 was prepared by alcoholysis-hydrolysis of tetraethyl orthosilicate using hexadecyltrimethylammonium bromide as a template agent. (2) Add toluene solvent to the reaction flask and purge the air with nitrogen gas. Add mesoporous nano SiO2 and isophorone diisocyanate. After dispersing evenly, perform isocyanate treatment. Centrifuge to remove solvent. Wash the solid product with toluene and acetone respectively to obtain isocyanate-functionalized mesoporous SiO2. (3) Add methyl ethyl ketone solvent to the reaction flask, purge with nitrogen, add isocyanate-functionalized mesoporous SiO2 and tris(2-hydroxyethyl) isocyanurate, disperse evenly, add dibutyltin dilaurate catalyst, perform isocyanurate functionalization treatment, centrifuge to remove solvent, wash solid product with tetrahydrofuran and acetone respectively, and obtain isocyanurate-functionalized mesoporous SiO2. (4) Add pyridine solvent, diphenoxyphosphoryl chloride and isocyanurate-functionalized mesoporous SiO2 to the reaction flask, disperse evenly, add catalyst 4-dimethylaminopyridine and promoter triethylamine, perform phosphate ester functionalization treatment, filter solvent, wash solid product with tetrahydrofuran and acetone respectively, and obtain phosphate ester-isocyanurate-functionalized mesoporous SiO2. (5) Toluene solvent is added to the reaction flask, nitrogen gas is introduced, and then acrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate and phosphate ester-isocyanurate functionalized mesoporous SiO2 are added. After uniform dispersion, azobisisobutyronitrile initiator is added dropwise to carry out the polymerization process. Then mineral oil defoamer and aziridine crosslinking agent are added. After high-speed emulsification, functionalized mesoporous SiO2 modified acrylate pressure-sensitive adhesive is obtained; the mass ratio of mesoporous nano-SiO2 and isophorone diisocyanate in step (2) is 100:120-180; the temperature of isocyanate functionalization treatment in step (2) is 80-100℃, and the treatment time is 5-10h; the mass ratio of isocyanate functionalized mesoporous SiO2, tris(2-hydroxyethyl) isocyanurate and dibutyltin dilaurate in step (3) is 100:85-130:0.2-0.4 ... (3) The temperature for isocyanurate functionalization treatment is 75-90℃, and the treatment time is 10-20h; the mass ratio of diphenoxyphosphoryl chloride, isocyanurate functionalized mesoporous SiO2, 4-dimethylaminopyridine and triethylamine in step (4) is 50-80:100:0.65-1:20-32; the temperature for phosphate functionalization treatment in step (4) is 40-60℃, and the treatment time is 24-48h; the mass ratio of acrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, phosphate-isocyanurate functionalized mesoporous SiO2, mineral oil defoamer and aziridine crosslinking agent in step (5) is 10-14:25-30:100:30-40:1-4:0.2-0.5:1-3.5; the temperature for polymerization in step (5) is 75-85℃, and the polymerization time is 4-8h.

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