Insulation board with high barrier property and anti-aging property and preparation method thereof

Abstract

The invention discloses an insulation board with high barrier and aging resistance and a preparation method thereof, and relates to the technical field of insulation boards. The high-barrier aluminized film is adopted to perform vacuum packaging on the core material filler, so that on one hand, the core material filler is wrapped by the high-barrier aluminized film to isolate outside air, and the interior of the core material filler is kept in a vacuum degree, and on the other hand, the high-barrier aluminized film is a compact material; the waterproof anti-aging master batch can effectively prevent nitrogen, oxygen, water vapor and the like from permeating into the vacuum insulation panel through a barrier film, and can also reduce the influence of heat conduction and heat radiation. The phenomenon that the surface of a traditional aluminum laminated film is corroded and falls off under the humid and hot condition is avoided, and the service life of the aluminum laminated film is effectively prolonged.

Description

Technical Field

[0001] The present invention relates to the technical field of thermal insulation boards, and specifically to a thermal insulation board with high barrier and anti-aging properties and a preparation method thereof. Background Art

[0002] At present, the core material of the thermal insulation board is mostly made by coating the core material with aluminized film and then evacuating it to produce a thermal insulation core material; there are many problems with traditional aluminized films during use, such as easy corrosion and peeling on the surface under humid and hot conditions, which seriously affect its service life and the protection effect on the core material. At the same time, for the core material filler, external nitrogen, oxygen, water vapor, etc. are easily infiltrated into the interior through the barrier film, and it is also affected by heat conduction and heat radiation, which is not conducive to maintaining good heat insulation performance; and in harsh environments, its film material is prone to aging; Under this background, the core material of the thermal insulation board of this application uses a vacuum insulation panel and makes improvements. On the one hand, a high-barrier aluminized film is used to vacuum-pack the core material filler. With its compactness, it effectively isolates external air, maintains the internal vacuum degree, blocks the infiltration of various gases and water vapor, and can also reduce the influence of heat conduction and heat radiation. On the other hand, a macromolecular antioxidant is innovatively used to prepare a hydrolysis-resistant and anti-aging masterbatch. The macromolecular antioxidant uses hexachlorocyclotriphosphazene as the core and constructs a network structure through a series of reactions to synergistically improve thermal stability, anti-aging efficiency, etc., and further enhances the adhesion with PET with vinyltrimethoxysilane to reduce the precipitation of antioxidants and comprehensively improve the comprehensive performance of the vacuum insulation panel. Summary of the Invention

[0003] The purpose of the present invention is to provide a thermal insulation board with high barrier and anti-aging properties and a preparation method thereof to solve the problems existing in the prior art.

[0004] To solve the above technical problems, the present invention provides the following technical solutions: A preparation method of a thermal insulation board with high barrier and anti-aging properties includes the following preparation steps: After drying the core material filler until the moisture content reaches below 0.5%, it is filled into a non-woven fabric bag, and then the opening of the non-woven fabric bag is heat-sealed. After heat-sealing, it is leveled and pressed into shape to obtain a thermal insulation core board; The thermal insulation core board is placed in a high-barrier aluminized bag and evacuated to 0.02 - 5 Pa, and the high-barrier aluminized bag is heat-sealed. Then, the excess flanges of the high-barrier aluminized bag are folded and pasted and fixed on the back to obtain a vacuum insulation panel; A connecting agent layer is coated on both sides of the vacuum insulation panel. After coating, it is embedded inside a polymeric polystyrene board, and then pressed into shape to prepare a thermal insulation board.

[0005] Preferably, the high-barrier aluminized bag is prepared by vacuum evaporation of aluminum on the surface of a high-barrier PET film to form a high-barrier PET aluminized film and then cutting it.

[0006] Preferably, the high-barrier PET film is prepared through the following steps: Weigh 4-6% of a hydrolysis-proof and anti-aging masterbatch, 7-9% of silicon dioxide, 9-11% of titanium dioxide, and 76-78% of PET chips by mass fraction. After mixing and extruding with a screw, it is prepared through biaxial stretching.

[0007] Preferably, the hydrolysis-proof and anti-aging masterbatch is prepared through the following steps: Weigh 67-69% of PET chips, 1-3% of polycarbodiimide, 14-16% of a light stabilizer, and 14-16% of a macromolecular antioxidant by mass fraction. After extruding and pelletizing with a screw, it is prepared.

[0008] Preferably, the light stabilizer is prepared by mixing UV360 and UV622 in a mass ratio of 3:1.

[0009] Preferably, the macromolecular antioxidant is prepared through the following steps: Weigh vinyltrimethoxysilane and a small molecule antioxidant in a mass ratio of 1:0.85-0.9. Under the protection of nitrogen, add vinyltrimethoxysilane and the small molecule antioxidant to cyclohexanone which is 15-18 times the mass of vinyltrimethoxysilane. Then, heat up to 50-55°C and stir for 10-15 minutes. Next, add azobisisobutyronitrile which is 0.02-0.03 times the mass of vinyltrimethoxysilane. Then, heat up to 95-100°C and react for 3-3.5 hours. After the reaction is completed, pour the reaction solution into petroleum ether, let it stand for precipitation, filter, and dry to obtain the macromolecular antioxidant.

[0010] Preferably, the small molecule antioxidant is prepared through the following steps: Weigh 3,5-di-tert-butyl-4-hydroxybenzoic acid and hexakis(4-formylphenoxy)cyclotriphosphazene in a mass ratio of 6:1-1.2. Under the protection of nitrogen, add 3,5-di-tert-butyl-4-hydroxybenzoic acid and hexakis(4-formylphenoxy)cyclotriphosphazene to anhydrous pyridine which is 3.5-3.8 times the mass of 3,5-di-tert-butyl-4-hydroxybenzoic acid. Stir evenly and heat up to 80-85°C to react for 3-3.5 hours. After the reaction is completed, cool to 25-35°C, add a hydrochloric acid solution with a pH of 4-4.5 which is 5-6 times the mass of anhydrous pyridine. Stir evenly, let it stand, and extract with ethyl acetate. After extraction, wash with saturated brine 3-4 times, dry with anhydrous sodium sulfate, and evaporate the solvent under reduced pressure to obtain the small molecule antioxidant.

[0011] Preferably, the preparation steps of the hexakis(4-formylphenoxy)cyclotriphosphazene are as follows: Weigh p-hydroxybenzaldehyde, tetrahydrofuran, and anhydrous potassium carbonate according to a mass ratio of 1:0.75 - 0.8:12.5 - 13. Add p-hydroxybenzaldehyde and anhydrous potassium carbonate to tetrahydrofuran, stir for 1 - 1.2 h, and then uniformly dropwise add a hexachlorocyclotriphosphazene solution 2.8 - 3 times the mass of p-hydroxybenzaldehyde within 30 - 35 min. After the addition, stir evenly and raise the temperature to 65 - 70 °C for reaction for 22 - 24 h. After the reaction, filter, and wash the filtered product with tetrahydrofuran 3 - 5 times. After washing, under the condition of a temperature of 60 - 65 °C, vacuum dry for 12 - 14 h to obtain hexakis(4-formylphenoxy)cyclotriphosphazene.

[0012] A heat-insulating board with high barrier and anti-aging properties includes a polymerized polystyrene board and a vacuum insulation panel. The polymerized polystyrene board is formed by pressing a polymerized polystyrene board bottom surface and a polymerized polystyrene board top surface. An edge strip is provided at the edge of the polymerized polystyrene board bottom surface. A vacuum insulation panel is embedded in the cavity formed by the edge strip on the polymerized polystyrene board bottom surface, and an adhesive layer is coated between the polymerized polystyrene board bottom surface and the vacuum insulation panel.

[0013] Preferably, the thickness of the adhesive layer is less than 1 mm.

[0014] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: In this application, a high-barrier aluminized film is used for vacuum packaging the core material filler. On the one hand, the core material filler is wrapped by the high-barrier aluminized film to isolate the outside air and keep the inside in a vacuum state. On the other hand, it is a dense material itself, which can effectively prevent nitrogen, oxygen, water vapor, etc. from infiltrating into the vacuum insulation panel through the barrier film, and can also reduce the influence of heat conduction and heat radiation. In this application, a macromolecular antioxidant is used to prepare a hydrolysis-resistant and anti-aging masterbatch, which avoids the phenomenon of surface corrosion and peeling of the traditional aluminized film under humid and hot conditions and effectively improves the service life of the aluminized film; Among them, the macromolecular antioxidant introduces p-hydroxybenzaldehyde through nucleophilic substitution with hexachlorocyclotriphosphazene as the core, and then bridges 3,5-di-tert-butyl-4-hydroxybenzoic acid through p-hydroxybenzaldehyde. The added 3,5-di-tert-butyl-4-hydroxybenzoic acid is a monophenolic hindered phenol antioxidant. Its relative molecular weight is relatively small. Therefore, by grafting onto the network structure formed by hexachlorocyclotriphosphazene, it can effectively increase the relative molecular weight, reduce volatility, and thus improve the anti-aging efficiency. And hexachlorocyclotriphosphazene in this application has good thermal stability. The two work together to effectively improve the thermal stability of the macromolecular antioxidant; the bridged large molecular weight network structure also helps to enhance the overall thermal stability, so that it can also exhibit good anti-aging performance in a humid and hot environment; A carbon-carbon double bond is formed during the bridging of 3,5-di-tert-butyl-4-hydroxybenzoic acid, and then it is polymerized with vinyltrimethoxysilane by azobisisobutyronitrile. By linking vinyltrimethoxysilane to it, an effective end-capping effect can be achieved. Moreover, vinyltrimethoxysilane can also form intermolecular hydrogen bonds with PET, firmly fixing the macromolecular antioxidant between the PET chain segments, not only slowing down the precipitation of the antioxidant but also improving the adhesion between PET and the surface aluminum film, making it not easy to fall off. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 It is a schematic structural diagram of the present invention; Figure 2 It is a schematic diagram of the combined installation of the present invention; Figure 3 It is a schematic diagram of the implementation and application of the present invention.

[0016] Explanation of the reference numerals in the figure: 1, polymerized polystyrene board; 2, vacuum insulation panel; 3, side strip; 4, adhesive layer. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0017] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0018] Example 1:

[0019] S1. Weigh p-hydroxybenzaldehyde, tetrahydrofuran, and anhydrous potassium carbonate according to a mass ratio of 1:0.775:12.75. Add p-hydroxybenzaldehyde and anhydrous potassium carbonate to tetrahydrofuran, stir for 1.1 h, and then uniformly drop a solution of hexachlorocyclotriphosphazene 2.9 times the mass of p-hydroxybenzaldehyde within 32.5 min. After the dropping is completed, stir evenly and raise the temperature to 67.5 °C for reaction for 23 h. After the reaction is completed, filter, and wash the filtered product 4 times with tetrahydrofuran. After the washing is completed, vacuum dry at 62.5 °C for 13 h to obtain hexakis(4-formylphenoxy)cyclotriphosphazene; S2. Weigh 3,5 - di - tert - butyl - 4 - hydroxybenzoic acid and hexakis(4 - aldehyde phenoxy) cyclotriphosphazene according to a mass ratio of 6:1.1. Under nitrogen protection, add 3,5 - di - tert - butyl - 4 - hydroxybenzoic acid and hexakis(4 - aldehyde phenoxy) cyclotriphosphazene to anhydrous pyridine which is 3.65 times the mass of 3,5 - di - tert - butyl - 4 - hydroxybenzoic acid. Stir evenly and heat up to 82.5 °C for reaction for 3.25 h. After the reaction is completed, cool to 30 °C, add a hydrochloric acid solution with a pH of 4.25 which is 5.5 times the mass of anhydrous pyridine. Stir evenly, let it stand, and extract with ethyl acetate. After extraction, wash with saturated brine for 3.5 times, and dry with anhydrous sodium sulfate. Evaporate the solvent under reduced pressure to obtain a small - molecule antioxidant; S3. Weigh vinyltrimethoxysilane and the small - molecule antioxidant according to a mass ratio of 1:0.875. Under nitrogen protection, add vinyltrimethoxysilane and the small - molecule antioxidant to cyclohexanone which is 16.5 times the mass of vinyltrimethoxysilane. Then heat up to 52.5 °C and stir for 12.5 min. Then add azobisisobutyronitrile which is 0.025 times the mass of vinyltrimethoxysilane. Then heat up to 97.5 °C and react for 3.25 h. After the reaction is completed, pour the reaction solution into petroleum ether, let it stand for precipitation, and then filter and dry to obtain a macromolecule antioxidant; S4. The preparation steps of the high - barrier PET film include: weigh 5% of the hydrolysis - proof and anti - aging masterbatch, 8% of silicon dioxide, 10% of titanium dioxide, and 77% of PET chips by mass fraction. After mixing and extruding with a screw, it is prepared by biaxial stretching; The preparation steps of the hydrolysis - proof and anti - aging masterbatch include: weigh 68% of PET chips, 2% of polycarbodiimide, 15% of light stabilizer, and 15% of macromolecule antioxidant by mass fraction. After extruding and pelletizing with a screw, it is prepared; The light stabilizer is prepared by mixing UV360 and UV622 according to a mass ratio of 3:1; S5. After drying the core - material filler until the moisture content reaches below 0.5%, fill it into a non - woven fabric bag. Then heat - seal the opening of the non - woven fabric bag. After heat - sealing, level and press - form to obtain a heat - insulating core board; Place the heat - insulating core board into a high - barrier aluminized bag, evacuate to 2.51 Pa, and heat - seal the high - barrier aluminized bag. Then fold the excess flanges of the high - barrier aluminized bag and paste and fix them on the back to obtain a vacuum insulation panel 2; Coat the connecting agent on the four - side edge area of the bottom surface of the polymerized polystyrene board, accurately position the side strip 3 on the connecting agent, and press for 5 - 8 s to bond the bottom surface of the polymerized polystyrene board and the side strip 3 into a whole. The side strip 3 is also made of polymerized polystyrene (polystyrene material). Coat the connecting agent on both sides of the vacuum insulation panel 2 to form a connecting agent layer 4. After coating, embed it into the cavity formed by the bottom surface of the polymerized polystyrene board and the side strip 3. Then coat the connecting agent on the side strip 3, and press - form the top surface of the polymerized polystyrene board and the side strip 3 to prepare a heat - insulating board; The high - barrier aluminized bag is prepared by vacuum - evaporating aluminum on the surface of the high - barrier PET film to obtain a high - barrier PET aluminized film and then cutting it.

[0020] Example 2:

[0021] S1. Weigh p-hydroxybenzaldehyde, tetrahydrofuran and anhydrous potassium carbonate according to the mass ratio of 1:0.775:12.75. Add p-hydroxybenzaldehyde and anhydrous potassium carbonate into tetrahydrofuran, stir for 1.1 h, and then uniformly dropwise add a solution of hexachlorocyclotriphosphazene which is 2.9 times the mass of p-hydroxybenzaldehyde within 32.5 min. After the dropwise addition, stir evenly and heat up to 67.5 °C for reaction for 23 h. After the reaction is completed, filter and wash the filtered product 4 times with tetrahydrofuran. After the washing is completed, vacuum dry at 62.5 °C for 13 h to obtain hexakis(4-formylphenoxy)cyclotriphosphazene; S2. Weigh 3,5-di-tert-butyl-4-hydroxybenzoic acid and hexakis(4-formylphenoxy)cyclotriphosphazene according to the mass ratio of 6:1.1. Under the protection of nitrogen, add 3,5-di-tert-butyl-4-hydroxybenzoic acid and hexakis(4-formylphenoxy)cyclotriphosphazene into anhydrous pyridine which is 3.65 times the mass of 3,5-di-tert-butyl-4-hydroxybenzoic acid, stir evenly and heat up to 82.5 °C for reaction for 3.25 h. After the reaction is completed, cool to 30 °C, add a hydrochloric acid solution with a pH of 4.25 which is 5.5 times the mass of anhydrous pyridine, stir evenly, stand still and extract with ethyl acetate. After the extraction is completed, wash 3.5 times with saturated brine and dry with anhydrous sodium sulfate. Evaporate the solvent under reduced pressure to obtain a small molecule antioxidant; S3. Weigh vinyltrimethoxysilane and the small molecule antioxidant according to the mass ratio of 1:0.875. Under the protection of nitrogen, add vinyltrimethoxysilane and the small molecule antioxidant into cyclohexanone which is 16.5 times the mass of vinyltrimethoxysilane, then heat up to 52.5 °C and stir for 12.5 min, add azobisisobutyronitrile which is 0.025 times the mass of vinyltrimethoxysilane, and then heat up to 97.5 °C for reaction for 3.25 h. After the reaction is completed, pour the reaction solution into petroleum ether, stand still for precipitation, and then filter and dry to obtain a macromolecule antioxidant; S4. The high-barrier PET film includes the following preparation steps: Weigh 5% of a hydrolysis-proof and anti-aging masterbatch, 8% of silicon dioxide, 10% of titanium dioxide and 77% of PET chips according to mass fraction, mix and extrude with a screw, and then prepare by biaxial stretching; The hydrolysis-proof and anti-aging masterbatch includes the following preparation steps: Weigh 68% of PET chips, 2% of polycarbodiimide, 15% of a light stabilizer and 15% of a macromolecule antioxidant according to mass fraction, and then prepare by extrusion granulation with a screw; The light stabilizer is prepared by mixing UV360 and UV622 according to the mass ratio of 3:1; S5. After drying the core material filler until the moisture content reaches below 0.5%, it is filled into a non-woven fabric bag. Then, the opening of the non-woven fabric bag is heat-sealed. After heat-sealing, it is leveled and pressed into shape to obtain a heat-insulating core board. The heat-insulating core board is placed into a high-barrier aluminized bag and evacuated to 2.51 Pa, and then the high-barrier aluminized bag is heat-sealed. Then, the excess frills of the high-barrier aluminized bag are folded and pasted and fixed on the back to obtain a vacuum insulation panel 2. The bottom edges of the four sides of the polymer polystyrene board are coated with a bonding agent, and the side strip 3 is accurately positioned on the bonding agent and pressed for 5 - 8 s to bond the bottom surface of the polymer polystyrene board and the side strip 3 into a whole. The side strip 3 is also made of polymer polystyrene (polystyrene material). A bonding agent layer 4 is formed by coating the two sides of the vacuum insulation panel 2 with the bonding agent. After coating, it is embedded into the cavity formed by the bottom surface of the polymer polystyrene board and the side strip 3. Then, after coating the side strip 3 with the bonding agent, the top surface of the polymer polystyrene board and the side strip 3 are pressed into shape to prepare a heat-insulating board. The high-barrier aluminized bag is prepared by vacuum evaporation and aluminizing on the surface of a high-barrier PET film and then cutting the high-barrier PET aluminized film.

[0022] Example 3:

[0023] S1. Weigh p-hydroxybenzaldehyde, tetrahydrofuran, and anhydrous potassium carbonate according to the mass ratio of 1:0.75:12.5. Add p-hydroxybenzaldehyde and anhydrous potassium carbonate to tetrahydrofuran and stir for 1 h. Then, uniformly drop a solution of hexachlorocyclotriphosphazene that is 2.8 times the mass of p-hydroxybenzaldehyde within 30 min. After dropping, stir evenly and heat up to 65 °C for reaction for 22 h. After the reaction ends, filter and wash the filtered product 5 times with tetrahydrofuran. After washing, under the condition of a temperature of 60 °C, vacuum dry for 12 h to obtain hexakis(4-formylphenoxy)cyclotriphosphazene. S2. Weigh 3,5-di-tert-butyl-4-hydroxybenzoic acid and hexakis(4-formylphenoxy)cyclotriphosphazene according to the mass ratio of 6:1. Under the protection of nitrogen, add 3,5-di-tert-butyl-4-hydroxybenzoic acid and hexakis(4-formylphenoxy)cyclotriphosphazene to anhydrous pyridine that is 3.5 times the mass of 3,5-di-tert-butyl-4-hydroxybenzoic acid, stir evenly and heat up to 80 °C for reaction for 3 h. After the reaction ends, cool to 25 °C, add a hydrochloric acid solution with a pH of 4 that is 5 times the mass of anhydrous pyridine, stir evenly and then let it stand and extract with ethyl acetate. After extraction, wash 3 times with saturated brine and dry with anhydrous sodium sulfate, and evaporate the solvent under reduced pressure to obtain a small molecule antioxidant. S3. Weigh vinyltrimethoxysilane and small molecule antioxidant according to the mass ratio of 1:0.85. Under the protection of nitrogen, add vinyltrimethoxysilane and small molecule antioxidant into cyclohexanone which is 15 times the mass of vinyltrimethoxysilane. Then heat up to 50 °C and stir for 10 min. Add azobisisobutyronitrile which is 0.02 times the mass of vinyltrimethoxysilane. Then heat up to 95 °C and react for 3 h. After the reaction is completed, pour the reaction solution into petroleum ether, let it stand for precipitation, and then filter and dry to obtain the macromolecule antioxidant. S4. The high-barrier PET film includes the following preparation steps: Weigh 6% of hydrolysis-proof and anti-aging masterbatch, 9% of silicon dioxide, 11% of titanium dioxide and 78% of PET chips according to mass fraction. After mixing and extruding with a screw, it is prepared by biaxial stretching. The hydrolysis-proof and anti-aging masterbatch includes the following preparation steps: Weigh 69% of PET chips, 3% of polycarbodiimide, 16% of light stabilizer and 16% of macromolecule antioxidant according to mass fraction. After extruding and pelletizing with a screw, it is prepared. The light stabilizer is prepared by mixing UV360 and UV622 according to the mass ratio of 3:1. S5. After drying the core filler until the moisture content reaches below 0.5%, fill it into a non-woven fabric bag. Then heat-seal the opening of the non-woven fabric bag. After heat-sealing, level and press it into shape to obtain the heat-insulating core board. Place the heat-insulating core board into a high-barrier aluminized bag, evacuate to 5 Pa and heat-seal the high-barrier aluminized bag. Then fold the excess fringing of the high-barrier aluminized bag and paste it on the back to obtain the vacuum insulation panel 2. Coat the connecting agent on the four edges of the bottom surface of the polymerized polystyrene board, accurately position the side strip 3 on the connecting agent, and press for 5 - 8 s to bond the bottom surface of the polymerized polystyrene board and the side strip 3 into a whole. The side strip 3 is also made of polymerized polystyrene board (polystyrene material). Coat the two sides of the vacuum insulation panel 2 with the connecting agent to form the connecting agent layer 4. After coating, embed it into the cavity formed by the bottom surface of the polymerized polystyrene board and the side strip 3. Then coat the connecting agent on the side strip 3, and press and form the top surface of the polymerized polystyrene board and the side strip 3 to prepare the heat-insulating board. The high-barrier aluminized bag is prepared by vacuum evaporation aluminizing on the surface of the high-barrier PET film and then cutting.

[0024] Example 4:

[0025] The difference from Example 2 is only in step S4: Replace the macromolecule antioxidant in step S4 with hexakis(4-formylphenoxy)cyclotriphosphazene prepared in step S1. Example 5:

[0026] The difference from Example 2 is only in step S4: Replace the macromolecule antioxidant in step S4 with the small molecule antioxidant prepared in step S2. Example 6:

[0027] The difference from Example 2 is only in step S4: in step S4, the macromolecular antioxidant is replaced with a mixture of hexakis(4-formylphenoxy)cyclotriphosphazene, 3,5-di-tert-butyl-4-hydroxybenzoic acid and vinyltrimethoxysilane mixed in a molar ratio of 1:6:6 and having the same mass; Test Example 1: Test of flame retardancy performance Test method: Prepare standard specimens from the high-barrier PET films prepared in Examples 1 to 6 according to GB / T 2406, and test the limiting oxygen index of the standard specimens. The results are shown in Table 1.

[0028] Table 1 - Test data of limiting oxygen index performance

[0029] From the comparison of the experimental data of Examples 1 to 6 in Table 1, it can be found that the high-barrier PET film prepared by the present invention has good flame retardancy performance.

[0030] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Examples 4 to 6, indicating that the macromolecular antioxidant is introduced with p-hydroxybenzaldehyde through nucleophilic substitution using hexachlorocyclotriphosphazene as the core, and then 3,5-di-tert-butyl-4-hydroxybenzoic acid is bridged through p-hydroxybenzaldehyde. A carbon-carbon double bond is generated during the bridging of 3,5-di-tert-butyl-4-hydroxybenzoic acid, and then it is polymerized with vinyltrimethoxysilane by initiating with azobisisobutyronitrile. By linking vinyltrimethoxysilane thereto, an effective capping effect can be achieved, and vinyltrimethoxysilane can also form intermolecular hydrogen bonds with PET to firmly fix the macromolecular antioxidant. Compared with the general and simple addition of hexachlorocyclotriphosphazene or small molecule antioxidants, the flame retardancy performance is better, thereby excellent flame retardancy performance can be imparted to the fireproof and flame-retardant insulation board.

[0031] Test Example 2: Test of anti-aging performance Test method: Prepare standard specimens from the high-barrier PET films prepared in Examples 1 to 6 according to GB 8813, and test the compressive strength of the standard specimens using an electronic universal testing machine; irradiate the standard specimens with a xenon arc lamp for 5 days, test the compressive strength of the standard specimens after ultraviolet aging treatment, and calculate the change rate of the compressive strength of the examples and the comparative examples before and after ultraviolet aging treatment. The change rate of compressive strength = (original compressive strength of the specimen - compressive strength after ultraviolet aging treatment) / original compressive strength of the specimen × 100%. The results are shown in Table 2.

[0032] Table 2 - Test data of anti-aging performance

[0033] From the comparison of the experimental data of Examples 1 to 6 in Table 2, it can be found that the high-barrier PET film prepared by the present invention has good anti-aging performance.

[0034] By comparison, the change rate of the compressive strength of Examples 1 to 3 is less than that of Examples 4 to 6. The main reason may be that the macromolecular antioxidant in them can be better fixed in PET and is not easily precipitated, while the smaller antioxidant is more likely to precipitate. This can be seen from Examples 5 and 6. The small-molecule antioxidant in Example 5 is definitely larger than the simply added antioxidant. Therefore, it is more stable in the polyester and can play a better role.

[0035] Test Example 3: Barrier performance test: Water vapor transmission rate: Referring to the standard ASTM F-1249, using a PERMATRAN-W3 / 33 water vapor transmission rate tester, the test area is 5 cm 2 , and the relative humidity is 90%; after the test, irradiate with a xenon arc lamp for 5 days, and then test the water vapor transmission rate after ultraviolet aging treatment again according to the same parameters; calculate the change rate of the water vapor transmission rate before and after aging; Gas transmission rate: Referring to the standard ASTM D3985, using a MOCON 2 / 21 oxygen transmission rate tester, the test area is 5 cm 2 , and the relative humidity is 0%; after the test, irradiate with a xenon arc lamp for 5 days, and then test the gas transmission rate after ultraviolet aging treatment again according to the same parameters; calculate the change rate of the gas transmission rate before and after aging; the test results are shown in Table 3.

[0036] Table 3 - Experimental data of barrier performance test

[0037] By comparison, the change rate of Examples 1 to 3 is smaller, but the change rate is larger in Examples 4 to 6, and the main change is in the gas transmission rate. We found through later inspection that there is partial peeling of the aluminum layer on the surface of the sample in Example 4, which is also consistent with the problems summarized in our previous development process. Due to the lack of anti-aging performance, after the surface aluminum layer peels off, its barrier property drops significantly, resulting in the failure of the internal core material to contact the external environment, and thus the overall heat insulation performance drops significantly; the changes of Examples 1 to 3 before and after aging are not large, and good barrier performance has been maintained all the time. Therefore, the service life of this vacuum insulation panel will be greatly improved.

[0038] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above-described exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, in any aspect, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be embraced within the present invention. Any reference signs in the claims should not be construed as limiting the claims involved.

Claims

1. A method for preparing an insulation board with high barrier and anti-aging properties, characterized in that: The preparation method comprises the following steps: drying the core material filler until the moisture content reaches below 0.5%, filling the core material filler into a non-woven bag, then heat-sealing the opening of the non-woven bag, and flattening and pressing the bag into shape after heat-sealing; Producing a thermal insulation core board; The insulation core board is placed in a high-barrier aluminized bag, vacuumed to 0.02-5 Pa, and the high-barrier aluminized bag is heat-sealed. The excess burrs of the high-barrier aluminized bag are folded and then glued to the back to obtain a vacuum insulation board (2). The vacuum insulation board (2) is coated with a connecting agent layer (4) on both sides, and after coating, is embedded in the polymerized polystyrene board (1), and then pressed into shape to prepare an insulation board.

2. The method for preparing the thermal insulation board with high barrier and anti-aging properties according to claim 1, characterized in that: The high-barrier aluminized bag is prepared by vacuum evaporating aluminum on the surface of a high-barrier PET film to form a high-barrier PET aluminized film, and then cutting the film.

3. The method for preparing the thermal insulation board with high barrier and anti-aging properties according to claim 2, characterized in that: The high barrier PET film comprises the following preparation steps: 4-6% of anti-hydrolysis and anti-aging masterbatch, 7-9% of silicon dioxide, 9-11% of titanium dioxide and 76-78% of PET slices are weighed by mass fraction, extruded by a mixing screw, and then prepared by biaxial stretching.

4. The method for preparing the thermal insulation board with high barrier and anti-aging properties according to claim 3, characterized in that: The anti-hydrolysis and anti-aging masterbatch comprises the following preparation steps: 67-69% of PET chips, 1-3% of polycarbodiimide, 14-16% of light stabilizer and 14-16% of macromolecular antioxidant are weighed by mass fraction, and the mixture is prepared by screw extrusion and granulation.

5. The method for preparing the thermal insulation board with high barrier and anti-aging properties according to claim 4, characterized in that: The light stabilizer is prepared by mixing UV360 and UV622 in a mass ratio of 3:

1.

6. The method for preparing the thermal insulation board with high barrier and anti-aging properties according to claim 4, characterized in that: The macromolecular antioxidant comprises the following preparation steps: vinyl trimethoxysilane and a small molecule antioxidant are weighed in a mass ratio of 1:0.85-0.9, and under nitrogen protection conditions, the vinyl trimethoxysilane and the small molecule antioxidant are added to cyclohexanone with a mass of 15-18 times that of the vinyl trimethoxysilane, and then the temperature is raised to 50-55° C. and stirred for 10-15 minutes, and then azobisisobutyronitrile with a mass of 0.02-0.03 times that of the vinyl trimethoxysilane is added, and then the temperature is raised to 95-100° C. and reacted for 3-3.5 hours. After the reaction is completed, the reaction solution is poured into petroleum ether and allowed to stand for precipitation, and then filtered and dried to obtain the macromolecular antioxidant.

7. The method for preparing the thermal insulation board with high barrier and anti-aging properties according to claim 6, characterized in that: The small molecule antioxidant comprises the following preparation steps: weighing 3,5-di-tert-butyl-4-hydroxybenzoic acid and hexa(4-formylphenoxy)cyclotriphosphazene according to a mass ratio of 6:1-1.2, adding 3,5-di-tert-butyl-4-hydroxybenzoic acid and hexa(4-formylphenoxy)cyclotriphosphazene to anhydrous pyridine with a mass of 3.5-3.8 times that of 3,5-di-tert-butyl-4-hydroxybenzoic acid under nitrogen protection, stirring evenly, heating to 80-85° C., reacting for 3-3.5 hours, cooling to 25-35° C. after the reaction is completed, adding hydrochloric acid solution with a pH of 4-4.5 with a mass of 5-6 times that of anhydrous pyridine, stirring evenly, standing and extracting with ethyl acetate, washing with saturated brine for 3-4 times after the extraction is completed, drying with anhydrous sodium sulfate, and removing the solvent by evaporation under reduced pressure to prepare the small molecule antioxidant.

8. The method for preparing the thermal insulation board with high barrier and anti-aging properties according to claim 7, characterized in that: The hexa(4-formylphenoxy)cyclotriphosphazene comprises the following preparation steps: p-hydroxybenzaldehyde, tetrahydrofuran and anhydrous potassium carbonate are weighed in a mass ratio of 1:0.75-0.8:12.5-13, p-hydroxybenzaldehyde and anhydrous potassium carbonate are added to tetrahydrofuran, stirred for 1-1.2 hours, and then a hexachlorocyclotriphosphazene solution with a mass of 2.8-3 times of that of p-hydroxybenzaldehyde is evenly added dropwise within 30-35 minutes, and after the dropwise addition is completed, the solution is evenly stirred and heated to 65-70°C for reaction for 22-24 hours, and after the reaction is completed, the solution is filtered, and the filtered product is washed with tetrahydrofuran for 3-5 times, and after the washing is completed, the solution is vacuum dried at a temperature of 60-65°C for 12-14 hours to obtain the hexa(4-formylphenoxy)cyclotriphosphazene.

9. An insulation board with high barrier and anti-aging properties, characterized in that: The invention comprises a polymerized polystyrene board (1) and a vacuum insulation board (2), wherein the polymerized polystyrene board (1) is formed by pressing a bottom surface of the polymerized polystyrene board and a top surface of the polymerized polystyrene board together, a side strip (3) is arranged at the edge of the bottom surface of the polymerized polystyrene board, the vacuum insulation board (2) is embedded in the cavity formed by the side strip (3) on the bottom surface of the polymerized polystyrene board, and a connecting agent layer (4) is coated between the bottom surface of the polymerized polystyrene board and the vacuum insulation board (2).

10. The thermal insulation board with high barrier and anti-aging properties according to claim 9, characterized in that: The thickness of the connecting agent layer (4) is less than 1 mm.

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