Multifunctional fireproof and explosion-proof plate and preparation method thereof

Abstract

The present invention relates to a multifunctional fireproof and explosion-proof plate and a preparation method thereof, belonging to the technical field of composite plate. The plate is formed by hot pressing a perforated aluminum plate with wood chips through a modified adhesive. The modified adhesive comprises methylvinyldichlorosilane and diallylamine to replace the grafted nitrogen-containing double bond structure, and then click-addition is performed with mercaptoethanol to introduce a thioether structure and polyhydroxy groups as polyol monomers. The wood chips are cross-linked and cured with PMDI resin to bond the wood chips. The polyol monomer introduces a sulfur-nitrogen structure into the polymer chain, which forms a chelating effect on the aluminum plate and strengthens the bonding performance of the adhesive with the aluminum plate, so that the aluminum plate, wood chips and adhesive form a high-strength integral body that is not easy to delaminate or peel off during use. The silicon-nitrogen structure in the structure is easily decomposed during combustion and has certain flame retardant properties. The introduced sulfur element promotes the carbonization of organic matter, which is conducive to the formation of a carbonized layer to hinder the deepening of combustion, so that the plate as a whole has good flame retardancy.

Description

Technical Field

[0001] The present invention belongs to the technical field of composite panels, and in particular relates to a multifunctional fireproof and explosion-proof panel and a preparation method thereof. Background Art

[0002] Particleboard is a type of man-made board. It is made by cutting various branches, small-diameter wood, fast-growing wood, sawdust, etc. into pieces of a certain size. After drying, mixing with glue, and pressing under a certain temperature and pressure, compared with traditional solid wood boards, it has a high wood utilization rate, balanced mechanical properties in all directions, a smooth surface, and high decorative properties. It is widely used in furniture materials.

[0003] However, single particle board has low strength and is easily deformed or even destroyed under external forces. It has poor explosion-proof performance. For example, its application in door panels or load-bearing panels is greatly limited. At present, most exterior doors of buildings use metal door panels, which are heavy and inconvenient to install. The existing aluminum-frame solid wood composite panels are only aluminum foil panels bonded to the surface of solid wood panels. The packaging area of the aluminum foil panels is large. Considering the production cost and the weight of the panels, the thickness of the aluminum foil panels is selected to be low, which does not greatly improve the strength of the panels, and the surface aluminum foil panels cover the natural texture of the wood. The particle board composite panel with aluminum plate sandwich can minimize the use of aluminum plates. Under the premise of controlling the weight of the panels, thicker aluminum plates can be selected as reinforcement layers and retain the natural texture of the wood. However, in existing research, the bonding performance of the adhesive suitable for particle board bonding and the aluminum plate is not high, and the aluminum plate layer and the particle board layer are easy to separate, affecting the use of the panels. Summary of the Invention

[0004] In order to solve the technical problems mentioned in the background technology, the purpose of the present invention is to provide a multifunctional fireproof and explosion-proof plate and a preparation method thereof.

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

[0006] A multifunctional fireproof and explosion-proof plate comprises a perforated aluminum plate and a filling layer hot-pressed and packaged on the surface of the perforated aluminum plate, wherein the filling layer is composed of wood chips and a modified adhesive.

[0007] The modified adhesive is prepared by the following method:

[0008] Step A1: Diallylamine, triethylamine, and tetrahydrofuran are mixed, and dry nitrogen is introduced into the mixture. The temperature is controlled at 5-15°C in an ice-water bath, and mechanical stirring is applied at 120-180 rpm. Methylvinyldichlorosilane is added at a constant rate, and the mixture is stirred at a constant temperature for 5-6 hours. After the reaction is completed, the insoluble matter is filtered out and the tetrahydrofuran is removed by rotary evaporation to obtain a branched intermediate.

[0009] Furthermore, the usage ratio of methylvinyldichlorosilane, diallylamine, triethylamine and tetrahydrofuran is 0.1 mol: 0.2 mol: 12-16 mL: 45-60 mL, and the highly active chlorosilane group reacts with the secondary amine in diallylamine to graft the nitrogen-containing double bond into the methylvinyldichlorosilane to form a multi-double bond compound.

[0010] Step A2: The branched intermediate, dimethylphenylphosphine and toluene were mixed, nitrogen was introduced, the temperature was raised to 80-90°C, mechanical stirring was applied at 180-240 rpm, and the mixture was heated at 220-280 W / m 2 UV irradiation, slowly adding mercaptoethanol, controlling the total reaction time to be 2.5-3.2h, and removing toluene by vacuum rotary evaporation after the reaction to obtain a polyol monomer;

[0011] Furthermore, the usage ratio of the branched intermediate, mercaptoethanol, dimethylphenylphosphine and toluene is 0.1 mol: 0.51-0.52 mol: 20-30 mg: 70-90 mL, and the thiol group of mercaptoethanol undergoes click addition with the double bond of the branched intermediate under the initiation effect, introducing a thioether structure and polyhydroxyl groups.

[0012] Step A3: pre-mix and dilute the polyol monomer, rheological additive, defoamer, and ethyl acetate, then add PMDI resin, mix well, and vacuum degas to obtain a modified adhesive;

[0013] Furthermore, the mass ratio of PMDI resin, polyol monomer, rheological additive, defoaming agent and ethyl acetate is 100:8-12:0.15-0.2:0.1-0.13:5-7.

[0014] The preparation method of the multifunctional fireproof and explosion-proof plate comprises the following steps:

[0015] Step S1: Alkaline-washing and acid-washing the perforated aluminum plate to remove oil and oxide layer, and drying the plate after washing to obtain a clean substrate. Wood shavings and modified adhesive are mixed to obtain a filler.

[0016] Step S2: The filler is loaded into the mold for pre-pressing, and then a clean substrate is placed in the mold for closing the mold, hot pressing to shape the substrate, and demoulding the mold after cooling to obtain a multifunctional fireproof and explosion-proof plate.

[0017] Furthermore, the sizing amount of the filler is 6.5-8.2 wt %.

[0018] Furthermore, the hot pressing process parameters are as follows: the temperature of the high pressure zone is 145-160°C, the hot pressing pressure is 27-30MPa, the holding time is 2-3min, the temperature of the holding zone is 120-130°C, the hot pressing pressure is 12-15MPa, the holding time is 5-8min, the temperature of the thickness setting zone is 90-100°C, the hot pressing pressure is 10-12MPa, and the holding time is 3-5min.

[0019] Furthermore, the moisture content of the wood chips is not higher than 6%.

[0020] Beneficial effects of the present invention:

[0021] 1. The present invention uses perforated aluminum plate as the core layer, and forms a composite plate with wood shavings through hot pressing with a modified adhesive, giving full play to the high strength performance of the aluminum plate. It has good anti-deformation and explosion-proof performance when used in building materials such as door panels and load-bearing panels. Compared with metal plates, it has lower density and is lightweight and high-strength.

[0022] 2. The present invention uses a polyurethane-based modified adhesive in the wood shavings filling layer. The polyurethane-based modified adhesive is obtained by a substitution reaction between methylvinyldichlorosilane and diallylamine, grafting a nitrogen-containing double bond structure to obtain a branched intermediate with a branched double bond. Then, mercaptoethanol is added to the intermediate by click addition to introduce a thioether structure and polyhydroxy groups as a polyol monomer. The polyol monomer is blended with PMDI resin and other additives to form an adhesive. During the hot pressing process, the polyol monomer and PMDI resin are cross-linked and cured. The polyurethane matrix has good bonding properties to the wood shavings, so that the wood shavings and the adhesive form a highly cross-linked and high-strength composite, which is beneficial to improving the overall quality of the filling layer. Mechanical properties; In addition, the polyol monomer introduces a sulfur-nitrogen structure into the polymer chain, which forms a chelating effect on the aluminum plate, and strengthens the bonding performance of the adhesive and the aluminum plate, so that the aluminum plate, wood shavings and adhesive form a high-strength whole, which is not easy to delaminate and peel off during use; In addition, the polyol monomer introduces a silicon-nitrogen structure into the polymer network, which is easy to decompose during the combustion process and has certain flame retardant properties. The introduced sulfide structure promotes the carbonization of organic matter during the combustion process, which is conducive to the formation of a carbonized layer to hinder the deepening of combustion, so that the whole plate has good flame retardancy, and the aluminum plate at the core is fire-resistant and non-combustible, so that the plate has good fire resistance. DETAILED DESCRIPTION

[0023] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0024] Example 1: Preparation of a multifunctional fireproof and explosion-proof plate. The implementation process is as follows:

[0025] 1. Preparation of modified adhesive

[0026] Step A1: Diallylamine, triethylamine, and tetrahydrofuran were added and mixed, and dry nitrogen was introduced to protect the reaction to prevent the influence of oxygen and moisture in the air on the reaction. The temperature was controlled at 15°C using an ice-water bath, and mechanical stirring was applied at 180 rpm. Methylvinyldichlorosilane was added at a constant rate of 10 minutes using a feeder, and the reaction was stirred at a constant temperature for 5 hours. During the reaction, the amount ratio of methylvinyldichlorosilane, diallylamine, triethylamine, and tetrahydrofuran was 0.1 mol:0.2 mol:12 mL:60 mL. After the reaction, the insoluble matter was filtered out and the tetrahydrofuran was removed by rotary evaporation to obtain a branched intermediate.

[0027] Step A2: Take the branched intermediate, dimethylphenylphosphine and toluene, mix them evenly, introduce nitrogen protection to prevent oxidation caused by air, heat to 90 ° C, apply mechanical stirring at 240 rpm, and use UVA lamp at 280 W / m 2 The method comprises the following steps: ultraviolet irradiation, slowly adding mercaptoethanol within 1 hour through a feeder, continuing the constant temperature irradiation and stirring reaction after complete addition, controlling the total addition reaction time of mercaptoethanol to be 2.5 hours, and controlling the amount ratio of the branched intermediate, mercaptoethanol, dimethylphenylphosphine and toluene to be 0.1 mol: 0.52 mol: 20 mg: 90 mL. After the reaction is completed, the toluene is removed by vacuum rotary evaporation to obtain a polyol monomer.

[0028] Step A3: Take a polyol monomer, a rheological additive (BYK-410 raw material is used during the implementation process), and a defoamer (BYK-028 raw material is used during the implementation process), add ethyl acetate to pre-mix and dilute, and then add PMDI resin (Wanhua PM-200 raw material is used during the implementation process, with an -NCO content of approximately 32%). The mass ratio of PMDI resin, polyol monomer, rheological additive, defoamer and ethyl acetate is 100:12:0.15:0.13:7. Mix at room temperature for 20 minutes and vacuum degas to obtain a modified adhesive.

[0029] 2. Preparation of Plates

[0030] Step S1: A perforated aluminum plate (3 mm thick general-purpose plate was used in the implementation process) was sequentially alkali-washed to remove oil, then acid-washed to remove the oxide layer, rinsed with water, and then dried to obtain a clean substrate. Wood shavings (eucalyptus shavings from the same batch were used in the implementation process, with a moisture content of approximately 5%) and a modified adhesive were mixed at a sizing amount of 6.5 wt% to obtain a filler;

[0031] Step S2: The filler is loaded into the mold and pre-pressed at 1.2 MPa. Then, a clean substrate is placed between the pre-pressed plates and the mold is closed. The plate is sent to a hot press for hot pressing and shaping to form a filling layer on the surface of the perforated aluminum plate. The hot press is divided into a high-pressure zone, a holding zone, and a constant thickness zone. The process parameters of each zone are set as follows: the temperature of the high-pressure zone is 145°C, the hot pressing pressure is 27 MPa, and the holding time is 3 minutes. The temperature of the holding zone is 120°C, the hot pressing pressure is 12 MPa, and the holding time is 8 minutes. The temperature of the constant thickness zone is 90°C, the hot pressing pressure is 10 MPa, and the holding time is 5 minutes. After cooling, the plate is demolded to obtain a multifunctional fireproof and explosion-proof plate.

[0032] Example 2: Preparation of a multifunctional fireproof and explosion-proof plate. The implementation process is as follows:

[0033] 1. Preparation of modified adhesive

[0034] Step A1: Diallylamine, triethylamine, and tetrahydrofuran were added and mixed, and dry nitrogen was introduced for protection. The temperature of the mixture was controlled at 5°C in an ice-water bath. Mechanical stirring was applied at 120 rpm. Methylvinyldichlorosilane was added at a uniform rate over 10 minutes using a feeder. The mixture was stirred at a constant temperature for 6 hours. During the reaction, the amount ratio of methylvinyldichlorosilane, diallylamine, triethylamine, and tetrahydrofuran was 0.1 mol:0.2 mol:16 mL:45 mL. After the reaction, the insoluble matter was filtered out and the tetrahydrofuran was removed by rotary evaporation to obtain a branched intermediate.

[0035] Step A2: Take the branched intermediate, dimethylphenylphosphine and toluene, mix them evenly, introduce nitrogen protection to prevent oxidation caused by air, heat to 80°C, apply mechanical stirring at 180 rpm, and use UVA lamp at 220 W / m 2 The method comprises the following steps: ultraviolet irradiation, slowly adding mercaptoethanol within 1.5 hours using a feeder, continuing the constant temperature irradiation and stirring reaction after complete addition, controlling the total addition reaction time of mercaptoethanol to be 3.2 hours, and controlling the amount ratio of the branched intermediate, mercaptoethanol, dimethylphenylphosphine and toluene to be 0.1 mol: 0.51 mol: 30 mg: 70 mL. After the reaction is completed, the toluene is removed by vacuum rotary evaporation to obtain a polyol monomer.

[0036] Step A3: Take a polyol monomer, a rheological additive, and a defoaming agent, add ethyl acetate to premix and dilute, and then add PMDI resin, wherein the mass ratio of PMDI resin, polyol monomer, rheological additive, defoaming agent, and ethyl acetate is 100:8:0.2:0.1:5. Mix at room temperature for 20 minutes and vacuum degas to obtain a modified adhesive.

[0037] 2. Preparation of Plates

[0038] Step S1: taking a perforated aluminum plate, sequentially performing alkaline washing to remove oil, then acid washing to remove the oxide layer, washing with water, and drying to obtain a clean substrate, mixing wood shavings and a modified adhesive at a sizing amount of 8.2 wt% to obtain a filler;

[0039] Step S2: The filler is loaded into the mold and pre-pressed at 1.2 MPa. Then, a clean substrate is placed between the pre-pressed plates and the mold is closed. The plate is sent to a hot press for hot pressing and shaping to form a filling layer on the surface of the perforated aluminum plate. The hot press is divided into a high-pressure zone, a holding zone, and a constant thickness zone. The process parameters of each zone are set as follows: the temperature of the high-pressure zone is 160°C, the hot pressing pressure is 30 MPa, and the holding time is 2 minutes. The temperature of the holding zone is 130°C, the hot pressing pressure is 15 MPa, and the holding time is 5 minutes. The temperature of the constant thickness zone is 100°C, the hot pressing pressure is 12 MPa, and the holding time is 3 minutes. After cooling, the plate is demolded to obtain a multifunctional fireproof and explosion-proof plate.

[0040] Example 3: Preparation of multifunctional fireproof and explosion-proof panels. The implementation process is as follows:

[0041] 1. Preparation of modified adhesive

[0042] Step A1: Diallylamine, triethylamine, and tetrahydrofuran were added and mixed, and dry nitrogen was introduced to protect the reaction to prevent the influence of oxygen and moisture in the air on the reaction. The temperature was controlled at 10°C using an ice-water bath, and mechanical stirring was applied at 180 rpm. Methylvinyldichlorosilane was added at a uniform rate over 10 minutes using a feeder, and the reaction was stirred at a constant temperature for 5.5 hours. During the reaction, the amount ratio of methylvinyldichlorosilane, diallylamine, triethylamine, and tetrahydrofuran was 0.1 mol:0.2 mol:14 mL:55 mL. After the reaction was completed, the insoluble matter was filtered out and the tetrahydrofuran was removed by rotary evaporation to obtain a branched intermediate.

[0043] Step A2: Take the branched intermediate, dimethylphenylphosphine and toluene, mix them evenly, introduce nitrogen protection to prevent oxidation caused by air, heat to 85 ° C, apply mechanical stirring at 240 rpm, and use UVA lamp at 240 W / m 2 The method comprises the following steps: ultraviolet irradiation, slowly adding mercaptoethanol within 1.2 hours using a feeder, continuing the constant temperature irradiation and stirring reaction after complete addition, controlling the total addition reaction time of mercaptoethanol to be 2.8 hours, and controlling the amount ratio of the branched intermediate, mercaptoethanol, dimethylphenylphosphine and toluene to be 0.1 mol: 0.51 mol: 25 mg: 85 mL. After the reaction is completed, the toluene is removed by vacuum rotary evaporation to obtain a polyol monomer.

[0044] Step A3: Take a polyol monomer, a rheological additive, and a defoaming agent, add ethyl acetate to premix and dilute, and then add PMDI resin, wherein the mass ratio of PMDI resin, polyol monomer, rheological additive, defoaming agent, and ethyl acetate is 100:10:0.17:0.12:6.5. Mix at room temperature for 20 minutes and vacuum degas to obtain a modified adhesive.

[0045] 2. Preparation of Plates

[0046] Step S1: taking a perforated aluminum plate, sequentially performing alkaline washing to remove oil, then acid washing to remove the oxide layer, washing with water, and drying to obtain a clean substrate, mixing wood shavings and a modified adhesive at a sizing amount of 7.5 wt% to obtain a filler;

[0047] Step S2: The filler is loaded into the mold and pre-pressed at 1.2 MPa. Then, a clean substrate is placed between the pre-pressed plates and the mold is closed. The plate is sent to a hot press for hot pressing and shaping to form a filling layer on the surface of the perforated aluminum plate. The hot press is divided into a high-pressure zone, a holding zone, and a constant thickness zone. The process parameters of each zone are set as follows: the temperature of the high-pressure zone is 155°C, the hot pressing pressure is 28 MPa, and the holding time is 3 minutes. The temperature of the holding zone is 120°C, the hot pressing pressure is 13 MPa, and the holding time is 7 minutes. The temperature of the constant thickness zone is 100°C, the hot pressing pressure is 12 MPa, and the holding time is 4 minutes. After cooling, the plate is demolded to obtain a multifunctional fireproof and explosion-proof plate.

[0048] Comparative Example

[0049] In this comparative example, polyether polyol 3050 was used to replace the polyol monomer to prepare the adhesive, and the adhesive was applied to wood shavings gluing. The specific implementation process is as follows:

[0050] Step D1: polyether polyol 3050, a rheological additive, a defoamer, and a flame retardant TCEP were added to ethyl acetate for premixing and dilution, and then PMDI resin was added and mixed, wherein the mass ratio of PMDI resin, polyether polyol 3050, rheological additive, defoamer, flame retardant TCEP, and ethyl acetate was 100:17:0.16:0.11:5.5:6.5 to obtain an adhesive;

[0051] Step D2: Referring to Example 3, the wood chips and the adhesive are mixed evenly according to a sizing amount of 10%. The mold setting and hot pressing shaping operations and their process parameters are exactly the same as those in Example 3 to obtain a board.

[0052] The prepared panels were placed in a constant temperature room at 23±2°C and 60±5% humidity for 7 days. The internal bonding strength of the filling layer and the static bending strength of the entire panel were tested according to GB / T 4897-2015. The filling layer was cut to form overlapping specimens according to GB / T 2790-1995, and the peel strength of the filling layer and the perforated aluminum plate was tested. The FIGRA index of the burning rate growth was measured according to GB / T 16172-2007. 0.4MJ And 600s total heat release THR 600s The test was carried out, and the specific test data is shown in Table 1:

[0053] Table 1

[0054]

[0055] It can be seen from the data in Table 1 that the static bending strength of the composite board using perforated aluminum plate and wood particle filling layer reaches more than 70 MPa, which is much higher than the traditional particle board. The internal bonding strength of the filling layer is slightly lower than that of the comparative example, which may be due to the high cross-linking degree in the modified adhesive, affecting its bonding performance, but it is still higher than the standard 0.7 MPa. The peel strength of the perforated aluminum plate and the wood particle filling layer in the embodiment reaches about 9 N / mm, which is much higher than the comparative example. The bonding strength of the filling layer and the perforated aluminum plate is high, the burning rate growth index of the filling layer is lower than 250 W / s, and the total heat release in 600s is lower than 15 MJ, which shows good flame retardancy compared with the comparative example.

[0056] Throughout the specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0057] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in similar ways. As long as they do not deviate from the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A multifunctional fireproof and explosion-proof plate, characterized in that: The invention comprises a perforated aluminum plate and a filling layer on the surface thereof, wherein the filling layer is composed of wood chips and a modified adhesive; The modified adhesive is prepared by the following method: Step A1: Diallylamine, triethylamine, and tetrahydrofuran are mixed, and dry nitrogen is introduced into the mixture. The temperature is controlled at 5-15°C in an ice-water bath. Methylvinyldichlorosilane is added at a constant rate while stirring. The mixture is stirred at the constant temperature for 5-6 hours. After the reaction is completed, the mixture is filtered and the tetrahydrofuran is removed by rotary evaporation to obtain a branched intermediate. Step A2: Mix the branched intermediate, dimethylphenylphosphine and toluene, introduce nitrogen protection, heat to 80-90°C, stir and add 220-280W / m 2 UV irradiation, slowly adding mercaptoethanol, controlling the total reaction time to be 2.5-3.2h, and removing toluene by vacuum rotary evaporation after the reaction to obtain a polyol monomer; Step A3: pre-mix and dilute the polyol monomer, rheological additive, defoamer and ethyl acetate, then add PMDI resin, mix well, and vacuum degas to obtain a modified adhesive.

2. The multifunctional fireproof and explosion-proof plate according to claim 1, characterized in that: The usage ratio of methylvinyldichlorosilane, diallylamine, triethylamine and tetrahydrofuran is 0.1 mol: 0.2 mol: 12-16 mL: 45-60 mL.

3. The multifunctional fireproof and explosion-proof plate according to claim 2, characterized in that: The usage ratio of the branched intermediate, mercaptoethanol, dimethylphenylphosphine and toluene is 0.1 mol: 0.51-0.52 mol: 20-30 mg: 70-90 mL.

4. The multifunctional fireproof and explosion-proof plate according to claim 3, characterized in that: The mass ratio of PMDI resin, polyol monomer, rheological additive, defoaming agent and ethyl acetate is 100:8-12:0.15-0.2:0.1-0.13:5-7.

5. The method for preparing a multifunctional fireproof and explosion-proof plate according to claim 4, characterized in that: The steps include: Step S1: Alkaline-washing and acid-washing the perforated aluminum plate to remove oil and oxide layer, and drying the plate after washing to obtain a clean substrate. Wood shavings and modified adhesive are mixed to obtain a filler. Step S2: The filler is loaded into the mold for pre-pressing, and then a clean substrate is placed in the mold for closing the mold, hot pressing to shape the substrate, and demoulding the mold after cooling to obtain a multifunctional fireproof and explosion-proof plate.

6. The method for preparing a multifunctional fireproof and explosion-proof plate according to claim 5, characterized in that: The sizing amount of the filler is 6.5-8.2 wt%.

7. The method for preparing a multifunctional fireproof and explosion-proof plate according to claim 5, characterized in that: The hot pressing process parameters are: high pressure zone temperature is 145-160℃, hot pressing pressure is 27-30MPa, holding time is 2-3min, holding zone temperature is 120-130℃, hot pressing pressure is 12-15MPa, holding time is 5-8min, thickness setting zone temperature is 90-100℃, hot pressing pressure is 10-12MPa, holding time is 3-5min.

8. The method for preparing a multifunctional fireproof and explosion-proof plate according to claim 5, characterized in that: The moisture content of the shavings is not higher than 6%.

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