Polyvinyl alcohol modified silicate / polyisocyanate thermosetting composite material and preparation method thereof

Abstract

The invention belongs to the technical field of thermosetting composite materials, and particularly relates to a polyvinyl alcohol modified silicate / polyisocyanate thermosetting composite material and a preparation method thereof. A component A is mainly composed of silicate water glass, glycerol, polyvinyl alcohol powder with different molecular weights and alcoholysis degrees, an A33 catalyst, a DMAEE catalyst, a DMP-30 accelerant, a water-based defoaming agent and the like; the component B is composed of polyphenyl polymethylene polyisocyanate, a PTMEG type polyurethane prepolymer, diethylene glycol dibenzoate, chlorinated paraffin, a TCEP flame retardant and the like; mixing the material A and the material B according to the volume ratio of 1: 1, and performing curing reaction to form the polyvinyl alcohol modified silicate / polyisocyanate thermosetting composite material. The polyvinyl alcohol with different molecular weights and different alcoholysis degrees can improve the toughness and brittleness of the thermosetting composite material, also can improve the compression deformation quantity and corresponding mechanical properties of the composite material, and also has the characteristics of high antistatic property and low temperature in the polymerization reaction curing process.

Description

Technical Field

[0001] The present invention belongs to the technical field of thermosetting composite materials, and in particular relates to a polyvinyl alcohol modified silicate / polyisocyanate thermosetting composite material and a preparation method thereof. Background Art

[0002] With the increase in mining depth and the emergence of complex terrain, dangerous accidents such as roof collapse and spalling caused by fault fracture zones and unstable strata not only affect the production efficiency of enterprises but also seriously threaten the lives of miners. Therefore, grouting reinforcement is generally required during the production process. Currently, the most widely used are pure polyurethane organic reinforcement materials and silicate / polyisocyanate composite reinforcement materials. Pure polyurethane organic reinforcement materials have advantages such as good permeability, fast gelation rate, good adhesion, and high strength. However, the reaction temperature during curing is high and the cost is high. The resulting polyurethane reinforcement material has poor conductivity and antistatic properties, necessitating the addition of a large amount of antistatic agent. The addition of antistatic agent will lead to a decrease in the mechanical properties of organic thermosetting reinforcement materials. Mining silicate / polyisocyanate reinforcement materials have a low reaction temperature and low cost. Due to the high water content in the system, they have excellent antistatic properties, but their toughness is lower than that of organic polyurethane thermosetting reinforcement materials. Compared with polyurethane organic thermosetting reinforcement materials, they are more brittle, resulting in lower deformation, compressive strength, shear strength, and tensile strength. Summary of the Invention

[0003] The technical problem to be solved by the present invention is that the existing technology has technical problems such as greater brittleness compared to polyurethane organic thermosetting reinforcement materials, resulting in lower deformation, compressive strength, shear strength and tensile strength.

[0004] To solve the above technical problems, the present invention provides a polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material and a preparation method thereof, comprising component A and component B, wherein component A and component B are calculated in parts by mass: Component A: 91-94 parts of silicate water glass, 1-2 parts of glycerol, 1-2 parts of 1799 polyvinyl alcohol powder, 1-2 parts of 2688 polyvinyl alcohol powder, 0.5-1 part of A33 catalyst, 0.5-1 part of DMAEE catalyst, 0.5-1 part of DMP-30 accelerator, 0.5-1 part of BYK-012 water-based defoamer, and 1-2 parts of industrial water; Component B: 64-68 parts of polyphenyl polymethylene polyisocyanate, 7-10 parts of PTMEG type polyurethane prepolymer, 11-13 parts of diethylene glycol dibenzoate, 9-11 parts of chlorinated paraffin, and 5-7 parts of TCEP flame retardant.

[0005] Further technical solution, the preparation method of the PTMEG type polyurethane prepolymer is as follows: Accurately weigh 100 parts of polytetrahydrofuran diol PTMEG1000 and 200 parts of polytetrahydrofuran diol PTMEG2000, place them in a reactor, stir and dehydrate at 120°C, -0.09MPa for 2 hours, and when the temperature drops to 50°C, accurately add 500 parts of polyphenyl polymethylene polyisocyanate, react at 50°C for 30 minutes, then heat to 80-82°C and react for 2.0 hours. Vacuum degassing for 30 minutes until the reactant becomes a transparent liquid, thereby obtaining a PTMEG type polyurethane prepolymer with an -NCO mass content of 18.3%.

[0006] A further technical solution is that the silicate water glass is a mixture of 85 parts of sodium silicate water glass, 10 parts of potassium silicate water glass, and 5 parts of lithium silicate water glass, and the modulus of sodium silicate water glass is 2.2-2.4, and the density is 1.4-1.5 g / cm³ (20°C); the modulus of lithium silicate water glass is 4.6-4.9, and the density is 1.1-1.2 g / cm³ (20°C); the modulus of potassium silicate water glass is 3.0-3.3, and the density is 1.3-1.4 g / cm³ (20°C).

[0007] According to a further technical solution, the particle size of the 1799 type polyvinyl alcohol powder and the 2688 type polyvinyl alcohol powder are both less than 50 microns and are commercially available industrial products; The glycerol is a commercially available industrial product with a content of 99%; The polyphenyl polymethylene polyisocyanate is an isocyanate product with a mass content of -NCO groups of 31% to 31.5% produced by Yantai Wanhua Chemical, code-named PM200; The A33 catalyst is a 33% triethylenediamine 67% diethylene glycol solution; The DMAEE catalyst is a commercially available industrial product of N,N-dimethylaminoethoxyethylene glycol; The DMP-30 accelerator is a commercially available industrial product of 2,4,6-tris(dimethylaminomethyl)phenol; The diethylene glycol dibenzoate is a commercially available industrial product; The BYK-012 water-based defoamer is a product produced and sold by BYK in Germany; Described PTMEG1000 polytetrahydrofuran diol and PTMEG2000 polytetrahydrofuran diol are commercially available industrial products; The chlorinated paraffin is chlorinated paraffin 52 with a content of 99%; The TCEP flame retardant is a commercially available industrial product with a content of 99%.

[0008] The method for preparing the polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material is as follows: Step 1: Preparation of component A Add 91-94 parts of silicate water glass and 1-2 parts of industrial water into a stirring mixer and stir to mix evenly. Then add 1-2 parts of glycerol, 0.5-1 part of A33 catalyst, 0.5-1 part of DMAEE catalyst, 0.5-1 part of DMP-30 accelerator, and 0.5-1 part of BYK-012 aqueous defoamer into the silicate water glass and stir to mix evenly at a stirring rate of 30-40 r / min. Finally, add 1-2 parts of 1799 type polyvinyl alcohol powder and 1-2 parts of 2688 type polyvinyl alcohol powder into the above mixture, stir and disperse thoroughly for 20-30 minutes, and vacuum degas to obtain component A. Step 2: Preparation of component B Add 64-68 parts of polyphenyl polymethylene polyisocyanate into a mixing container, then add 7-10 parts of PTMEG type polyurethane prepolymer, 11-13 parts of diethylene glycol dibenzoate, 9-11 parts of chlorinated paraffin, and 5-7 parts of TCEP flame retardant into the mixer in sequence, stir and mix at room temperature, and vacuum degas for 20-30 minutes to obtain component B; Step 3: Preparation of polyvinyl alcohol modified silicate / polyisocyanate thermosetting composite material The prepared component A material and component B material were rapidly stirred and mixed in a volume ratio of 1:1 for 15 to 20 seconds to ensure uniform mixing of the materials. The materials were then poured into a cylindrical metal mold with a height of 100 mm and a diameter of 50 mm. A liquid release agent was applied to the inner surface of the mold. After curing for 3 to 5 minutes, the mold was demolded to obtain a polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material.

[0009] Currently, silicate / polyisocyanate reinforcement materials are widely used in coal mines. Silicates are water-soluble components, while polyisocyanates are oil-soluble. A mixed reaction between the two forms polyurethane urea polymer chains and -Si-O-Si- macromolecular chains, which interpenetrate to form a cross-linked inorganic / organic thermosetting polymer with high mechanical strength. Polyvinyl alcohol (PVA) is a water-soluble, flexible polymer with a high number of hydroxyl groups on its macromolecular chains. When its powder is dispersed in a silicate aqueous solution, it swells instead of dissolving. In this way, the hydroxyl groups on its surface are exposed, allowing the hydroxyl groups on its surface to react with the isocyanate groups in the polyisocyanate to generate macromolecular chains with a certain degree of branching and cross-linking. The high molecular weight and low molecular weight undissolved polyvinyl alcohol particles can synergistically play a stress dispersion and elastic role, which can significantly improve the toughness of the silicate / polyisocyanate composite thermosetting composite material, greatly improve the brittleness of the silicate / polyisocyanate thermosetting composite material, increase its compressive deformation and corresponding mechanical properties, and effectively reduce the temperature of the polymerization reaction process.

[0010] The polyvinyl alcohol used is powdered polyvinyl alcohol with different molecular weights and different alcoholysis degrees. It is used to improve the toughness of thermosetting composite materials, improve their brittleness, and increase their compressive deformation and corresponding mechanical properties. It also has high antistatic properties and low polymerization reaction curing process temperature characteristics. It can meet the comprehensive performance and use requirements of thermosetting reinforcement materials used in coal mines, and can also be used to reinforce cracks in tunnel excavation and as a rapid repair adhesive for cracks in concrete dams.

[0011] Compared with the prior art, the present invention has the following innovations and positive effects: ① The addition of polyvinyl alcohol with different molecular weights and different alcoholysis degrees can significantly reduce the reaction temperature of the curing process by 6 to 8°C, increase the toughness of the composite material, greatly improve the brittleness of the silicate / polyisocyanate thermosetting composite material, and improve its compressive deformation and corresponding mechanical properties. The addition of polyvinyl alcohol is a special contribution to the preparation process and performance of silicate / polyisocyanate thermosetting composite materials.

[0012] ② The addition of water-based defoaming agent can effectively eliminate bubbles generated during the mixing process of materials A and B, increase the internal density of the composite material, and effectively improve the mechanical properties of the composite material.

[0013] ③ Sodium silicate water glass, potassium silicate water glass and lithium silicate water glass are mixed together. Sodium silicate water glass has strong bonding force, high strength, excellent acid resistance and heat resistance; potassium silicate water glass has high corrosion resistance; lithium silicate water glass has the characteristics of self-drying, wear resistance, water resistance and weather resistance. The water glass solidified material formed by the mixture of the three improves the water resistance and bonding properties of the mixed water glass solidified material.

[0014] ④ The mixed use of DMAEE, A-33 catalyst and DMP-30 accelerator increased the reaction conversion rate of water-soluble water glass and oil-soluble isocyanate materials, and further improved the comprehensive mechanical properties of the product.

[0015] ⑤ Diethylene glycol dibenzoate can promote the solidification of water glass, and synergistically act with polyvinyl alcohol to reduce the brittleness of the solidified material and improve the mechanical properties of silicate / polyisocyanate composite thermosetting materials.

[0016] ⑥ This thermosetting composite material has excellent comprehensive performance and a wide range of applications. It can be used to reinforce loose coal seams in coal mines, to reinforce cracks in tunnel excavation, and as a quick repair adhesive for cracks in concrete dams and concrete pavement. DETAILED DESCRIPTION Example 1

[0017] The polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material described in this embodiment is composed of component A and component B. The content and composition of each component are as follows, in parts by mass: Component A: 91 parts of silicate water glass, 2 parts of glycerol, 2 parts of 1799 polyvinyl alcohol powder, 2 parts of 2688 polyvinyl alcohol powder, 1 part of A33 catalyst, 1 part of DMAEE catalyst, 1 part of DMP-30 accelerator, 1 part of BYK-012 water-based defoamer, and 2 parts of industrial water; Component B: 64 parts of polyphenyl polymethylene polyisocyanate, 10 parts of PTMEG type polyurethane prepolymer, 13 parts of diethylene glycol dibenzoate, 11 parts of chlorinated paraffin, and 7 parts of TCEP flame retardant.

[0018] The silicate water glass is a mixture of 85 parts of sodium silicate water glass, 10 parts of potassium silicate water glass, and 5 parts of lithium silicate water glass, and the modulus of the sodium silicate water glass is 2.2-2.4, and the density is 1.4-1.5 g / cm³ (20°C); the modulus of the lithium silicate water glass is 4.6-4.9, and the density is 1.1-1.2 g / cm³ (20°C); the modulus of the potassium silicate water glass is 3.0-3.3, and the density is 1.3-1.4 g / cm³ (20°C).

[0019] The particle size of the 1799 type polyvinyl alcohol powder and the 2688 type polyvinyl alcohol powder are both less than 50 microns and are commercially available industrial products; the propylene glycol is a commercially available industrial product with a content of 99%; the polyphenyl polymethylene polyisocyanate is an isocyanate product with a mass content of -NCO groups of 31% to 31.5% produced by Yantai Wanhua Chemical, code-named PM200; the A33 catalyst is a 33% triethylenediamine 67% diethylene glycol solution; the DMAEE catalyst is N,N-dimethylaminoethoxyethylenediamine The alcohol is a commercially available industrial product; the DMP-30 accelerator is a commercially available industrial product of 2,4,6-tris(dimethylaminomethyl)phenol; the diethylene glycol dibenzoate is a commercially available industrial product; the BYK-012 water-based defoamer is a product produced by BYK of Germany; the polytetramethylene glycol (PTMEG1000) and polytetramethylene glycol (PTMEG2000) are commercially available industrial products; the chlorinated paraffin is a chlorinated paraffin 52 with a content of 99%; and the TCEP flame retardant is a commercially available industrial product with a content of 99%.

[0020] The preparation method of the polyurethane prepolymer is as follows: Accurately weigh 100 parts of polytetrahydrofuran diol PTMEG1000 and 200 parts of polytetrahydrofuran diol PTMEG2000, place them in a reactor, stir and dehydrate at 120°C, -0.09MPa for 2 hours, and when the temperature drops to 50°C, accurately add 500 parts of polyphenyl polymethylene polyisocyanate, react at 50°C for 30 minutes, then heat to 80-82°C and react for 2.0 hours. Vacuum degassing for 30 minutes until the reactant becomes a transparent liquid, thereby obtaining a PTMEG type polyurethane prepolymer with an -NCO mass content of 18.3%.

[0021] The preparation method of the polyvinyl alcohol modified silicate / polyisocyanate thermosetting composite material is prepared according to the following steps: Step 1: Preparation of component A Add 91 parts of silicate water glass and 2 parts of industrial water into a stirring mixer and stir to mix evenly. Then add 2 parts of glycerol, 1 part of A33 catalyst, 1 part of DMAEE catalyst, 1 part of DMP-30 accelerator, and 1 part of BYK-012 aqueous defoamer into the silicate water glass and stir to mix evenly at a stirring rate of 30 to 40 r / min. Finally, add 2 parts of 1799 type polyvinyl alcohol powder and 2 parts of 2688 type polyvinyl alcohol powder into the above mixture, stir and disperse thoroughly for 20 to 30 minutes, and vacuum degas to obtain component A.

[0022] Step 2: Preparation of component B Add 64 parts of polyphenyl polymethylene polyisocyanate into a mixing container, and then add 10 parts of PTMEG type polyurethane prepolymer, 13 parts of diethylene glycol dibenzoate, 11 parts of chlorinated paraffin, and 7 parts of TCEP flame retardant into the mixer in sequence, stir and mix at room temperature, and vacuum degas for 20 to 30 minutes to obtain component B.

[0023] Step 3: Preparation of polyvinyl alcohol modified silicate / polyisocyanate thermosetting composite material The prepared component A material and component B material were rapidly stirred and mixed in a volume ratio of 1:1 for 15 to 20 seconds to ensure uniform mixing of the materials. The materials were then poured into a cylindrical metal mold with a height of 100 mm and a diameter of 50 mm. A liquid release agent was applied to the inner surface of the mold. After curing for 3 to 5 minutes, the mold was demolded to obtain a polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material. Example 2

[0024] The polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material described in this embodiment is composed of component A and component B. The content and composition of each component are as follows, in parts by mass: Component A: 94 parts of silicate water glass, 1 part of glycerol, 1 part of 1799 type polyvinyl alcohol powder, 1 part of 2688 type polyvinyl alcohol powder, 0.5 part of A33 catalyst, 0.5 part of DMAEE catalyst, 0.5 part of DMP-30 accelerator, 0.5 part of BYK-012 water-based defoamer, and 1 part of industrial water.

[0025] Component B: 68 parts of polyphenyl polymethylene polyisocyanate, 7 parts of PTMEG type polyurethane prepolymer, 11 parts of diethylene glycol dibenzoate, 9 parts of chlorinated paraffin, and 5 parts of TCEP flame retardant.

[0026] The silicate water glass is a mixture of 85 parts of sodium silicate water glass, 10 parts of potassium silicate water glass, and 5 parts of lithium silicate water glass, and the modulus of the sodium silicate water glass is 2.2-2.4, and the density is 1.4-1.5 g / cm³ (20°C); the modulus of the lithium silicate water glass is 4.6-4.9, and the density is 1.1-1.2 g / cm³ (20°C); the modulus of the potassium silicate water glass is 3.0-3.3, and the density is 1.3-1.4 g / cm³ (20°C).

[0027] The particle size of the 1799 type polyvinyl alcohol powder and the 2688 type polyvinyl alcohol powder are both less than 50 microns and are commercially available industrial products; the propylene glycol is a commercially available industrial product with a content of 99%; the polyphenyl polymethylene polyisocyanate is an isocyanate product with a mass content of -NCO groups of 31% to 31.5% produced by Yantai Wanhua Chemical, code-named PM200; the A33 catalyst is a 33% triethylenediamine 67% diethylene glycol solution; the DMAEE catalyst is N,N-dimethylaminoethoxyethylenediamine The alcohol is a commercially available industrial product; the DMP-30 accelerator is a commercially available industrial product of 2,4,6-tris(dimethylaminomethyl)phenol; the diethylene glycol dibenzoate is a commercially available industrial product; the BYK-012 water-based defoamer is a product produced by BYK of Germany; the polytetramethylene glycol (PTMEG1000) and polytetramethylene glycol (PTMEG2000) are commercially available industrial products; the chlorinated paraffin is a chlorinated paraffin 52 with a content of 99%; and the TCEP flame retardant is a commercially available industrial product with a content of 99%.

[0028] The preparation method of the polyurethane prepolymer is as follows: Accurately weigh 100 parts of polytetrahydrofuran diol PTMEG1000 and 200 parts of polytetrahydrofuran diol PTMEG2000, place them in a reactor, stir and dehydrate at 120°C, -0.09MPa for 2 hours, and when the temperature drops to 50°C, accurately add 500 parts of polyphenyl polymethylene polyisocyanate, react at 50°C for 30 minutes, then heat to 80-82°C and react for 2.0 hours. Vacuum degassing for 30 minutes until the reactant becomes a transparent liquid, thereby obtaining a PTMEG type polyurethane prepolymer with an -NCO mass content of 18.3%.

[0029] The preparation method of the polyvinyl alcohol modified silicate / polyisocyanate thermosetting composite material is prepared according to the following steps: Step 1: Preparation of component A Add 94 parts of silicate water glass and 1 part of industrial water into a stirring mixer and stir to mix evenly. Then add 1 part of glycerol, 0.5 parts of A33 catalyst, 0.5 parts of DMAEE catalyst, 0.5 parts of DMP-30 accelerator and 0.5 parts of BYK-012 aqueous defoamer into the silicate water glass and stir to mix evenly at a stirring rate of 30 to 40 r / min. Finally, add 1 part of 1799 type polyvinyl alcohol powder and 1 part of 2688 type polyvinyl alcohol powder into the above mixture, stir and disperse thoroughly for 20 to 30 minutes, and vacuum degas to obtain component A.

[0030] Step 2: Preparation of component B Add 68 parts of polyphenyl polymethylene polyisocyanate into a mixing container, and then add 7 parts of PTMEG type polyurethane prepolymer, 11 parts of diethylene glycol dibenzoate, 9 parts of chlorinated paraffin, and 5 parts of TCEP flame retardant into the mixer in sequence, stir and mix at room temperature, and vacuum degas for 20 to 30 minutes to obtain component B.

[0031] Step 3: Preparation of polyvinyl alcohol modified silicate / polyisocyanate thermosetting composite material The prepared component A material and component B material were rapidly stirred and mixed in a volume ratio of 1:1 for 15 to 20 seconds to ensure uniform mixing of the materials. The materials were then poured into a cylindrical metal mold with a height of 100 mm and a diameter of 50 mm. A liquid release agent was applied to the inner surface of the mold. After curing for 3 to 5 minutes, the mold was demolded to obtain a polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material. Example 3

[0032] The polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material described in this embodiment is composed of component A and component B. The content and composition of each component are as follows, in parts by mass: Component A: 92 parts of silicate water glass, 1 part of glycerol, 2 parts of 1799 type polyvinyl alcohol powder, 1 part of 2688 type polyvinyl alcohol powder, 1 part of A33 catalyst, 0.5 parts of DMAEE catalyst, 1 part of DMP-30 accelerator, 1 part of BYK-012 water-based defoamer, and 2 parts of industrial water.

[0033] Component B: 66 parts of polyphenyl polymethylene polyisocyanate, 8 parts of PTMEG type polyurethane prepolymer, 12 parts of diethylene glycol dibenzoate, 10 parts of chlorinated paraffin, and 6 parts of TCEP flame retardant.

[0034] The silicate water glass is a mixture of 85 parts of sodium silicate water glass, 10 parts of potassium silicate water glass, and 5 parts of lithium silicate water glass, and the modulus of the sodium silicate water glass is 2.2-2.4, and the density is 1.4-1.5 g / cm³ (20°C); the modulus of the lithium silicate water glass is 4.6-4.9, and the density is 1.1-1.2 g / cm³ (20°C); the modulus of the potassium silicate water glass is 3.0-3.3, and the density is 1.3-1.4 g / cm³ (20°C).

[0035] The particle size of the 1799 type polyvinyl alcohol powder and the 2688 type polyvinyl alcohol powder are both less than 50 microns and are commercially available industrial products; the propylene glycol is a commercially available industrial product with a content of 99%; the polyphenyl polymethylene polyisocyanate is an isocyanate product with a mass content of -NCO groups of 31% to 31.5% produced by Yantai Wanhua Chemical, code-named PM200; the A33 catalyst is a 33% triethylenediamine 67% diethylene glycol solution; the DMAEE catalyst is N,N-dimethylaminoethoxyethylenediamine The alcohol is a commercially available industrial product; the DMP-30 accelerator is a commercially available industrial product of 2,4,6-tris(dimethylaminomethyl)phenol; the diethylene glycol dibenzoate is a commercially available industrial product; the BYK-012 water-based defoamer is a product produced by BYK of Germany; the polytetramethylene glycol (PTMEG1000) and polytetramethylene glycol (PTMEG2000) are commercially available industrial products; the chlorinated paraffin is a chlorinated paraffin 52 with a content of 99%; and the TCEP flame retardant is a commercially available industrial product with a content of 99%.

[0036] The preparation method of the polyurethane prepolymer is as follows: Accurately weigh 100 parts of polytetrahydrofuran diol PTMEG1000 and 200 parts of polytetrahydrofuran diol PTMEG2000, place them in a reactor, stir and dehydrate at 120°C, -0.09MPa for 2 hours, and when the temperature drops to 50°C, accurately add 500 parts of polyphenyl polymethylene polyisocyanate, react at 50°C for 30 minutes, then heat to 80-82°C and react for 2.0 hours. Vacuum degassing for 30 minutes until the reactant becomes a transparent liquid, thereby obtaining a PTMEG type polyurethane prepolymer with an -NCO mass content of 18.3%.

[0037] The preparation method of the polyvinyl alcohol modified silicate / polyisocyanate thermosetting composite material is prepared according to the following steps: Step 1: Preparation of component A Add 92 parts of silicate water glass and 2 parts of industrial water into a stirring mixer and stir to mix evenly. Then add 1 part of glycerol, 1 part of A33 catalyst, 0.5 part of DMAEE catalyst, 1 part of DMP-30 accelerator, and 1 part of BYK-012 aqueous defoamer into the silicate water glass and stir to mix evenly at a stirring rate of 30 to 40 r / min. Finally, add 2 parts of 1799 type polyvinyl alcohol powder and 1 part of 2688 type polyvinyl alcohol powder into the above mixture, stir and disperse thoroughly for 20 to 30 minutes, and vacuum degas to obtain component A.

[0038] Step 2: Preparation of component B Add 66 parts of polyphenyl polymethylene polyisocyanate into a mixing container, then add 8 parts of PTMEG type polyurethane prepolymer, 12 parts of diethylene glycol dibenzoate, 10 parts of chlorinated paraffin, and 6 parts of TCEP flame retardant into the mixer in sequence, stir and mix at room temperature, and vacuum degas for 20 to 30 minutes to obtain component B; Step 3: Preparation of polyvinyl alcohol modified silicate / polyisocyanate thermosetting composite material The prepared component A material and component B material were rapidly stirred and mixed in a volume ratio of 1:1 for 15 to 20 seconds to ensure uniform mixing of the materials. The materials were then poured into a cylindrical metal mold with a height of 100 mm and a diameter of 50 mm. A liquid release agent was applied to the inner surface of the mold. After curing for 3 to 5 minutes, the mold was demolded to obtain a polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material. Example 4

[0039] The polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material described in this embodiment is composed of component A and component B. The content and composition of each component are as follows, in parts by mass: Component A: 93 parts of silicate water glass, 2 parts of glycerol, 2 parts of 1799 type polyvinyl alcohol powder, 2 parts of 2688 type polyvinyl alcohol powder, 0.5 parts of A33 catalyst, 1 part of DMAEE catalyst, 1 part of DMP-30 accelerator, 0.7 parts of BYK-012 water-based defoamer, and 1.5 parts of industrial water.

[0040] Component B: 67 parts of polyphenyl polymethylene polyisocyanate, 10 parts of PTMEG type polyurethane prepolymer, 12 parts of diethylene glycol dibenzoate, 10 parts of chlorinated paraffin, and 6 parts of TCEP flame retardant.

[0041] The silicate water glass is a mixture of 85 parts of sodium silicate water glass, 10 parts of potassium silicate water glass, and 5 parts of lithium silicate water glass, and the modulus of the sodium silicate water glass is 2.2-2.4, and the density is 1.4-1.5 g / cm³ (20°C); the modulus of the lithium silicate water glass is 4.6-4.9, and the density is 1.1-1.2 g / cm³ (20°C); the modulus of the potassium silicate water glass is 3.0-3.3, and the density is 1.3-1.4 g / cm³ (20°C).

[0042] The particle size of the 1799 type polyvinyl alcohol powder and the 2688 type polyvinyl alcohol powder are both less than 50 microns and are commercially available industrial products; the propylene glycol is a commercially available industrial product with a content of 99%; the polyphenyl polymethylene polyisocyanate is an isocyanate product with a mass content of -NCO groups of 31% to 31.5% produced by Yantai Wanhua Chemical, code-named PM200; the A33 catalyst is a 33% triethylenediamine 67% diethylene glycol solution; the DMAEE catalyst is N,N-dimethylaminoethoxyethylenediamine The alcohol is a commercially available industrial product; the DMP-30 accelerator is a commercially available industrial product of 2,4,6-tris(dimethylaminomethyl)phenol; the diethylene glycol dibenzoate is a commercially available industrial product; the BYK-012 water-based defoamer is a product produced by BYK of Germany; the polytetramethylene glycol (PTMEG1000) and polytetramethylene glycol (PTMEG2000) are commercially available industrial products; the chlorinated paraffin is a chlorinated paraffin 52 with a content of 99%; and the TCEP flame retardant is a commercially available industrial product with a content of 99%.

[0043] The preparation method of the polyurethane prepolymer is as follows: Accurately weigh 100 parts of polytetrahydrofuran diol PTMEG1000 and 200 parts of polytetrahydrofuran diol PTMEG2000, place them in a reactor, stir and dehydrate at 120°C, -0.09MPa for 2 hours, and when the temperature drops to 50°C, accurately add 500 parts of polyphenyl polymethylene polyisocyanate, react at 50°C for 30 minutes, then heat to 80-82°C and react for 2.0 hours. Vacuum degassing for 30 minutes until the reactant becomes a transparent liquid, thereby obtaining a PTMEG type polyurethane prepolymer with an -NCO mass content of 18.3%.

[0044] The preparation method of the polyvinyl alcohol modified silicate / polyisocyanate thermosetting composite material is prepared according to the following steps: Step 1: Preparation of component A Add 93 parts of silicate water glass and 1.5 parts of industrial water into a stirring mixer and stir to mix evenly. Then add 2 parts of glycerol, 0.5 parts of A33 catalyst, 1 part of DMAEE catalyst, 1 part of DMP-30 accelerator, and 0.7 parts of BYK-012 aqueous defoamer into the silicate water glass and stir to mix evenly at a stirring rate of 30 to 40 r / min. Finally, add 2 parts of 1799 type polyvinyl alcohol powder and 2 parts of 2688 type polyvinyl alcohol powder into the above mixture, stir and disperse thoroughly for 20 to 30 minutes, and vacuum degas to obtain component A.

[0045] Step 2: Preparation of component B Add 67 parts of polyphenyl polymethylene polyisocyanate into a mixing container, and then add 10 parts of PTMEG type polyurethane prepolymer, 12 parts of diethylene glycol dibenzoate, 10 parts of chlorinated paraffin, and 6 parts of TCEP flame retardant into the mixer in sequence, stir and mix at room temperature, and vacuum degas for 20 to 30 minutes to obtain component B.

[0046] Step 3: Preparation of polyvinyl alcohol modified silicate / polyisocyanate thermosetting composite material The prepared component A material and component B material were rapidly stirred and mixed in a volume ratio of 1:1 for 15 to 20 seconds to ensure uniform mixing of the materials. The materials were then poured into a cylindrical metal mold with a height of 100 mm and a diameter of 50 mm. A liquid release agent was applied to the inner surface of the mold. After curing for 3 to 5 minutes, the mold was demolded to obtain a polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material. Example 5

[0047] The polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material described in this embodiment is composed of component A and component B. The content and composition of each component are as follows, in parts by mass: Component A: 92 parts of silicate water glass, 1 part of glycerol, 2 parts of 1799 type polyvinyl alcohol powder, 1 part of 2688 type polyvinyl alcohol powder, 0.8 parts of A33 catalyst, 0.8 parts of DMAEE catalyst, 0.7 parts of DMP-30 accelerator, 0.7 parts of BYK-012 water-based defoamer, and 1 part of industrial water.

[0048] Component B: 67 parts of polyphenyl polymethylene polyisocyanate, 9 parts of PTMEG type polyurethane prepolymer, 13 parts of diethylene glycol dibenzoate, 11 parts of chlorinated paraffin, and 7 parts of TCEP flame retardant.

[0049] The silicate water glass is a mixture of 85 parts of sodium silicate water glass, 10 parts of potassium silicate water glass, and 5 parts of lithium silicate water glass, and the modulus of the sodium silicate water glass is 2.2-2.4, and the density is 1.4-1.5 g / cm³ (20°C); the modulus of the lithium silicate water glass is 4.6-4.9, and the density is 1.1-1.2 g / cm³ (20°C); the modulus of the potassium silicate water glass is 3.0-3.3, and the density is 1.3-1.4 g / cm³ (20°C).

[0050] The particle size of the 1799 type polyvinyl alcohol powder and the 2688 type polyvinyl alcohol powder are both less than 50 microns and are commercially available industrial products; the propylene glycol is a commercially available industrial product with a content of 99%; the polyphenyl polymethylene polyisocyanate is an isocyanate product with a mass content of -NCO groups of 31% to 31.5% produced by Yantai Wanhua Chemical, code-named PM200; the A33 catalyst is a 33% triethylenediamine 67% diethylene glycol solution; the DMAEE catalyst is N,N-dimethylaminoethoxyethylenediamine The alcohol is a commercially available industrial product; the DMP-30 accelerator is a commercially available industrial product of 2,4,6-tris(dimethylaminomethyl)phenol; the diethylene glycol dibenzoate is a commercially available industrial product; the BYK-012 water-based defoamer is a product produced by BYK of Germany; the polytetramethylene glycol (PTMEG1000) and polytetramethylene glycol (PTMEG2000) are commercially available industrial products; the chlorinated paraffin is a chlorinated paraffin 52 with a content of 99%; and the TCEP flame retardant is a commercially available industrial product with a content of 99%.

[0051] The preparation method of the polyurethane prepolymer is as follows: Accurately weigh 100 parts of polytetrahydrofuran diol PTMEG1000 and 200 parts of polytetrahydrofuran diol PTMEG2000, place them in a reactor, stir and dehydrate at 120°C, -0.09MPa for 2 hours, and when the temperature drops to 50°C, accurately add 500 parts of polyphenyl polymethylene polyisocyanate, react at 50°C for 30 minutes, then heat to 80-82°C and react for 2.0 hours. Vacuum degassing for 30 minutes until the reactant becomes a transparent liquid, thereby obtaining a PTMEG type polyurethane prepolymer with an -NCO mass content of 18.3%.

[0052] The preparation method of the polyvinyl alcohol modified silicate / polyisocyanate thermosetting composite material is prepared according to the following steps: Step 1: Preparation of component A Add 92 parts of silicate water glass and 1 part of industrial water into a stirring mixer and stir to mix evenly. Then add 1 part of glycerol, 0.8 parts of A33 catalyst, 0.8 parts of DMAEE catalyst, 0.7 parts of DMP-30 accelerator and 0.7 parts of BYK-012 aqueous defoamer into the silicate water glass and stir to mix evenly at a stirring rate of 30 to 40 r / min. Finally, add 2 parts of 1799 type polyvinyl alcohol powder and 1 part of 2688 type polyvinyl alcohol powder into the above mixture, stir and disperse thoroughly for 20 to 30 minutes, and vacuum degas to obtain component A.

[0053] Step 2: Preparation of component B Add 67 parts of polyphenyl polymethylene polyisocyanate into a mixing container, and then add 9 parts of PTMEG type polyurethane prepolymer, 13 parts of diethylene glycol dibenzoate, 11 parts of chlorinated paraffin, and 7 parts of TCEP flame retardant into the mixer in sequence, stir and mix at room temperature, and vacuum degas for 20 to 30 minutes to obtain component B.

[0054] Step 3: Preparation of polyvinyl alcohol modified silicate / polyisocyanate thermosetting composite material The prepared component A material and component B material were rapidly stirred and mixed in a volume ratio of 1:1 for 15 to 20 seconds to ensure uniform mixing of the materials. The materials were then poured into a cylindrical metal mold with a height of 100 mm and a diameter of 50 mm. A liquid release agent was applied to the inner surface of the mold. After curing for 3 to 5 minutes, the mold was demolded to obtain a polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material.

[0055] With reference to the test method AQ1089-2020 for polymer materials for coal mine reinforcement, GB / T6328-2021 for test method for shear impact strength of adhesives, and MT113-1995 for test method and judgment rule for flame retardancy and antistatic properties of polymer products for underground coal mines, the properties of the polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material of the present invention are shown in Table 1: Table 1. Properties of polyvinyl alcohol modified silicate / polyisocyanate thermosetting composites name performance Curing process reaction temperature / ℃, ≤ 98 Hardness / Shore D, ≥ 40 Compression strength / MPa, ≥ 43 Shear strength / MPa, ≥ 16 Tensile strength / MPa, ≥ 6 Bending strength / Mpa, ≥ 24 Impact strength / (KJ / m2), ≥ 6 Pull-out bond strength / Mpa, ≥ 4 Compression 40MPa deformation / %, ≥ 37 Oxygen index / %, ≥ 30 Surface resistance / Ω, ≤ 1.85×107

Claims

1. A polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material, characterized by: Including component A and component B, both components A and B are calculated in parts by mass: Component A: 91-94 parts of silicate water glass, 1-2 parts of glycerol, 1-2 parts of 1799 polyvinyl alcohol powder, 1-2 parts of 2688 polyvinyl alcohol powder, 0.5-1 part of A33 catalyst, 0.5-1 part of DMAEE catalyst, 0.5-1 part of DMP-30 accelerator, 0.5-1 part of BYK-012 water-based defoamer, and 1-2 parts of industrial water; Component B: 64-68 parts of polyphenyl polymethylene polyisocyanate, 7-10 parts of PTMEG type polyurethane prepolymer, 11-13 parts of diethylene glycol dibenzoate, 9-11 parts of chlorinated paraffin, and 5-7 parts of TCEP flame retardant.

2. The polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material according to claim 1, characterized in that: The preparation method of the PTMEG type polyurethane prepolymer is as follows: Accurately weigh 100 parts of polytetrahydrofuran diol PTMEG1000 and 200 parts of polytetrahydrofuran diol PTMEG2000, place them in a reactor, stir and dehydrate at 120°C, -0.09MPa for 2 hours, and when the temperature drops to 50°C, accurately add 500 parts of polyphenyl polymethylene polyisocyanate, react at 50°C for 30 minutes, then heat to 80-82°C and react for 2.0 hours. Vacuum degassing for 30 minutes until the reactant becomes a transparent liquid, thereby obtaining a PTMEG type polyurethane prepolymer with an -NCO mass content of 18.3%.

3. The polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material according to claim 1, characterized in that: The silicate water glass is a mixture of 85 parts of sodium silicate water glass, 10 parts of potassium silicate water glass, and 5 parts of lithium silicate water glass, and the modulus of the sodium silicate water glass is 2.2-2.4, and the density is 1.4-1.5 g / cm³ (20°C); the modulus of the lithium silicate water glass is 4.6-4.9, and the density is 1.1-1.2 g / cm³ (20°C); the modulus of the potassium silicate water glass is 3.0-3.3, and the density is 1.3-1.4 g / cm³ (20°C).

4. The polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material according to claim 1, characterized in that: The particle size of the 1799 type polyvinyl alcohol powder and the 2688 type polyvinyl alcohol powder are both less than 50 microns and are commercially available industrial products; The glycerol is a commercially available industrial product with a content of 99%; The polyphenyl polymethylene polyisocyanate is an isocyanate product with a mass content of -NCO groups of 31% to 31.5% produced by Yantai Wanhua Chemical, code-named PM200; The A33 catalyst is a 33% triethylenediamine 67% diethylene glycol solution; The DMAEE catalyst is a commercially available industrial product of N,N-dimethylaminoethoxyethylene glycol; The DMP-30 accelerator is a commercially available industrial product of 2,4,6-tris(dimethylaminomethyl)phenol; The diethylene glycol dibenzoate is a commercially available industrial product; The BYK-012 water-based defoamer is a product produced and sold by BYK in Germany; Described PTMEG1000 polytetrahydrofuran diol and PTMEG2000 polytetrahydrofuran diol are commercially available industrial products; The chlorinated paraffin is chlorinated paraffin 52 with a content of 99%; The TCEP flame retardant is a commercially available industrial product with a content of 99%.

5. A method for preparing the polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material according to any one of claims 1 to 4, characterized in that: Prepare as follows: Step 1: Preparation of component A Add 91-94 parts of silicate water glass and 1-2 parts of industrial water into a stirring mixer and stir to mix evenly. Then add 1-2 parts of glycerol, 0.5-1 part of A33 catalyst, 0.5-1 part of DMAEE catalyst, 0.5-1 part of DMP-30 accelerator, and 0.5-1 part of BYK-012 aqueous defoamer into the silicate water glass and stir to mix evenly at a stirring rate of 30-40 r / min. Finally, add 1-2 parts of 1799 type polyvinyl alcohol powder and 1-2 parts of 2688 type polyvinyl alcohol powder into the above mixture, stir and disperse thoroughly for 20-30 minutes, and vacuum degas to obtain component A. Step 2: Preparation of component B Add 64-68 parts of polyphenyl polymethylene polyisocyanate into a mixing container, then add 7-10 parts of PTMEG type polyurethane prepolymer, 11-13 parts of diethylene glycol dibenzoate, 9-11 parts of chlorinated paraffin, and 5-7 parts of TCEP flame retardant into the mixer in sequence, stir and mix at room temperature, and vacuum degas for 20-30 minutes to obtain component B; Step 3: Preparation of polyvinyl alcohol modified silicate / polyisocyanate thermosetting composite material The prepared component A material and component B material were rapidly stirred and mixed in a volume ratio of 1:1 for 15 to 20 seconds to ensure uniform mixing of the materials. The materials were then poured into a cylindrical metal mold with a height of 100 mm and a diameter of 50 mm. A liquid release agent was applied to the inner surface of the mold. After curing for 3 to 5 minutes, the mold was demolded to obtain a polyvinyl alcohol-modified silicate / polyisocyanate thermosetting composite material.