A flame retardant high-quality silicon thermal insulation material and preparation method thereof

Abstract

The present invention relates to the technical field of polymer thermal insulation materials, and in particular to a flame retardant superior silicon thermal insulation material and a preparation method thereof. The flame retardant superior silicon thermal insulation material is prepared from component A, component B and component C; component A is prepared from the following raw materials in mass percentage: 19-28% polysilicon polyol containing catalyst II, 22-30% melamine polyether polyol, 5-10% crosslinking agent, 2-6% catalyst I, 8-15% liquid flame retardant, and 12-20% foaming agent; component B is polymerized isocyanate; component C is an inorganic flame retardant. The method of the present invention is to transfer component A, component B and component C into a mold or a laminator, and obtain them through foaming and maturation. The method of the present invention ensures that the prepared flame retardant superior silicon thermal insulation material achieves the corresponding flame retardant effect through polysilicon polyol, melamine polyether polyol, and the amount of flame retardant added, thereby solving the flammability problem of polyurethane rigid foam.

Description

Technical Field

[0001] The invention relates to the technical field of polymer thermal insulation materials, and in particular to a flame retardant high-quality silicon thermal insulation material and a preparation method thereof. Background Art

[0002] Polyurethane rigid foam, also known as PU rigid foam, is mainly prepared by foaming and aging polyether polyol and polymerized isocyanate through mold, and has the characteristics of light weight, sound insulation, shockproof, good heat insulation effect, etc., and is widely used in food refrigeration equipment, industrial pipeline insulation materials, building materials, transportation materials and other fields. Among them, low-density PU rigid foam, such as low-density ultra-low thermal conductivity rigid polyurethane foam with publication number CN115073694B, low-density low thermal conductivity polyurethane rigid foam with publication number CN115894853B, etc., are mainly used as insulation materials, which can be cast on site or sprayed to form, so as to be integrated with the insulation material to achieve a good insulation effect. Therefore, in the field of insulation materials, PU rigid foam is the preferred material.

[0003] However, the flammable nature of polyurethane rigid foam is a problem that plagues its promotion, especially when using more flammable ordinary pentane as a foaming agent. Therefore, the flame retardant problem of polyurethane rigid foam has become a major problem that needs to be solved urgently. Due to the flammable nature of ordinary pentane, it has certain limitations in polyurethane rigid foam. As for the non-flammable foaming agent 141b, it will be banned from use due to environmental safety issues caused by its high ODP and GWP values. ODP is a measure of the ability of a substance to destroy stratospheric ozone, expressed as an ozone depletion potential. GWP is expressed as an index of the greenhouse effect produced by a substance.

[0004] In order to solve the flame retardancy problem of polyurethane rigid foam using ordinary pentane as foaming agent, the flame retardancy of polyurethane is mainly improved by adding a large amount of flame retardants. For example, phosphorus-containing flame retardants are used to modify the flame retardancy of polyurethane rigid foam. However, the flame retardancy of polyurethane rigid foam prepared in this way is limited, and a large amount of flame retardants are likely to affect the performance of polyurethane. Summary of the invention

[0005] In order to solve the flammability problem of polyurethane rigid foam using ordinary pentane as a foaming agent, the purpose of the present invention is to provide a flame retardant high-quality silicon thermal insulation material and a preparation method thereof.

[0006] To achieve the above objectives, the technical solution of the present invention is as follows.

[0007] The first aspect of the present invention provides a flame retardant high-quality silicon thermal insulation material, which is prepared from component A, component B and component C;

[0008] The A component is prepared from the following raw materials in percentage by mass:

[0009] Containing 19-28% of polysilicone polyol of catalyst II, 22-30% of melamine polyether polyol, 5-10% of crosslinking agent, 2-6% of catalyst I, 8-15% of liquid flame retardant, and 12-20% of foaming agent;

[0010] The B component is a polymeric isocyanate; the C component is an inorganic flame retardant;

[0011] Among them, the mass ratio of component A, component B and component C is 1:1.0-1.5:0.1-0.3, or the mass ratio of component A, component B and component C is 1:1.0-1.5:2.2-2.6.

[0012] The present invention mainly ensures that the prepared flame-retardant excellent silicon thermal insulation material achieves the corresponding flame-retardant effect by using polysilicone polyol and melamine polyether polyol containing catalyst II and adding a certain amount of flame retardant, thereby solving the flame-retardant problem of polyurethane, especially polyurethane prepared by using ordinary pentane as a foaming agent.

[0013] Preferably, the polysilicone polyol containing catalyst II is prepared by reacting silica sol, catalyst II and diethylene glycol at 90-100° C. and simultaneously performing vacuum dehydration treatment.

[0014] On the one hand, the present invention replaces part of the flammable and easily decomposable carbon elements with non-flammable silicon dioxide, and at the same time ensures that the silicon dioxide is in a liquid state; on the other hand, a large amount of nitrogen-containing compounds (such as melamine polyether polyol) are introduced, and the flame retardant performance is improved by using the decomposition of nitrogen-containing compounds to form nitrogen (inert gas). Non-flammable silicon dioxide mainly comes from silica sol, and the present invention uses silica sol to synthesize polysilicon polyol under the catalytic action of catalyst II. Catalyst II is an organic amine catalyst, so the addition of catalyst II can not only catalyze the synthesis of polysilicon polyol, but also catalyze the synthesis of polyurethane rigid foam (flame retardant excellent silicon insulation material), thereby reducing the amount of catalyst I in component A to reduce costs. The introduction of a large amount of nitrogen-containing compounds mainly comes from melamine polyether polyol, which uses melamine to modify polyether polyol under the action of silicone oil to prepare emulsified melamine polyether polyol, which solves the problem of flammability while also solving the compatibility problem of melamine and polyether polyol.

[0015] Preferably, the catalyst II is an organic amine compound. Preferably, the catalyst II is any one of triethylenediamine, pentamethyldiethylenetriamine, hexamethylenetetramine, and dimethylcyclohexylamine. Catalyst II is used as a synthesis catalyst for polysilicone polyol on the one hand, and as a synthesis catalyst for polyurethane rigid foam on the other hand, thereby reducing the amount of catalyst I used to reduce costs.

[0016] Preferably, the mass percentage of SiO2 in the silica sol is 20-30%; the mass ratio of silica sol, catalyst II and diethylene glycol is 1000:2-4:500-700.

[0017] Preferably, the water content of the polysilicone polyol containing catalyst II is ≤ 0.5 wt.%.

[0018] Preferably, the melamine polyether polyol is prepared by uniformly mixing polyether polyol, silicone oil and melamine, and then shearing and emulsifying to obtain emulsified melamine polyether polyol. The emulsified melamine polyether polyol is formed by adding silicone oil and shearing and emulsifying, which can solve the compatibility problem between melamine and polyether polyol.

[0019] Preferably, the polyether polyol is polyether polyol 4110 or polyether polyol 635; and the silicone oil is any one of dimethyl silicone oil, methyl silicone oil 201 and methyl silicone oil 350.

[0020] Preferably, the mass ratio of polyether polyol, silicone oil and melamine is 1000:5-10:1000.

[0021] Preferably, the shear emulsification conditions are: rotation speed of 4000-8000 r / min; temperature of 120-130° C.; and time of 3-4 h.

[0022] Preferably, the crosslinking agent is polyether polyol 403 or triethanolamine; the catalyst I is cyclohexylamine; the liquid flame retardant is tris(2-chloropropyl) phosphate; and the blowing agent is pentane.

[0023] Preferably, the inorganic flame retardant is aluminum oxide.

[0024] The second aspect of the present invention provides a method for preparing a flame retardant high-quality silicon thermal insulation material, comprising the following steps: reacting silica sol and diethylene glycol at 90-100° C. under the action of catalyst II, and performing vacuum dehydration treatment at the same time to prepare polysilicone polyol containing catalyst II; uniformly mixing polyether polyol, silicone oil and melamine, and performing shear emulsification to prepare emulsified melamine polyether polyol;

[0025] After the polysilicone polyol containing catalyst II, emulsified melamine polyether polyol, crosslinking agent, catalyst I, liquid flame retardant and foaming agent are stirred and mixed, polymerized isocyanate is added first, and the mixture is uniformly mixed by high-pressure impact mixing or high-speed shearing, and then the inorganic flame retardant is added, and the mixture is continued to be stirred and mixed at high speed, and then the mixture is transferred into a mold or a laminator for foaming and aging to obtain a flame-retardant silicone foam thermal insulation material.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] 1. The present invention mainly ensures that the flame retardant silicone thermal insulation material prepared by the polysilicone polyol and melamine polyether polyol containing catalyst II and the amount of flame retardant added achieves the corresponding flame retardant effect, thereby solving the flame retardant problem of polyurethane, especially polyurethane rigid foam prepared with ordinary pentane as a foaming agent.

[0028] 2. The present invention utilizes the hydroxyl groups on diethylene glycol and the silicate groups on the silica sol to undergo an esterification reaction under alkaline conditions to generate polysilicon polyol containing catalyst II and water, and vacuum dehydration is performed to ensure the smooth progress of the reaction. In addition, the organic amine catalyst used in the reaction process can be used as a catalyst for polyurethane rigid foam, which not only does not require separation treatment, but also reduces the amount of catalyst I in component A, thereby reducing costs.

[0029] 3. The present invention introduces a large amount of nitrogen-containing compounds through melamine, and forms nitrogen during the decomposition process, which is beneficial to improve the flame retardant effect. In order to solve the compatibility problem between melamine and polyether polyols, the present invention first adds silicone oil to reduce the surface tension of the polyols, so that melamine can be quickly wetted by the polyether polyols, thereby significantly reducing the viscosity; then through shear emulsification, the melamine is sheared into extremely fine powders, and then forms an emulsion state, which is not easy to precipitate; at the same time, during the shear emulsification process, the hydroxyl groups on the polyether polyols can also undergo a dehydration condensation reaction with the amino groups on the melamine to form amides, chemically modifying the melamine, solving the compatibility problem between melamine and polyether polyols. DETAILED DESCRIPTION

[0030] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0031] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without making any creative work shall fall within the scope of protection of the present invention.

[0032] Since the commonly used blowing agent 141b for polyurethane rigid foam will be completely banned in 2025, and the price of another blowing agent 245FA is more than 7 times that of ordinary pentane, after comprehensive consideration, ordinary pentane is selected as the blowing agent for the preparation of polyurethane rigid foam. However, polyurethane rigid foam itself is a flammable material, which is mainly due to the large amount of flammable and easily decomposable carbon elements contained in polyurethane rigid foam. The use of more flammable ordinary pentane as a blowing agent will bring great difficulties to the improvement of the flame retardant properties of polyurethane rigid foam.

[0033] In order to solve the flammability problem of polyurethane, the present invention mainly considers two aspects to solve the flame retardant problem of polyurethane rigid foam: on the one hand, non-flammable silicon dioxide is used to replace part of the flammable and easily decomposable carbon element, while ensuring that the silicon dioxide is in liquid state; on the other hand, a large amount of nitrogen-containing compounds (such as melamine polyether polyol) is introduced to improve the flame retardant performance by decomposing the nitrogen-containing compounds to form nitrogen (inert gas).

[0034] Based on this, the present invention first uses silica sol to synthesize polysilicon polyol containing catalyst II. Silica sol is a polycondensate of silicic acid and also a dispersion of silicon dioxide in water. The surface of silica sol has a large number of silicate functional groups. By adding diethylene glycol to silica sol, under alkaline conditions, the silicate on the surface of silica sol and the hydroxyl on diethylene glycol undergo esterification reaction to generate polysilicon polyol containing catalyst II and water. Since this reaction is a reversible reaction, in order to promote the forward progress of the reaction, the water in the reaction product is removed by vacuuming, thereby ensuring the smooth progress of the reaction. The present invention mainly determines the degree of reaction by controlling the water content. At the same time, since diethylene glycol is far in excess, the forward progress of the reaction can be further promoted. In addition, the catalyst II used in the esterification reaction process of the present invention is an organic amine catalyst, which is also a catalyst for polyurethane rigid foam. Therefore, the reaction not only does not need to be separated and processed, but also reduces the amount of catalyst I in component A, reducing costs.

[0035] Secondly, the present invention also utilizes melamine to modify polyether polyol to prepare emulsified melamine polyether polyol, which solves the problem of flammability and the compatibility problem of melamine and polyether polyol. Melamine is a flame retardant with high cost performance, but melamine is a solid powder material. When adding solid powder melamine to liquid polyether polyol, two problems are inevitable: one is that the viscosity of the liquid will increase, especially when the amount of solid powder added is relatively large, and the flame retardant is unqualified when the amount of solid powder added is too small; the second is the precipitation and stratification problem. The solid powder melamine is easy to precipitate to the bottom during the process of adding liquid polyether polyol and cannot be used. Based on this, the present invention mainly adds silicone oil to polyether polyol to reduce the surface tension of polyether polyol by using silicone oil. After melamine is added, melamine can be quickly wetted by polyether polyol, which plays a role of greatly reducing viscosity. Then, shear emulsification is used to shear melamine into extremely fine powder, and then an emulsion state is formed, thereby avoiding the precipitation and stratification problem of melamine. At the same time, during the shear emulsification process, the hydroxyl groups on the polyether polyol also undergo a dehydration condensation reaction with the amino groups on the melamine to form amides, which are used to chemically modify the melamine, thereby improving the flame retardant performance and solving the compatibility problem between melamine and polyether polyol.

[0036] However, after the above-mentioned improvement scheme, it was found that the following problem still exists: the method of changing the elemental composition and molecular structure of polyurethane to improve the flame retardant effect still cannot make its flame retardant performance meet the requirements. Therefore, on the basis of the above-mentioned improvement, the present invention also needs to add additional inorganic flame retardants. When a small amount of inorganic flame retardant is added, B1 level flame retardancy can be achieved, but to achieve A2 level flame retardancy, relatively more inorganic flame retardants need to be added. For example, when the mass ratio of component A, component B and component C is 1:1.0~1.5:0.1~0.3, the flame retardant level of the prepared flame retardant excellent silicon thermal insulation material reaches B1 level; when the mass ratio of component A, component B and component C is 1:1.0~1.5:2.2~2.6, the flame retardant level of the prepared flame retardant excellent silicon thermal insulation material reaches the highest A2 level.

[0037] The present invention provides a method for preparing a flame retardant high-quality silicon thermal insulation material, comprising the following steps:

[0038] (1) Preparation of polysilicone polyol containing catalyst II: reacting silica sol and diethylene glycol at 90-100° C. under the action of catalyst II, and performing vacuum dehydration treatment to prepare polysilicone polyol containing catalyst II;

[0039] (2) preparing melamine polyether polyol: uniformly mixing polyether polyol, silicone oil and melamine, and then performing shear emulsification to prepare emulsified melamine polyether polyol;

[0040] (3) Preparation of flame-retardant silicone thermal insulation material: After mixing polysilicone polyol containing catalyst II, melamine polyether polyol, crosslinking agent, catalyst I, liquid flame retardant, and foaming agent, first add polymeric isocyanate, mix evenly by high-pressure impact mixing or high-speed shear mixing, then add inorganic flame retardant, continue to stir and mix at high speed, and then transfer into a mold or a laminator for foaming and maturation to obtain flame-retardant silicone foam thermal insulation material.

[0041] Step (1) prepares polysilicon polyol containing catalyst II: a part of flammable and easily decomposable carbon elements in polyurethane is changed to non-flammable silicon dioxide (silicon sol), wherein, silicon sol is a condensation product of silicic acid, is a dispersion of silicon dioxide in water, has a large amount of silicate functional groups on the surface, adds diethylene glycol, the hydroxyl groups on diethylene glycol can react with the silicate on the silica sol, and esterification reaction occurs under alkaline conditions to generate polysilicon polyol containing catalyst II and water, which is a reversible reaction, so by vacuumizing, the water in the reaction product is removed, thereby ensuring the smooth progress of the reaction. The degree of reaction is determined by controlling the water content, and diethylene glycol is far in excess at the same time, thereby ensuring the forward progress of the reaction. The catalyst II used in the reaction is an organic amine compound, which is also a catalyst for polyurethane rigid foam, not only does not need to be separated and processed, but also reduces the amount of catalyst I in component A, which can reduce costs.

[0042] Preferably, the catalyst II is an organic amine compound. Preferably, the catalyst II is any one of triethylenediamine, pentamethyldiethylenetriamine, hexamethylenetetramine, and dimethylcyclohexylamine. Preferably, the catalyst II is hexamethylenetetramine or triethylenediamine.

[0043] Preferably, the mass percentage of SiO2 in the silica sol is 20-30%, for example, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, etc. Preferably, the mass ratio of the silica sol, the catalyst II and the diethylene glycol is 1000:2-4:500-700. For example, 1000:2:500, 1000:2:550, 1000:2:600, 1000:2:650, 1000:2:700, 1000:3:500, 1000:3:550, 1000:3:600, 1000:3:650, 1000:3:700, 1000:4:500, 1000:4:550, 1000:4:600, 1000:4:650, 1000:4:700, etc. Preferably, in the process of preparing the polysilicone polyol containing catalyst II, the reaction temperature is 90-100°C, for example, 90°C, 95°C, 100°C, etc.

[0044] Step (2) Preparation of melamine polyether polyol: By introducing a large amount of nitrogen-containing compounds (melamine), nitrogen is formed during the decomposition process, which is beneficial to improve the flame retardant effect. Melamine is a flame retardant with a high cost performance, but it is a solid powder. When solid powder melamine is added to liquid polyol, there are inevitably two problems: one is that the viscosity will increase, especially when the addition amount is relatively large, and if too little is added, the flame retardant will fail to meet the requirements; the other is the precipitation and stratification problem, which will precipitate to the bottom and cannot be used. In order to solve the compatibility problem between melamine and polyether polyol, the present invention first adds silicone oil to reduce the surface tension of polyol so that melamine can be quickly wetted by polyether polyol, thereby significantly reducing viscosity; then, through shear emulsification, melamine is sheared into extremely fine powder to form an emulsion state, which is not easy to precipitate; at the same time, during the shear emulsification process, the hydroxyl groups on the polyether polyol can also undergo a dehydration condensation reaction with the amino groups on the melamine to form amides, thereby chemically modifying the melamine and solving the compatibility problem between melamine and polyether polyol.

[0045] Preferably, the polyether polyol is polyether polyol 4110 or polyether polyol 635. Preferably, the silicone oil is any one of dimethyl silicone oil, methyl silicone oil 201 and methyl silicone oil 350.

[0046] Preferably, the mass ratio of polyether polyol, silicone oil and melamine is 1000:5 to 10:1000, for example, 1000:5:1000, 1000:6:1000, 1000:7:1000, 1000:8:1000, 1000:9:1000, 1000:10:1000, etc.

[0047] Preferably, the conditions for shear emulsification are: a rotation speed of 4000-8000 r / min; for example, 4000 r / min, 4500 r / min, 5000 r / min, 5500 r / min, 6000 r / min, 6500 r / min, 7000 r / min, 7500 r / min, 8000 r / min, etc.; a temperature of 120-130°C, for example, 120°C, 125°C, 130°C, etc.; and a time of 3-4h, for example, 3h, 4h, etc.

[0048] Step (3) Preparation of flame retardant excellent silicon insulation material: The aforementioned steps (1) and (2) solve the flame retardant problem mainly through two aspects: one is by changing a part of the flammable and easily decomposable carbon elements in the polyurethane to non-flammable silicon dioxide, while ensuring that it is liquid, so silica sol is introduced; the second is by introducing a large amount of nitrogen-containing compounds (melamine), which decompose to form nitrogen, which is conducive to flame retardancy. However, relying on the above means is not enough to meet the flame retardant requirements, so it is necessary to add additional inorganic flame retardants. By controlling the amount of inorganic flame retardants, the obtained product can reach different flame retardant levels. For example, adding a small amount of inorganic flame retardants can achieve B1 grade flame retardancy; but to reach A2 grade, the amount of inorganic flame retardant to be added is relatively large. The high-pressure counter-mixing or high-speed shear mixing is carried out according to the existing mixing conditions, and the high-speed stirring mixing is carried out according to the existing mixing conditions. For example, the speed of high-speed stirring is 1000-2000r / min. The present invention does not limit the specific mixing method, as long as it can meet the uniform mixing state before foaming.

[0049] Preferably, when the mass ratio of component A, component B and component C is 1:1.0~1.5:0.1~0.3, the flame retardant level of the prepared flame retardant superior silicone thermal insulation material reaches B1 level; when the mass ratio of component A, component B and component C is 1:1.0~1.5:2.2~2.6, the flame retardant level of the prepared flame retardant superior silicone thermal insulation material reaches the highest A2 level.

[0050] Preferably, the crosslinking agent is polyether polyol 403 or triethanolamine; the catalyst is cyclohexylamine; the liquid flame retardant is tris(2-chloropropyl) phosphate; and the foaming agent is pentane.

[0051] The crosslinking agent described in the present invention refers to a polyol organic substance having more than 3 active hydroxyl groups, which can be polyether polyol 403 or triethanolamine, wherein polyether polyol 403 is preferred. In the present invention, the silicone oil used refers to a silicone oil with a relatively small molecular weight, such as dimethyl silicone oil with the chemical formula (CH3)2SiO, and dimethyl silicone oil with the chemical formula C6H 18 OSi2 methyl silicone oil 201, chemical formula C6H 18 O4Si3 methyl silicone oil 350, etc.

[0052] The inorganic flame retardant described in the present invention refers to a highly inert substance that does not or slightly decomposes or oxidizes at 750° C., such as aluminum oxide.

[0053] In the present invention, since the non-flammable foaming agent 141b is about to be banned from use, the price of 245FA is more than 7 times that of ordinary pentane. Therefore, based on cost and other factors, the present invention still uses ordinary pentane as the foaming agent. However, polyurethane rigid foam is flammable, especially when more flammable ordinary pentane is used as the foaming agent. Therefore, the present invention mainly ensures that the prepared flame-retardant excellent silicon insulation material achieves the corresponding flame retardant effect by using polysilicone polyol and melamine polyether polyol containing catalyst II and the amount of flame retardant added, thereby solving the flame retardant problem of polyurethane, especially polyurethane prepared with ordinary pentane as the foaming agent.

[0054] The technical solution proposed in the present invention is further described below in conjunction with specific embodiments.

[0055] Unless otherwise specified, the methods described in the following examples are all conventional methods; the reagents and materials described are all commercially available unless otherwise specified.

[0056] Example 1

[0057] A method for preparing a flame retardant high-quality silicon thermal insulation material comprises the following steps:

[0058] (1) Using triethylenediamine as catalyst II, 1000 g of silica sol with a mass percentage of 20% was added to 2 g of catalyst II in a vacuum reactor, and after stirring evenly, 600 g of diethylene glycol was added, and the mixture was reacted at 90-100° C., while vacuuming was performed, and the vacuum degree was controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After naturally cooling to room temperature, the mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0059] (2) Take 1000g of low-viscosity polyether polyol 4110, add 8g of dimethyl silicone oil, and then add 1000g of melamine, stir evenly, put it into a high-speed emulsifying shearing machine for shear emulsification, control the speed to 5000r / min, control the temperature to 120°C, shear for 3h, naturally cool to room temperature, filter with a 200-mesh stainless steel filter, and prepare an emulsified melamine polyether polyol.

[0060] (3) Polyether polyol 403 is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 28% of polysilicone polyol containing catalyst II, 30% of emulsified melamine polyether polyol, 8% of crosslinking agent, 4% of catalyst I, 14% of liquid flame retardant, and 16% of foaming agent are mixed and stirred rapidly as component A. Polyisocyanate is used as component B, and alumina is used as component C. The mass ratio of component A, component B and component C is 1:1:0.1. First, add component B to component A, mix evenly by high-pressure impact mixing or high-speed shearing, then add component C, continue to stir and mix at high speed, and then inject into the mold for foaming, and mature at 20°C to prepare a flame-retardant excellent silicone thermal insulation material.

[0061] Example 2

[0062] A method for preparing a flame retardant high-quality silicon thermal insulation material comprises the following steps:

[0063] (1) Using triethylenediamine as catalyst II, 1000 g of silica sol with a mass percentage of 20% was added to 3 g of catalyst II in a vacuum reactor. After stirring, 600 g of diethylene glycol was added and reacted at 90-100° C. while evacuating the reaction mixture. The vacuum degree was controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After naturally cooling to room temperature, the reaction mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0064] (2) Take 1000g of low-viscosity polyether polyol 4110, add 8g of dimethyl silicone oil, and then add 1000g of melamine, stir evenly, put it into a high-speed emulsifying shearing machine for shear emulsification, control the speed to 5000r / min, control the temperature to 120°C, shear for 3h, naturally cool to room temperature, filter with a 200-mesh stainless steel filter, and prepare an emulsified melamine polyether polyol.

[0065] (3) Polyether polyol 403 is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 28% of polysilicone polyol containing catalyst II, 30% of emulsified melamine polyether polyol, 8% of crosslinking agent, 4% of catalyst I, 14% of liquid flame retardant, and 16% of foaming agent are mixed and stirred rapidly as component A. Polyisocyanate is used as component B, and alumina is used as component C. The mass ratio of component A, component B and component C is 1:1:0.1. First, add component B to component A, mix evenly by high-pressure impact mixing or high-speed shearing, then add component C, continue to stir and mix at high speed, and then inject into the mold for foaming, and mature at 20°C to prepare a flame-retardant excellent silicone thermal insulation material.

[0066] Example 3

[0067] A method for preparing a flame retardant high-quality silicon thermal insulation material comprises the following steps:

[0068] (1) Using triethylenediamine as catalyst II, 1000 g of silica sol with a mass percentage of 20% was added to 4 g of catalyst II in a vacuum reactor. After stirring, 600 g of diethylene glycol was added and reacted at 90-100° C. while evacuating the reaction mixture. The vacuum degree was controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After naturally cooling to room temperature, the reaction mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0069] (2) Take 1000g of low-viscosity polyether polyol 4110, add 8g of dimethyl silicone oil, and then add 1000g of melamine, stir evenly, put it into a high-speed emulsifying shearing machine for shear emulsification, control the speed to 5000r / min, control the temperature to 120°C, shear for 3h, naturally cool to room temperature, filter with a 200-mesh stainless steel filter, and prepare an emulsified melamine polyether polyol.

[0070] (3) Polyether polyol 403 is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 28% of polysilicone polyol containing catalyst II, 30% of emulsified melamine polyether polyol, 8% of crosslinking agent, 4% of catalyst I, 14% of liquid flame retardant, and 16% of foaming agent are mixed and stirred rapidly as component A. Polyisocyanate is used as component B, and alumina is used as component C. The mass ratio of component A, component B and component C is 1:1:0.1. First, add component B to component A, mix evenly by high-pressure impact mixing or high-speed shearing, then add component C, continue to stir and mix at high speed, and then inject into the mold for foaming, and mature at 20°C to prepare a flame-retardant excellent silicone thermal insulation material.

[0071] Example 4

[0072] A method for preparing a flame retardant high-quality silicon thermal insulation material comprises the following steps:

[0073] (1) Using triethylenediamine as catalyst II, 1000 g of silica sol with a mass percentage of 30% was added to 4 g of catalyst II in a vacuum reactor. After stirring evenly, 700 g of diethylene glycol was added and reacted at 90-100° C. while evacuating the reaction mixture with a vacuum degree controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After naturally cooling to room temperature, the reaction mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0074] (2) Take 1000g of low-viscosity polyether polyol 4110, add 8g of methyl silicone oil 201, and then add 1000g of melamine. After stirring evenly, put it into a high-speed emulsifying shearing machine for shear emulsification. The speed is controlled at 5000r / min and the temperature is controlled at 120°C. After shearing for 3h, it is naturally cooled to room temperature and filtered through a 200-mesh stainless steel filter to prepare an emulsified melamine polyether polyol.

[0075] (3) Polyether polyol 403 is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 28% of polysilicone polyol containing catalyst II, 30% of emulsified melamine polyether polyol, 8% of crosslinking agent, 4% of catalyst I, 14% of liquid flame retardant, and 16% of foaming agent are mixed and stirred rapidly as component A. Polyisocyanate is used as component B, and alumina is used as component C. The mass ratio of component A, component B and component C is 1:1:0.1. First, add component B to component A, mix evenly by high-pressure impact mixing or high-speed shearing, then add component C, continue to stir and mix at high speed, and then inject into the mold for foaming, and mature at 20°C to prepare a flame-retardant excellent silicone thermal insulation material.

[0076] Example 5

[0077] A method for preparing a flame retardant high-quality silicon thermal insulation material comprises the following steps:

[0078] (1) With hexamethylenetetramine as catalyst II, 1000 g of silica sol with a mass percentage of 20% was added with 3 g of catalyst II in a vacuum reactor, and after being stirred evenly, 500 g of diethylene glycol was added, and the mixture was reacted at 90-100° C., while vacuuming was performed, and the vacuum degree was controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After naturally cooling to room temperature, the mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0079] (2) Take 1000g of low-viscosity polyether polyol 635, add 8g of methyl silicone oil 350, and then add 1000g of melamine. After stirring evenly, put it into a high-speed emulsifying shearing machine for shear emulsification. The speed is controlled at 5000r / min and the temperature is controlled at 120°C. After shearing for 3h, it is naturally cooled to room temperature and filtered through a 200-mesh stainless steel filter to prepare an emulsified melamine polyether polyol.

[0080] (3) Polyether polyol 403 is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 28% of polysilicone polyol containing catalyst II, 30% of emulsified melamine polyether polyol, 8% of crosslinking agent, 4% of catalyst I, 14% of liquid flame retardant, and 16% of foaming agent are mixed and stirred rapidly as component A. Polyisocyanate is used as component B, and alumina is used as component C. The mass ratio of component A, component B and component C is 1:1:0.1. First, add component B to component A, mix evenly by high-pressure impact mixing or high-speed shearing, then add component C, continue to stir and mix at high speed, and then inject into the mold for foaming, and mature at 20°C to prepare a flame-retardant excellent silicone thermal insulation material.

[0081] Example 6

[0082] A method for preparing a flame retardant high-quality silicon thermal insulation material comprises the following steps:

[0083] (1) Pentamethyldiethylenetriamine was used as catalyst II. 1000 g of silica sol with a mass percentage of 20% was added with 3 g of catalyst II in a vacuum reactor. After stirring, 500 g of diethylene glycol was added and reacted at 90-100° C. while evacuating the reaction mixture. The vacuum degree was controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After cooling naturally to room temperature, the reaction mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0084] (2) Take 1000g of low-viscosity polyether polyol 4110, add 8g of dimethyl silicone oil, and then add 1000g of melamine, stir evenly, put it into a high-speed emulsifying shearing machine for shear emulsification, control the speed to 5000r / min, control the temperature to 120°C, shear for 3h, naturally cool to room temperature, filter with a 200-mesh stainless steel filter, and prepare an emulsified melamine polyether polyol.

[0085] (3) Polyether polyol 403 is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 28% of polysilicone polyol containing catalyst II, 30% of emulsified melamine polyether polyol, 8% of crosslinking agent, 4% of catalyst I, 14% of liquid flame retardant, and 16% of foaming agent are mixed and stirred rapidly as component A. Polyisocyanate is used as component B, and alumina is used as component C. The mass ratio of component A, component B and component C is 1:1:0.1. First, add component B to component A, mix evenly by high-pressure impact mixing or high-speed shearing, then add component C, continue to stir and mix at high speed, and then inject into the mold for foaming, and mature at 20°C to prepare a flame-retardant excellent silicone thermal insulation material.

[0086] Example 7

[0087] A method for preparing a flame retardant high-quality silicon thermal insulation material comprises the following steps:

[0088] (1) Using dimethylcyclohexylamine as catalyst II, 1000 g of silica sol with a mass percentage of 20% was added to 3 g of catalyst II in a vacuum reactor. After stirring, 500 g of diethylene glycol was added and reacted at 90-100° C. while evacuating the reaction mixture. The vacuum degree was controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After cooling naturally to room temperature, the reaction mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0089] (2) Take 1000g of low-viscosity polyether polyol 4110, add 8g of dimethyl silicone oil, and then add 1000g of melamine, stir evenly, put it into a high-speed emulsifying shearing machine for shear emulsification, control the speed to 5000r / min, control the temperature to 120°C, shear for 3h, naturally cool to room temperature, filter with a 200-mesh stainless steel filter, and prepare an emulsified melamine polyether polyol.

[0090] (3) Polyether polyol 403 is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 28% of polysilicone polyol containing catalyst II, 30% of emulsified melamine polyether polyol, 8% of crosslinking agent, 4% of catalyst I, 14% of liquid flame retardant, and 16% of foaming agent are mixed and stirred rapidly as component A. Polyisocyanate is used as component B, and alumina is used as component C. The mass ratio of component A, component B and component C is 1:1:0.1. First, add component B to component A, mix evenly by high-pressure impact mixing or high-speed shearing, then add component C, continue to stir and mix at high speed, and then inject into the mold for foaming, and mature at 20°C to prepare a flame-retardant excellent silicone thermal insulation material.

[0091] Example 8

[0092] A method for preparing a flame retardant high-quality silicon thermal insulation material, the specific method comprising the following steps:

[0093] (1) Using triethylenediamine as catalyst II, 1000 g of silica sol with a mass percentage of 20% was added to 3 g of catalyst II in a vacuum reactor. After stirring, 600 g of diethylene glycol was added and reacted at 90-100° C. while evacuating the reaction mixture. The vacuum degree was controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After naturally cooling to room temperature, the reaction mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0094] (2) Take 1000g of low-viscosity polyether polyol 4110, add 5g of dimethyl silicone oil, and then add 1000g of melamine, stir evenly, put it into a high-speed emulsifying shearing machine for shear emulsification, control the speed to 5000r / min, control the temperature to 120°C, shear for 3h, naturally cool to room temperature, filter with a 200-mesh stainless steel filter, and prepare an emulsified melamine polyether polyol.

[0095] (3) Polyether polyol 403 is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 28% of polysilicone polyol containing catalyst II, 30% of emulsified melamine polyether polyol, 8% of crosslinking agent, 4% of catalyst I, 14% of liquid flame retardant, and 16% of foaming agent are mixed and stirred rapidly as component A. Polyisocyanate is used as component B, and alumina is used as component C. The mass ratio of component A, component B and component C is 1:1:0.1. First, add component B to component A, mix evenly by high-pressure impact mixing or high-speed shearing, then add component C, continue to stir and mix at high speed, and then inject into the mold for foaming, and mature at 20°C to prepare a flame-retardant excellent silicone thermal insulation material.

[0096] Example 9

[0097] A method for preparing a flame retardant high-quality silicon thermal insulation material comprises the following steps:

[0098] (1) Using triethylenediamine as catalyst II, 1000 g of silica sol with a mass percentage of 20% was added to 3 g of catalyst II in a vacuum reactor. After stirring, 600 g of diethylene glycol was added and reacted at 90-100° C. while evacuating the reaction mixture. The vacuum degree was controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After naturally cooling to room temperature, the reaction mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0099] (2) Take 1000g of low-viscosity polyether polyol 4110, add 10g of dimethyl silicone oil, and then add 1000g of melamine, stir evenly, put it into a high-speed emulsifying shearing machine for shear emulsification, control the speed to 5000r / min, control the temperature to 120°C, shear for 3h, naturally cool to room temperature, filter with a 200-mesh stainless steel filter, and prepare an emulsified melamine polyether polyol.

[0100] (3) Polyether polyol 403 is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 28% of polysilicone polyol containing catalyst II, 30% of emulsified melamine polyether polyol, 8% of crosslinking agent, 4% of catalyst I, 14% of liquid flame retardant, and 16% of foaming agent are mixed and stirred rapidly as component A. Polyisocyanate is used as component B, and alumina is used as component C. The mass ratio of component A, component B and component C is 1:1:0.1. First, add component B to component A, mix evenly by high-pressure impact mixing or high-speed shearing, then add component C, continue to stir and mix at high speed, and then inject into the mold for foaming, and mature at 20°C to prepare a flame-retardant excellent silicone thermal insulation material.

[0101] Example 10

[0102] A method for preparing a flame retardant high-quality silicon thermal insulation material comprises the following steps:

[0103] (1) Using triethylenediamine as catalyst II, 1000 g of silica sol with a mass percentage of 20% was added to 3 g of catalyst II in a vacuum reactor. After stirring, 600 g of diethylene glycol was added and reacted at 90-100° C. while evacuating the reaction mixture. The vacuum degree was controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After naturally cooling to room temperature, the reaction mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0104] (2) Take 1000g of low-viscosity polyether polyol 4110, add 8g of dimethyl silicone oil, and then add 1000g of melamine, stir evenly, put it into a high-speed emulsifying shearing machine for shear emulsification, control the speed to 8000r / min, control the temperature to 130°C, shear for 4h, naturally cool to room temperature, filter with a 200-mesh stainless steel filter, and prepare an emulsified melamine polyether polyol.

[0105] (3) Triethanolamine is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 28% of polysilicone polyol containing catalyst II, 22% of emulsified melamine polyether polyol, 10% of crosslinking agent, 6% of catalyst I, 14% of liquid flame retardant, and 20% of foaming agent are quickly mixed and stirred as component A. Polyisocyanate is used as component B, and aluminum oxide is used as component C. The mass ratio of component A, component B and component C is 1:1:0.1. First, add component B to component A, mix evenly by high-pressure impact mixing or high-speed shearing, and then add component C, continue to stir and mix at high speed, and then inject into the mold for foaming, and mature at 20°C to prepare a flame-retardant excellent silicone insulation material.

[0106] Embodiment 11

[0107] A method for preparing a flame retardant high-quality silicon thermal insulation material comprises the following steps:

[0108] (1) Using triethylenediamine as catalyst II, 1000 g of silica sol with a mass percentage of 20% was added to 3 g of catalyst II in a vacuum reactor. After stirring, 600 g of diethylene glycol was added and reacted at 90-100° C. while evacuating the reaction mixture. The vacuum degree was controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After naturally cooling to room temperature, the reaction mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0109] (2) Take 1000g of low-viscosity polyether polyol 4110, add 8g of dimethyl silicone oil, and then add 1000g of melamine, stir evenly, put it into a high-speed emulsifying shearing machine for shear emulsification, control the speed to 4000r / min, control the temperature to 125°C, shear for 4h, naturally cool to room temperature, filter with a 200-mesh stainless steel filter, and prepare an emulsified melamine polyether polyol.

[0110] (3) Polyether polyol 403 is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 28% of polysilicone polyol containing catalyst II, 30% of emulsified melamine polyether polyol, 10% of crosslinking agent, 6% of catalyst I, 14% of liquid flame retardant, and 12% of foaming agent are mixed and stirred rapidly as component A. Polyisocyanate is used as component B, and alumina is used as component C. The mass ratio of component A, component B and component C is 1:1:0.1. First, add component B to component A, mix evenly by high-pressure impact mixing or high-speed shearing, then add component C, continue to stir and mix at high speed, and then inject into the mold for foaming, and mature at 20°C to prepare a flame-retardant excellent silicone thermal insulation material.

[0111] Example 12

[0112] A method for preparing a flame retardant high-quality silicon thermal insulation material comprises the following steps:

[0113] (1) Using triethylenediamine as catalyst II, 1000 g of silica sol with a mass percentage of 20% was added to 3 g of catalyst II in a vacuum reactor. After stirring, 600 g of diethylene glycol was added and reacted at 90-100° C. while evacuating the reaction mixture. The vacuum degree was controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After naturally cooling to room temperature, the reaction mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0114] (2) Take 1000g of low-viscosity polyether polyol 4110, add 8g of dimethyl silicone oil, and then add 1000g of melamine, stir evenly, put it into a high-speed emulsifying shearing machine for shear emulsification, control the speed to 5000r / min, control the temperature to 120°C, shear for 3h, naturally cool to room temperature, filter with a 200-mesh stainless steel filter, and prepare an emulsified melamine polyether polyol.

[0115] (3) Polyether polyol 403 is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 26% of polysilicone polyol containing catalyst II, 28% of emulsified melamine polyether polyol, 10% of crosslinking agent, 6% of catalyst I, 15% of liquid flame retardant, and 15% of foaming agent are quickly mixed and stirred as component A. Polyisocyanate is used as component B, and alumina is used as component C. The mass ratio of component A, component B and component C is 1:1:0.1. First, add component B to component A, mix evenly by high-pressure impact mixing or high-speed shearing, then add component C, continue to stir and mix at high speed, and then inject into the mold for foaming, and mature at 20°C to prepare a flame-retardant excellent silicone insulation material.

[0116] Example 13

[0117] A method for preparing a flame retardant high-quality silicon thermal insulation material comprises the following steps:

[0118] (1) Using triethylenediamine as catalyst II, 1000 g of silica sol with a mass percentage of 20% was added to 3 g of catalyst II in a vacuum reactor. After stirring, 600 g of diethylene glycol was added and reacted at 90-100° C. while evacuating the reaction mixture. The vacuum degree was controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After naturally cooling to room temperature, the reaction mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0119] (2) Take 1000g of low-viscosity polyether polyol 4110, add 8g of dimethyl silicone oil, and then add 1000g of melamine, stir evenly, put it into a high-speed emulsifying shearing machine for shear emulsification, control the speed to 5000r / min, control the temperature to 120°C, shear for 3h, naturally cool to room temperature, filter with a 200-mesh stainless steel filter, and prepare an emulsified melamine polyether polyol.

[0120] (3) Polyether polyol 403 is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 28% of polysilicone polyol containing catalyst II, 30% of emulsified melamine polyether polyol, 10% of crosslinking agent, 6% of catalyst I, 8% of liquid flame retardant, and 18% of foaming agent are mixed and stirred quickly as component A. Polyisocyanate is used as component B, and alumina is used as component C. The mass ratio of component A, component B and component C is 1:1:0.1. First, add component B to component A, mix evenly by high-pressure impact mixing or high-speed shearing, then add component C, continue to stir and mix at high speed, and then inject into the mold for foaming, and mature at 20°C to prepare a flame-retardant excellent silicone insulation material.

[0121] Embodiment 14

[0122] A method for preparing a flame retardant high-quality silicon thermal insulation material comprises the following steps:

[0123] (1) Using triethylenediamine as catalyst II, 1000 g of silica sol with a mass percentage of 20% was added to 3 g of catalyst II in a vacuum reactor. After stirring, 600 g of diethylene glycol was added and reacted at 90-100° C. while evacuating the reaction mixture. The vacuum degree was controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After naturally cooling to room temperature, the reaction mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0124] (2) Take 1000g of low-viscosity polyether polyol 4110, add 8g of dimethyl silicone oil, and then add 1000g of melamine, stir evenly, put it into a high-speed emulsifying shearing machine for shear emulsification, control the speed to 5000r / min, control the temperature to 120°C, shear for 3h, naturally cool to room temperature, filter with a 200-mesh stainless steel filter, and prepare an emulsified melamine polyether polyol.

[0125] (3) Polyether polyol 403 is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 19% of polysilicone polyol containing catalyst II, 30% of emulsified melamine polyether polyol, 10% of crosslinking agent, 6% of catalyst I, 15% of liquid flame retardant, and 20% of foaming agent are mixed and stirred rapidly as component A. Polyisocyanate is used as component B, and alumina is used as component C. The mass ratio of component A, component B and component C is 1:1:0.3. First, add component B to component A, mix evenly by high-pressure impact mixing or high-speed shearing, then add component C, continue to stir and mix at high speed, and then inject into the mold for foaming, and mature at 20°C to prepare a flame-retardant excellent silicone thermal insulation material.

[0126] Embodiment 15

[0127] A method for preparing a flame retardant high-quality silicon thermal insulation material comprises the following steps:

[0128] (1) Using triethylenediamine as catalyst II, 1000 g of silica sol with a mass percentage of 20% was added to 3 g of catalyst II in a vacuum reactor. After stirring, 600 g of diethylene glycol was added and reacted at 90-100° C. while evacuating the reaction mixture. The vacuum degree was controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After naturally cooling to room temperature, the reaction mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0129] (2) Take 1000g of low-viscosity polyether polyol 4110, add 8g of dimethyl silicone oil, and then add 1000g of melamine, stir evenly, put it into a high-speed emulsifying shearing machine for shear emulsification, control the speed to 5000r / min, control the temperature to 120°C, shear for 3h, naturally cool to room temperature, filter with a 200-mesh stainless steel filter, and prepare an emulsified melamine polyether polyol.

[0130] (3) Polyether polyol 403 is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 28% of polysilicone polyol containing catalyst II, 30% of emulsified melamine polyether polyol, 5% of crosslinking agent, 2% of catalyst I, 15% of liquid flame retardant, and 20% of foaming agent are mixed and stirred rapidly as component A. Polyisocyanate is used as component B, and alumina is used as component C. The mass ratio of component A, component B and component C is 1:1:2.2. First, add component B to component A, mix evenly by high-pressure impact mixing or high-speed shear mixing, then add component C, continue to stir and mix at high speed, and then inject into the mold for foaming, and mature at 20°C to prepare a flame-retardant excellent silicone insulation material.

[0131] Example 16

[0132] A method for preparing a flame retardant high-quality silicon thermal insulation material comprises the following steps:

[0133] (1) Using triethylenediamine as catalyst II, 1000 g of silica sol with a mass percentage of 20% was added to 3 g of catalyst II in a vacuum reactor. After stirring, 600 g of diethylene glycol was added and reacted at 90-100° C. while evacuating the reaction mixture. The vacuum degree was controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After naturally cooling to room temperature, the reaction mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0134] (2) Take 1000g of low-viscosity polyether polyol 4110, add 8g of dimethyl silicone oil, and then add 1000g of melamine, stir evenly, put it into a high-speed emulsifying shearing machine for shear emulsification, control the speed to 5000r / min, control the temperature to 120°C, shear for 3h, naturally cool to room temperature, filter with a 200-mesh stainless steel filter, and prepare an emulsified melamine polyether polyol.

[0135] (3) Polyether polyol 403 is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 28% of polysilicone polyol containing catalyst II, 30% of emulsified melamine polyether polyol, 8% of crosslinking agent, 4% of catalyst I, 14% of liquid flame retardant, and 16% of foaming agent are mixed and stirred rapidly as component A. Polyisocyanate is used as component B, and alumina is used as component C. The mass ratio of component A, component B and component C is 1:1:2.6. First, add component B to component A, mix evenly by high-pressure impact mixing or high-speed shear mixing, then add component C, continue to stir and mix at high speed, and then inject into the mold for foaming, and mature at 20°C to prepare a flame-retardant excellent silicone insulation material.

[0136] Embodiment 17

[0137] A method for preparing a flame retardant high-quality silicon thermal insulation material comprises the following steps:

[0138] (1) Using triethylenediamine as catalyst II, 1000 g of silica sol with a mass percentage of 20% was added to 3 g of catalyst II in a vacuum reactor. After stirring, 600 g of diethylene glycol was added and reacted at 90-100° C. while evacuating the reaction mixture. The vacuum degree was controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After naturally cooling to room temperature, the reaction mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0139] (2) Take 1000g of low-viscosity polyether polyol 4110, add 8g of dimethyl silicone oil, and then add 1000g of melamine, stir evenly, put it into a high-speed emulsifying shearing machine for shear emulsification, control the speed to 5000r / min, control the temperature to 120°C, shear for 3h, naturally cool to room temperature, filter with a 200-mesh stainless steel filter, and prepare an emulsified melamine polyether polyol.

[0140] (3) Polyether polyol 403 is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 28% of polysilicone polyol containing catalyst II, 30% of emulsified melamine polyether polyol, 8% of crosslinking agent, 4% of catalyst I, 14% of liquid flame retardant, and 16% of foaming agent are mixed and stirred rapidly as component A. Polyisocyanate is used as component B, and alumina is used as component C. The mass ratio of component A, component B and component C is 1:1.5:0.1. First, add component B to component A, mix evenly by high-pressure impact mixing or high-speed shearing, then add component C, continue to stir and mix at high speed, and then inject into the mold for foaming, and mature at 20°C to prepare a flame-retardant excellent silicone insulation material.

[0141] Embodiment 18

[0142] A method for preparing a flame retardant high-quality silicon thermal insulation material comprises the following steps:

[0143] (1) Using triethylenediamine as catalyst II, 1000 g of silica sol with a mass percentage of 20% was added to 3 g of catalyst II in a vacuum reactor. After stirring, 600 g of diethylene glycol was added and reacted at 90-100° C. while evacuating the reaction mixture. The vacuum degree was controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After naturally cooling to room temperature, the reaction mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0144] (2) Take 1000g of low-viscosity polyether polyol 4110, add 8g of dimethyl silicone oil, and then add 1000g of melamine, stir evenly, put it into a high-speed emulsifying shearing machine for shear emulsification, control the speed to 5000r / min, control the temperature to 120°C, shear for 3h, naturally cool to room temperature, filter with a 200-mesh stainless steel filter, and prepare an emulsified melamine polyether polyol.

[0145] (3) Polyether polyol 403 is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 28% of polysilicone polyol containing catalyst II, 30% of emulsified melamine polyether polyol, 8% of crosslinking agent, 4% of catalyst I, 14% of liquid flame retardant, and 16% of foaming agent are quickly mixed and stirred as component A. Polyisocyanate is used as component B, and alumina is used as component C. The mass ratio of component A, component B and component C is 1:1.5:2.6. First, add component B to component A, mix evenly by high-pressure impact mixing or high-speed shearing, then add component C, continue to stir and mix at high speed, and then inject into the mold for foaming, and mature at 20°C to prepare a flame-retardant excellent silicone insulation material.

[0146] Comparative Example 1

[0147] A method for preparing a flame retardant high-quality silicon thermal insulation material comprises the following steps:

[0148] (1) Using triethylenediamine as catalyst II, 1000 g of silica sol with a mass percentage of 20% was added to 3 g of catalyst II in a vacuum reactor. After stirring, 600 g of diethylene glycol was added and reacted at 90-100° C. while evacuating the reaction mixture. The vacuum degree was controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After naturally cooling to room temperature, the reaction mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0149] (2) Take 1000 g of low-viscosity polyether polyol 4110, add 8 g of dimethyl silicone oil, and then add 1000 g of melamine, stir evenly at 120° C., cool naturally to room temperature, and filter through a 200-mesh stainless steel filter to prepare melamine polyether polyol.

[0150] (3) Polyether polyol 403 is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 28% of polysilicone polyol containing catalyst II, 30% of melamine polyether polyol, 8% of crosslinking agent, 4% of catalyst I, 14% of liquid flame retardant, and 16% of foaming agent are quickly mixed and stirred as component A. Polyisocyanate is used as component B, and aluminum oxide is used as component C. The mass ratio of component A, component B and component C is 1:1:0.1. First, add component B to component A, mix evenly by high-pressure impact mixing or high-speed shearing, then add component C, continue to stir and mix at high speed, and then inject into the mold for foaming, and mature at 20°C to prepare a flame-retardant excellent silicone insulation material.

[0151] Comparative Example 2

[0152] A method for preparing a flame retardant high-quality silicon thermal insulation material comprises the following steps:

[0153] (1) Using triethylenediamine as catalyst II, 1000 g of silica sol with a mass percentage of 20% was added to 3 g of catalyst II in a vacuum reactor. After stirring, 600 g of diethylene glycol was added and reacted at 90-100° C. while evacuating the reaction mixture. The vacuum degree was controlled at 1 kPa to remove water from the reaction solution until the water content of the reaction solution in the reactor was less than 0.5% (mass). After naturally cooling to room temperature, the reaction mixture was filtered with a 200-mesh stainless steel filter to prepare a polysilicone polyol containing catalyst II.

[0154] (2) Take 1000g of low-viscosity polyether polyol 4110, add 8g of dimethyl silicone oil, and then add 1000g of melamine, stir evenly, put it into a high-speed emulsifying shearing machine for shear emulsification, control the speed to 5000r / min, control the temperature to 120°C, shear for 3h, naturally cool to room temperature, filter with a 200-mesh stainless steel filter, and prepare an emulsified melamine polyether polyol.

[0155] (3) Polyether polyol 403 is used as a crosslinking agent, cyclohexylamine is used as a catalyst I, tris(2-chloropropyl) phosphate is used as a liquid flame retardant, and ordinary pentane is used as a foaming agent. According to the mass percentage, 28% of polysilicone polyol containing catalyst II, 30% of emulsified melamine polyether polyol, 8% of crosslinking agent, 4% of catalyst I, 14% of liquid flame retardant, and 16% of foaming agent are quickly mixed and stirred as component A. Polyisocyanate is used as component B. The mass ratio of component A to component B is 1:1. First, component B is added to component A, and the mixture is evenly mixed by high-pressure impact mixing or high-speed shear mixing, and then injected into a mold for foaming, and aged at 20°C to prepare a flame-retardant silicone thermal insulation material.

[0156] Effect test:

[0157] Test basis: (1) Density test is based on GB / T 6343-2009 "Determination of apparent density of cellular plastics and rubber"; (2) Compressive strength test is based on GB / T8813-2008 "Determination of compression properties of rigid cellular plastics"; (3) Thermal conductivity test is based on GB / T 10294-2008 "Determination of steady-state thermal resistance and related properties of insulating materials - Guarded hot plate method"; (4) Combustion grade classification test is based on GB 8624-2012 "Combustion performance classification standard for building materials and products".

[0158] Test Example 1: The effect of the ratio of raw materials for preparing polysilicone polyol containing catalyst II on the product performance is shown in Table 1.

[0159] Table 1 Performance comparison data of products prepared in Examples 1 to 4

[0160]

[0161] Note: Ratio a represents the mass ratio of silica, catalyst II and diethylene glycol.

[0162] As shown in Table 1, with the increase in the amount of catalyst II, on the one hand, the synthesis of polysilicon polyol is promoted, the molecular weight of polysilicon polyol is larger, and the mechanical strength is better; at the same time, catalyst II can also promote the reaction of polysilicon polyol and polymerized isocyanate, so that their reaction is more thorough, the organic matter is more cross-linked, the heat release is greater, the foaming agent volume is larger, and the density of the obtained polysilicon foam material decreases, but the compressive strength increases significantly, and the thermal conductivity is not greatly affected. As shown in Examples 3 and 4, with the increase in the content of silicon dioxide, after all, it still tends to belong to the field of inorganic substances, resulting in increased density, poor cross-linking, decreased compressive strength, and poor thermal conductivity; however, the flame retardancy has been significantly improved, and the oxygen index has increased significantly; it has increased from 30 to 32, which is significantly higher than the national standard.

[0163] Test Example 2: The effects of different catalysts II on the product properties in preparing polysilicone polyol containing catalyst II are shown in Table 2.

[0164] Table 2 Performance comparison data of products prepared in Examples 2 and 5 to 7

[0165]

[0166]

[0167] As shown in Table 2, triethylenediamine and dimethylcyclohexylamine In the molecular structure, nitrogen atoms form sp 3 Hybrid orbitals are all connected to carbon atoms, forming tertiary amines; compared with primary and secondary amines, the electron cloud density of the unshared electron pairs on the nitrogen atom is low, which is more conducive to the formation of coordination catalysis, and can slow down the early reaction rate, so that the reaction has sufficient mixing time, while the later reaction rate remains almost unchanged, making the reaction product stable. Therefore, their catalytic effects are similar, and the performance of the obtained polysilicon foam insulation material is basically the same; but dimethylcyclohexylamine is more toxic; similarly, the catalytic activity of pentamethyldiethylenetriamine is worse, and hexamethylenetetramine is even worse; in summary, triethylenediamine is the preferred catalyst. The amount of catalyst used is very small, and it has almost no effect on flame retardancy.

[0168] Test Example 3: Effect of shear emulsification on product performance, see Table 3.

[0169] Table 3 Performance comparison data of the products prepared in Example 2 and Comparative Example 1

[0170]

[0171] Note: Comparative Example 1 was not subjected to shear emulsification.

[0172] Example 2 is shear emulsified by a high-speed emulsifying shearing machine to prepare emulsified melamine polyether polyol, while Comparative Example 1 is not shear emulsified. As shown in Table 4, the role of shear dispersion is very important. Under the shearing action, the melamine solid powder forms extremely fine particles. Under the emulsifying action of silicone oil, the liquid polyether polyol 4110 fully wets the melamine powder, thereby forming a long-term stable and uniformly dispersed emulsion. Without shear dispersion, the melamine powder cannot form fine particles, and the wetting effect with the polyether polyol 4110 only stays on the surface of large particles. Once the shearing stops, the large melamine particles will precipitate and stratify. After precipitation and stratification, the melamine powder will be concentrated at the bottom of the barrel, resulting in a very uneven distribution of the melamine powder, thereby resulting in a very uneven product. In severe cases, a large amount of precipitated melamine powder will block the discharge port and damage the equipment.

[0173] Test Example 4: Effect of the ratio of component A, component B and component C on product performance, see Table 4 and Table 5.

[0174] Table 4 Mass percentage of component A in Examples 2, 10 to 15

[0175]

[0176] Note: The mass percentage of component A in Example 16 is the same as the mass percentage of component A in Example 2.

[0177] Table 5 Performance comparison data of products prepared with different component ratios

[0178]

[0179]

[0180] Note: Ratio b is the mass ratio of component A, component B and component C. c is the mass ratio of component A to component B.

[0181] As shown in Table 5, in Example 12, the total amount of the two polyols was slightly reduced, which had almost no effect on the flame retardancy of the polysilicone foam, but the blowing agent was reduced from 10 to 7, the density of the foam increased significantly, the corresponding compressive strength increased a lot, and the thermal conductivity increased slightly. For Example 13, the total amount of the two polyols was also slightly reduced, but the blowing agent was increased from 10 to 20, the density of the polysilicone foam decreased significantly, and thus the compressive strength also decreased significantly, the thermal conductivity decreased slightly, and the flame retardancy was still B1 grade because the flame retardant increased from 10 to 15, which was not much increased. For Example 14, the A and B components remained unchanged, but the inorganic flame retardant increased from 0.1 to 0.3, because the inorganic flame retardant did not participate in the foaming process, so the volume of the foam did not change, but the weight increased by 0.2, so the density increased; because the inorganic flame retardant did not increase much, the corresponding compressive strength, thermal conductivity and flame retardant grade almost did not change.

[0182] However, when the amount of inorganic flame retardant increases sharply (increase by more than 10 times), the polysilicon foam insulation material will be greatly improved to reach the A2 level. For Example 15, when the amount of inorganic flame retardant increases from 0.1 to 2.2, a large amount of flame retardant blocks the burning of the flame at high temperature, and the heat released during the combustion process is sharply reduced, thereby reaching the flame retardant A2 level. However, adding a large amount of inorganic flame retardant will cause the density of polysilicon foam to increase greatly, and the thermal conductivity will also increase significantly, but it is still far superior to the thermal insulation materials such as rock wool, foamed ceramics and siliceous boards currently used in large quantities on the market. With the further increase of the amount of flame retardant, Example 16, the flame retardancy of polysilicon foam is better (A level is already the highest level), and the compressive strength is also greatly increased, but the density will increase and the cost will increase.

[0183] The amount of component B is appropriately increased, such as in Example 17. As can be seen from the molecular formula of the polymerized isocyanate, the increased amount provides the entire system with more cross-linkable hanging energy groups and more rigid benzene rings, so the compressive strength of the polysilicone foam is increased. Because the blowing agent is in component A, it is equivalent to reducing the blowing agent, so the density increases and the flame retardancy decreases slightly, but it can still reach Class B1. The same is true for Example 18, where the density and compressive strength are significantly increased, and the flame retardancy and thermal conductivity do not change significantly.

[0184] It is worth noting that the inorganic flame retardant component C is a key material for solving the combustion grade. A small amount of addition can achieve flame retardancy of B1 grade (of course, the polysilicone polyol and melamine containing catalyst II also have a certain flame retardant effect); a large amount of addition will increase the flame retardancy of the foam insulation material and eventually reach the highest grade A. In comparative example 2, without adding the flame retardant component C, the flame retardancy will not reach grade B1, but only grade B2. This is because the inorganic flame retardant does not catch fire, oxidize, or release heat during the flame combustion process, which greatly reduces the total heat release during the combustion process.

[0185] Test Example 5:

[0186] In order to verify the effect of a single factor on product performance, we also conducted relevant research on the effect of different amounts of polysilicone polyol and melamine polyether polyol containing catalyst II on product performance according to the method of Example 2. Polyisocyanate was used as component B and aluminum oxide was used as component C. The mass ratio of component A, component B and component C was 1:1:0.1. See Table 6 and Table 7 for details. Table 6 Amount of component A of polysilicone polyol and melamine polyether polyol containing catalyst II in different proportions (parts by weight)

[0187]

[0188] Table 7 Effect of different weight ratios of polysilicone polyol and melamine polyether polyol containing catalyst II on product performance

[0189]

[0190] It can be seen from Tables 6 and 7 that a small reduction in the amount of melamine polyether polyol (Group 2) is equivalent to an increase in the percentage of foaming agent, a decrease in density, a slight decrease in the corresponding pressure resistance, and no significant effect on the thermal conductivity. However, when the melamine polyether polyol is reduced to 19 parts by weight (less than 22%, relative to component A) (Group 3), the flame retardancy will drop by one level to B2, which is equivalent to an increase in the percentage of foaming agent, a continuous decrease in density and pressure resistance, and a decrease in the corresponding thermal conductivity. Without adding melamine polyether polyol (Group 4), the flame retardancy is seriously deteriorated to B3 (the lowest flame retardancy level), and because of the decrease in density, the pressure resistance also drops significantly, the pore strength drops, and the foam wall strength is insufficient to form open pores, which leads to a significant increase in the thermal conductivity, reaching 0.041W / (m·K), which is almost worthless. When only melamine polyether polyol (group 5) is used, although the flame retardancy is restored to B1 level, the thermal conductivity increases significantly due to density and compression resistance, reaching 0.036W / (m·K), and the use value is very low. It should be noted that if the polysilicone polyol and melamine polyether polyol containing catalyst II are not added at all, they cannot react with polymerized isocyanate and cannot be foamed.

[0191] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A flame retardant high-quality silicon thermal insulation material, characterized in that: It is prepared from component A, component B and component C; The A component is prepared from the following raw materials in percentage by mass: Containing 19-28% of polysilicone polyol of catalyst II, 22-30% of melamine polyether polyol, 5-10% of crosslinking agent, 2-6% of catalyst I, 8-15% of liquid flame retardant, and 12-20% of foaming agent; The B component is a polymeric isocyanate; The C component is an inorganic flame retardant; Wherein, the mass ratio of component A, component B and component C is 1:1.0-1.5:0.1-0.3, or the mass ratio of component A, component B and component C is 1:1.0-1.5:2.2-2.6; The polysilicone polyol containing catalyst II is prepared by reacting silica sol and diethylene glycol at 90-100° C. under the action of catalyst II and performing vacuum dehydration treatment at the same time; The catalyst II is any one of triethylenediamine, pentamethyldiethylenetriamine, hexamethylenetetramine, and dimethylcyclohexylamine; The mass percentage of SiO2 in the silica sol is 20-30%; The mass ratio of silica sol, catalyst II and diethylene glycol is 1000:2-4:500-700; The melamine polyether polyol is prepared by uniformly mixing polyether polyol, silicone oil and melamine, and then performing shear emulsification. The polyether polyol is polyether polyol 4110 or polyether polyol 635; The silicone oil is any one of dimethyl silicone oil, methyl silicone oil 201, and methyl silicone oil 350; The mass ratio of polyether polyol, silicone oil and melamine is 1000:5-10:1000.

2. The flame retardant high-quality silicon thermal insulation material according to claim 1, characterized in that: The water content of the polysilicone polyol containing catalyst II is ≤ 0.5 wt.%.

3. The flame retardant high-quality silicon thermal insulation material according to claim 1, characterized in that: The cross-linking agent is polyether polyol 403 or triethanolamine; the catalyst I is cyclohexylamine; the liquid flame retardant is tris(2-chloropropyl) phosphate; and the foaming agent is pentane.

4. The flame retardant high-quality silicon thermal insulation material according to claim 1, characterized in that: The inorganic flame retardant is aluminum oxide.

5. A method for preparing the flame retardant high-quality silicon thermal insulation material according to claim 1, comprising the following steps: The silica sol and diethylene glycol are reacted at 90-100° C. under the action of catalyst II, and vacuum dehydration is performed simultaneously to prepare polysilicon polyol containing catalyst II; After the polyether polyol, silicone oil and melamine are uniformly mixed, shear emulsification is performed to prepare emulsified melamine polyether polyol; After the polysilicone polyol containing catalyst II, emulsified melamine polyether polyol, crosslinking agent, catalyst I, liquid flame retardant and foaming agent are stirred and mixed, polymerized isocyanate is added, and the mixture is uniformly mixed by high-pressure impact mixing or high-speed shearing. Then, an inorganic flame retardant is added, and the mixture is stirred and mixed continuously. The mixture is then transferred into a mold or a laminator for foaming and aging to obtain a flame-retardant silicone foam thermal insulation material.

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