Spraying rigid foam polyurethane material for building exterior wall and preparation method thereof

Abstract

The invention relates to a spraying rigid foam polyurethane material for building exterior walls, which is composed of a component A and a component B. The component A comprises the following raw material components in parts by weight: 65-76 parts of polymer polyol, 1.8-3.5 parts of a chain extender, 0.55-0.85 part of a foam stabilizer, 0.67-0.85 part of a catalyst I, 1.2-1.75 parts of epoxy vinyl ester resin, and 0.01-0.5 part of a weather-resistant auxiliary agent. And the component B is polyphenyl methane polyisocyanate. Compared with the prior art, by adopting the mutual combination of the polymer polyol, the chain extender, the foam stabilizer, the weather-resistant additive and the like, the flame retardance, the mechanical property and the weather resistance of the product are improved.

Description

Technical Field

[0001] The invention relates to the field of engineering materials, in particular to a spraying rigid foam polyurethane material for building exterior walls and a preparation method thereof. Background Art

[0002] In today's construction field, the choice of building exterior wall materials plays a vital role in the performance, life and safety of buildings. Traditional building exterior wall materials, such as bricks and concrete, have long occupied an important position due to their excellent structural bearing capacity. However, with the continuous improvement of people's requirements for building energy conservation and comfort, the shortcomings of these traditional materials have become increasingly prominent - their poor thermal insulation performance leads to serious heat loss in buildings in winter, and they easily absorb too much heat in summer, increasing energy consumption and air conditioning costs. In contrast, some new insulation materials such as polystyrene foam boards have emerged, and their outstanding thermal insulation effect has been highly favored. However, polystyrene foam boards have many disadvantages. Its flammable nature makes it very easy to become a combustion aid when a fire occurs, seriously threatening the safety of buildings and personnel. At the same time, its easy aging problem also causes the material performance to decline rapidly over time, and it cannot meet the needs of long-term use of buildings. As a polymer material, spray rigid foam polyurethane material has many excellent properties: it has extremely low thermal conductivity and can effectively prevent heat transfer; it is resistant to aging and has good adhesion to the base surface. It can maintain relatively stable performance under long-term exposure to the sun and rain.

[0003] Spray rigid foam polyurethane materials have been widely used in the field of building exterior wall insulation due to their excellent thermal insulation performance, waterproof performance and construction convenience. However, when spray rigid foam polyurethane materials are used for building exterior walls, they face complex and diverse environmental challenges. On the one hand, in terms of natural environmental factors, the exterior walls of buildings have to withstand long-term wind, sun and rain. Ultraviolet radiation will continuously damage the internal structure of the material. Rainwater erosion may cause erosion and peeling of the material. The drastic change in temperature will also cause the thermal expansion and contraction of the material, and then cracks will occur. Existing spray rigid foam polyurethane materials for building exterior walls are difficult to meet these complex conditions. The materials have cracking, shedding, water seepage and other phenomena, and cannot guarantee the structural stability, durability and safety of the building exterior walls. On the other hand, spray rigid foam polyurethane materials for building exterior walls have extremely high requirements for fire resistance. Spray rigid foam polyurethane materials for building exterior walls with excellent performance need further research and development. Summary of the invention

[0004] The purpose of the present invention is to provide a spray rigid foam polyurethane material for building exterior walls and a preparation method thereof in order to solve the above problems.

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

[0006] A spray rigid polyurethane foam material for building exterior walls is composed of component A and component B. Component A comprises the following raw material components in parts by weight: 65-76 parts of polymer polyol, 1.8-3.5 parts of chain extender, 0.55-0.85 parts of foam stabilizer, 0.67-0.85 parts of catalyst 1, 1.2-1.75 parts of epoxy vinyl ester resin, and 0.01-0.5 parts of weathering aid; component B is polyphenylmethane polyisocyanate.

[0007] As a preferred technical solution, the polymer polyol is composed of plant polyol and reactive flame retardant modified polyol, and the weight ratio of the plant polyol to the reactive flame retardant modified polyol is 1:3-5.

[0008] As a preferred technical solution, the plant polyol is castor oil polyol.

[0009] As a preferred technical solution, the reactive flame-retardant modified polyol is a phosphorus-containing flame-retardant polyol, which is prepared by the following method: in a reaction kettle, a small molecule alcohol and N,N-bis(2-hydroxyethyl)aminomethylenephosphonic acid diethyl ester (FRC-6) are added, stirring is started, heating is performed at 80-150°C for 1-3h, catalyst 2 is added, the temperature is maintained at 100-120°C, an epoxy compound is added, and the reaction is performed for 1-2h to obtain a phosphorus-containing flame-retardant polyol.

[0010] As a preferred technical solution, the weight ratio of the small molecule alcohol, N,N-bis(2-hydroxyethyl)aminomethylenephosphonic acid diethyl ester (FRC-6), epoxy compound, and catalyst 2 is 60-70:80-100:200-210:1-2;

[0011] The small molecule alcohol is selected from one or more of methanol, ethanol, propanol, ethylene glycol, and glycerol;

[0012] The catalyst is selected from one or more of tetraethylammonium bromide, tetraethylammonium chloride, benzyltrimethylammonium chloride, and dodecyltrimethylammonium chloride;

[0013] The epoxy compound is selected from one or more of ethylene oxide, propylene oxide and epichlorohydrin.

[0014] As a preferred technical solution, the chain extender is a diol or diamine compound containing an aromatic ring, selected from one or more of hydroquinone dihydroxyethyl ether (HQEE), metaphenylenediamine (MPD), and 4,4'-diaminodiphenylmethane (MDA).

[0015] As a preferred technical solution, the foam stabilizer is an organosilicon foam stabilizer selected from poly(dimethylsiloxane);

[0016] And / or, the catalyst 1 is formate or potassium acetate of 2-hydroxy-NNN-trimethyl-1-propylamine;

[0017] And / or, the epoxy vinyl ester resin is Derakane 510 flame retardant epoxy vinyl ester resin produced by Dow Chemical.

[0018] As a preferred technical solution, the weathering agent is a mixture of a hindered phenol antioxidant and a benzotriazole ultraviolet absorber in a ratio of 2:1.

[0019] As a preferred technical solution, the viscosity of the polyphenylmethane polyisocyanate is 300-600cp, preferably at least one of Wanhua Chemical PM400, PM700 and BASF M20S.

[0020] The method for preparing the above-mentioned spray rigid foam polyurethane material for building exterior walls comprises the following steps:

[0021] Preparation of component A: Add polymer polyol, chain extender, foam stabilizer, catalyst 1, epoxy vinyl ester resin and weathering agent into a stirring kettle and stir evenly;

[0022] When in use, component A and component B are prepared in a weight ratio of 1:1.05-1.15 and sprayed using a high-pressure foaming machine.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] The present invention adopts a composite polymer polyol, which is composed of castor oil polyol and reactive flame retardant modified polyol. Castor oil polyol has excellent weather resistance, chemical stability and hydrophobicity, which helps to improve waterproof performance. Reactive flame retardant modified polyol is obtained by reacting phosphorus-containing organic flame retardant with small molecule alcohol. The polyol body has excellent flame retardancy, which greatly improves the flame retardancy of the whole material and helps to maintain the stability of material performance. Chain extender adopts diol or diamine compound containing aromatic ring, which is inserted between molecular chains to increase molecular chain length and crosslinking density, improve the tensile strength and hardness of the material, and its aromatic ring structure helps to improve the weather resistance of the whole material, and cooperates with polymer polyol to resist environmental erosion. Foam stabilizer makes bubbles evenly dispersed and stably exist, forming a fine and uniform closed-cell foam structure, so that the material has good thermal insulation performance. Weathering aid is hindered phenol antioxidant and benzotriazole ultraviolet absorber, which improves the aging resistance of the material. The present invention has excellent overall performance through the mutual combination of various components. DETAILED DESCRIPTION

[0025] The present invention is described in detail below with reference to specific embodiments, but this is by no means a limitation of the present invention.

[0026] A spray rigid polyurethane foam material for building exterior walls, composed of component A and component B, wherein component A comprises the following raw material components in parts by weight: 65-76 parts of polymer polyol, 1.8-3.5 parts of chain extender, 0.55-0.85 parts of foam stabilizer, 0.67-0.85 parts of catalyst 1, 1.2-1.75 parts of epoxy vinyl ester resin, and 0.01-0.5 parts of weathering additive;

[0027] The component B is polyphenylmethane polyisocyanate.

[0028] As a preferred technical solution, the component A includes the following raw material components in parts by weight: 71 parts of polymer polyol, 2.7 parts of chain extender, 0.71 parts of foam stabilizer, 0.76 parts of catalyst 1, 1.55 parts of epoxy vinyl ester resin, and 0.35 parts of weathering agent;

[0029] As a preferred technical solution, the polymer polyol is composed of plant polyol and reactive flame retardant modified polyol, the weight ratio of the plant polyol to the reactive flame retardant modified polyol is 1:3-5, preferably, the weight ratio of the plant polyol to the reactive flame retardant modified polyol is 1:4.

[0030] As a preferred technical solution, the plant polyol is castor oil polyol, preferably SY750 modified castor oil polyol produced by Shanghai Shuyu Chemical Co., Ltd. SY750 modified castor oil polyol is used to prepare spray rigid foam polyurethane materials, and has excellent weather resistance, chemical stability and a certain hardness, and can provide good support and protection. At the same time, due to the hydrophobicity of castor oil polyol, it is less sensitive to moisture during the curing process, which can prevent moisture from entering the interior of the polyurethane material to cause performance degradation, and help improve the waterproof performance of the building exterior wall.

[0031] As a preferred technical solution, the reactive flame-retardant modified polyol is a phosphorus-containing flame-retardant polyol, which is prepared by the following method: in a reaction kettle, a small molecule alcohol and N,N-bis(2-hydroxyethyl)aminomethylenephosphonic acid diethyl ester (FRC-6) are added, stirring is started, heating is performed at 80-150°C for 1-3h, catalyst 2 is added, the temperature is maintained at 100-120°C, an epoxy compound is added, and the reaction is performed for 1-2h to obtain a phosphorus-containing flame-retardant polyol.

[0032] As a preferred technical solution, the weight ratio of the small molecule alcohol, N,N-bis(2-hydroxyethyl)aminomethylenephosphonic acid diethyl ester (FRC-6), epoxy compound, and catalyst two is 60-70:80-100:200-210:1-2. Further preferably, the weight ratio of the small molecule alcohol, N,N-bis(2-hydroxyethyl)aminomethylenephosphonic acid diethyl ester (FRC-6), epoxy compound, and catalyst two is 65:90:205:1.5.

[0033] As a preferred technical solution, the small molecule alcohol is selected from one or more of methanol, ethanol, propanol, ethylene glycol, and glycerol.

[0034] As a preferred technical solution, the catalyst is selected from one or more of tetraethylammonium bromide, tetraethylammonium chloride, benzyltrimethylammonium chloride, and dodecyltrimethylammonium chloride.

[0035] As a preferred technical solution, the epoxy compound is selected from one or more of ethylene oxide, propylene oxide and epichlorohydrin.

[0036] As a preferred technical solution, the chain extender is a diol or diamine compound containing an aromatic ring, selected from one or more of hydroquinone dihydroxyethyl ether (HQEE), metaphenylenediamine (MPD), and 4,4'-diaminodiphenylmethane (MDA). The chain extender reacts with polymer polyols and polyphenylmethane polyisocyanates, inserts between molecular chains, increases the length of molecular chains and cross-linking density, and improves the tensile strength and hardness of the material. At the same time, its aromatic ring structure helps to improve the overall weather resistance of the material and cooperates with the polymer polyol to resist environmental erosion.

[0037] As a preferred technical solution, the foam stabilizer is a silicone foam stabilizer selected from poly(dimethylsiloxane) and has a surface active structure. During the foaming process, it can effectively reduce the surface tension of the system, so that the bubbles are evenly dispersed and stably present, forming a fine and uniform closed-cell foam structure, which makes the material have good thermal insulation properties and reduces the risk of reduced weather resistance of the material due to problems such as uneven foam cells and rupture.

[0038] As a preferred technical solution, the catalyst 1 is 2-hydroxy-NNN-trimethyl-1-propylamine formate (TMR-2) or potassium acetate (KAc).

[0039] As a preferred technical solution, the epoxy vinyl ester resin adopts Dow Chemical Derakane510 flame retardant epoxy vinyl ester resin, which has excellent flame retardant properties and is suitable for occasions with high fire protection requirements.

[0040] As a preferred technical solution, the weathering aid is a mixture of a hindered phenol antioxidant and a benzotriazole ultraviolet absorber in a ratio of 2:1. The hindered phenol antioxidant can capture free radicals generated by the material under the action of light, heat, etc., inhibit oxidation chain reactions, and delay material aging. The benzotriazole ultraviolet absorber efficiently absorbs ultraviolet rays and dissipates energy in a harmless form. The two work together to enhance the weather resistance of the material and effectively reduce problems such as discoloration, cracking, and strength loss of the material under outdoor exposure.

[0041] As a preferred technical solution, the hindered phenol antioxidants include antioxidant 1010, antioxidant 1076, antioxidant 2246, and antioxidant 1035; the benzotriazole ultraviolet absorbers include 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole (ultraviolet absorber UV-326), 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole (ultraviolet absorber UV-327), etc.

[0042] As a preferred technical solution, the viscosity of the polyphenylmethane polyisocyanate is 300-600cp, preferably at least one of Wanhua Chemical PM400, PM700 and BASF M20S.

[0043] A method for preparing a spray rigid polyurethane foam material for building exterior walls comprises the following steps: preparing component A: adding polymer polyol, chain extender, foam stabilizer, catalyst 1, epoxy vinyl ester resin, and weathering agent into a stirring kettle and stirring evenly. When using, mix component A with component B 1:

[0044] The weight ratio of 1.05-1.15 is prepared on the spot and sprayed by a high-pressure foaming machine.

[0045] The following is a detailed description through specific examples. All those not described in the examples are conventional means in the art or commonly used commercially available reagents.

[0046] Example 1

[0047] A spray rigid polyurethane foam material for building exterior walls consists of component A and component B. Component A comprises the following raw material components in parts by weight: 71 parts of polymer polyol, 2.7 parts of chain extender, 0.71 parts of foam stabilizer, 0.76 parts of catalyst 1, 1.55 parts of epoxy vinyl ester resin, and 0.35 parts of weathering aid. Component B is polyphenylmethane polyisocyanate.

[0048] Among them, the polymer polyol is composed of plant polyol and reactive flame retardant modified polyol, and the weight ratio of the two is 1:4. In this embodiment, the plant polyol is castor oil polyol, and the grade SY750 modified castor oil polyol of Shanghai Shuyu Chemical Co., Ltd. is used. The reactive flame retardant modified polyol is a phosphorus-containing flame retardant polyol, which is prepared by the following method: in a reactor, add small molecule alcohol (ethylene glycol) and N, N-bis (2-hydroxyethyl) aminomethylenephosphonic acid diethyl ester (FRC-6), start stirring, heat at 115 ° C for 2h, add catalyst two (tetraethylammonium bromide), keep the temperature at 110 ° C, add epoxy compound (propylene oxide), react for 2h, and prepare phosphorus-containing flame retardant polyol. Among them, the weight ratio of small molecule alcohol, FRC-6, epoxy compound, and catalyst two is 65:90:205:1.5.

[0049] In this embodiment, the chain extender is hydroquinone dihydroxyethyl ether (HQEE, CAS No.: 104-38-1); the foam stabilizer is poly (dimethylsiloxane) (CAS No.: 156327-07-0); the catalyst one is 2-hydroxy-NNN-trimethyl-1-propylamine formate (TMR-2, CAS: 62314-25-4); the epoxy vinyl ester resin uses Derakane510 flame retardant epoxy vinyl ester resin from Dow Chemical. The weathering agent is a mixture of a hindered phenol antioxidant and a benzotriazole ultraviolet absorber in a ratio of 2:1, the hindered phenol antioxidant is antioxidant 1010, and the benzotriazole ultraviolet absorber is ultraviolet absorber UV-326. The polyphenylmethane polyisocyanate is Wanhua Chemical PM400.

[0050] Example 2

[0051] A spray rigid polyurethane foam material for building exterior walls consists of component A and component B. Component A comprises the following raw material components in parts by weight: 65 parts of polymer polyol, 2.2 parts of chain extender, 0.55 parts of foam stabilizer, 0.72 parts of catalyst 1, 1.24 parts of epoxy vinyl ester resin, and 0.45 parts of weathering aid. Component B is polyphenylmethane polyisocyanate.

[0052] Among them, the polymer polyol is composed of plant polyol and reactive flame retardant modified polyol, and the weight ratio of the two is 1:3.5. In this embodiment, the plant polyol is castor oil polyol, and the brand SY750 modified castor oil polyol of Shanghai Shuyu Chemical Co., Ltd. is used. The reactive flame retardant modified polyol is a phosphorus-containing flame retardant polyol, which is prepared by the following method: in a reactor, add small molecule alcohol (ethylene glycol) and N, N-bis (2-hydroxyethyl) aminomethylenephosphonic acid diethyl ester (FRC-6), start stirring, heat at 100 ° C for 2h, add catalyst two (tetraethylammonium chloride), keep the temperature at 105 ° C, add epoxy compound (ethylene oxide), react for 2h, and prepare phosphorus-containing flame retardant polyol. Among them, the weight ratio of small molecule alcohol, FRC-6, epoxy compound, and catalyst two is 63:87:204:1.8.

[0053] In this embodiment, the chain extender is m-phenylenediamine (MPD); the foam stabilizer is poly(dimethylsiloxane) (CAS No.: 156327-07-0); the catalyst 1 is 2-hydroxy-NNN-trimethyl-1-propylamine formate (TMR-2, CAS: 62314-25-4); the epoxy vinyl ester resin uses Derakane510 flame retardant epoxy vinyl ester resin from Dow Chemical. The weathering agent is a mixture of a hindered phenol antioxidant and a benzotriazole ultraviolet absorber in a ratio of 2:1, the hindered phenol antioxidant is antioxidant 1076, and the benzotriazole ultraviolet absorber is ultraviolet absorber UV-326. The polyphenylmethane polyisocyanate is Wanhua Chemical PM700.

[0054] Example 3

[0055] A spray rigid polyurethane foam material for building exterior walls consists of component A and component B. Component A comprises the following raw material components in parts by weight: 69 parts of polymer polyol, 1.8 parts of chain extender, 0.57 parts of foam stabilizer, 0.67 parts of catalyst 1, 1.65 parts of epoxy vinyl ester resin, and 0.09 parts of weathering aid. Component B is polyphenylmethane polyisocyanate.

[0056] Among them, the polymer polyol is composed of plant polyol and reactive flame retardant modified polyol, and the weight ratio of the two is 1:3. In this embodiment, the plant polyol is castor oil polyol, and the brand SY750 modified castor oil polyol of Shanghai Shuyu Chemical Co., Ltd. is used. The reactive flame retardant modified polyol is a phosphorus-containing flame retardant polyol, which is prepared by the following method: in a reactor, add small molecule alcohol (ethylene glycol) and N, N-bis (2-hydroxyethyl) aminomethylenephosphonic acid diethyl ester (FRC-6), start stirring, heat at 95 ° C for 2h, add catalyst di (dodecyl trimethyl ammonium chloride), keep the temperature at 110 ° C, add epoxy compound (ethylene oxide), react for 2h, and prepare phosphorus-containing flame retardant polyol. Among them, the weight ratio of small molecule alcohol, FRC-6, epoxy compound, and catalyst two is 60:85:200:1.

[0057] In this embodiment, the chain extender is 4,4'-diaminodiphenylmethane (MDA); the foam stabilizer is poly(dimethylsiloxane) (CAS No.: 156327-07-0); the catalyst 1 is potassium acetate (KAc); the epoxy vinyl ester resin uses Derakane510 flame retardant epoxy vinyl ester resin from Dow Chemical. The weathering agent is a mixture of a hindered phenol antioxidant and a benzotriazole ultraviolet absorber in a ratio of 2:1, the hindered phenol antioxidant is antioxidant 1035, and the benzotriazole ultraviolet absorber is ultraviolet absorber UV-326. The polyphenylmethane polyisocyanate is BASF M20S.

[0058] Example 4

[0059] A spray rigid polyurethane foam material for building exterior walls consists of component A and component B. Component A comprises the following raw material components in parts by weight: 76 parts of polymer polyol, 3.3 parts of chain extender, 0.83 parts of foam stabilizer, 0.83 parts of catalyst 1, 1.68 parts of epoxy vinyl ester resin, and 0.2 parts of weathering aid. Component B is polyphenylmethane polyisocyanate.

[0060] Among them, the polymer polyol is composed of plant polyol and reactive flame retardant modified polyol, and the weight ratio of the two is 1:5. In this embodiment, the plant polyol is castor oil polyol, and the brand SY750 modified castor oil polyol of Shanghai Shuyu Chemical Co., Ltd. is used. The reactive flame retardant modified polyol is a phosphorus-containing flame retardant polyol, which is prepared by the following method: in a reactor, add small molecule alcohol (ethylene glycol) and N, N-bis (2-hydroxyethyl) aminomethylenephosphonic acid diethyl ester (FRC-6), start stirring, heat at 95 ° C for 2h, add catalyst two (tetraethylammonium bromide), keep the temperature at 110 ° C, add epoxy compound (ethylene oxide), react for 2h, and prepare phosphorus-containing flame retardant polyol. Among them, the weight ratio of small molecule alcohol, FRC-6, epoxy compound, and catalyst two is 70:95:210:1.8.

[0061] In this embodiment, the chain extender is 4,4'-diaminodiphenylmethane (MDA); the foam stabilizer is poly(dimethylsiloxane) (CAS No.: 156327-07-0); the catalyst 1 is potassium acetate (KAc); the epoxy vinyl ester resin uses Derakane510 flame retardant epoxy vinyl ester resin from Dow Chemical. The weathering agent is a mixture of a hindered phenol antioxidant and a benzotriazole ultraviolet absorber in a ratio of 2:1, the hindered phenol antioxidant is antioxidant 1035, and the benzotriazole ultraviolet absorber is ultraviolet absorber UV-327. The polyphenylmethane polyisocyanate is BASF M20S.

[0062] Example 5

[0063] A spray rigid polyurethane foam material for building exterior walls consists of component A and component B. Component A comprises the following raw material components in parts by weight: 74 parts of polymer polyol, 3.5 parts of chain extender, 0.85 parts of foam stabilizer, 0.82 parts of catalyst 1, 1.75 parts of epoxy vinyl ester resin, and 0.45 parts of weathering aid. Component B is polyphenylmethane polyisocyanate.

[0064] Among them, the polymer polyol is composed of plant polyol and reactive flame retardant modified polyol, and the weight ratio of the two is 1:5. In this embodiment, the plant polyol is castor oil polyol, and the grade SY750 modified castor oil polyol of Shanghai Shuyu Chemical Co., Ltd. is used. The reactive flame retardant modified polyol is a phosphorus-containing flame retardant polyol, which is prepared by the following method: in a reactor, add small molecule alcohol (ethylene glycol) and N, N-bis (2-hydroxyethyl) aminomethylenephosphonic acid diethyl ester (FRC-6), start stirring, heat at 110°C for 2h, add catalyst two (tetraethylammonium bromide), keep the temperature at 110°C, add epoxy compound (propylene oxide), react for 2h, and prepare phosphorus-containing flame retardant polyol. Among them, the weight ratio of small molecule alcohol, FRC-6, epoxy compound, and catalyst two is 70:100:205:2.

[0065] In this embodiment, the chain extender is 4,4'-diaminodiphenylmethane (MDA); the foam stabilizer is poly(dimethylsiloxane) (CAS No.: 156327-07-0); the catalyst 1 is 2-hydroxy-NNN-trimethyl-1-propylamine formate (TMR-2, CAS: 62314-25-4); the epoxy vinyl ester resin uses Derakane510 flame retardant epoxy vinyl ester resin from Dow Chemical. The weathering agent is a mixture of a hindered phenol antioxidant and a benzotriazole ultraviolet absorber in a ratio of 2:1, the hindered phenol antioxidant is antioxidant 1010, and the benzotriazole ultraviolet absorber is ultraviolet absorber UV-326. The polyphenylmethane polyisocyanate is Wanhua Chemical PM700.

[0066] Example 6

[0067] A spray rigid polyurethane foam material for building exterior walls consists of component A and component B. Component A comprises the following raw material components in parts by weight: 65 parts of polymer polyol, 1.8 parts of chain extender, 0.65 parts of foam stabilizer, 0.7 parts of catalyst 1, 1.3 parts of epoxy vinyl ester resin, and 0.1 parts of weathering aid. Component B is polyphenylmethane polyisocyanate.

[0068] Among them, the polymer polyol is composed of plant polyol and reactive flame retardant modified polyol, and the weight ratio of the two is 1:4. In this embodiment, the plant polyol is castor oil polyol, and the brand SY750 modified castor oil polyol of Shanghai Shuyu Chemical Co., Ltd. is used. The reactive flame retardant modified polyol is a phosphorus-containing flame retardant polyol, which is prepared by the following method: in a reactor, add small molecule alcohol (ethylene glycol) and N, N-bis (2-hydroxyethyl) aminomethylenephosphonic acid diethyl ester (FRC-6), start stirring, heat at 110°C for 2h, add catalyst two (tetraethylammonium bromide), keep the temperature at 110°C, add epoxy compound (propylene oxide), react for 2h, and prepare phosphorus-containing flame retardant polyol. Among them, the weight ratio of small molecule alcohol, FRC-6, epoxy compound, and catalyst two is 66:96:208:1.6.

[0069] In this embodiment, the chain extender is 4,4'-diaminodiphenylmethane (MDA); the foam stabilizer is poly(dimethylsiloxane) (CAS No.: 156327-07-0); the catalyst 1 is 2-hydroxy-NNN-trimethyl-1-propylamine formate (TMR-2, CAS: 62314-25-4); the epoxy vinyl ester resin uses Derakane510 flame retardant epoxy vinyl ester resin from Dow Chemical. The weathering agent is a mixture of a hindered phenol antioxidant and a benzotriazole ultraviolet absorber in a ratio of 2:1, the hindered phenol antioxidant is antioxidant 1035, and the benzotriazole ultraviolet absorber is ultraviolet absorber UV-326. The polyphenylmethane polyisocyanate is BASF M20S.

[0070] Comparative Example 1

[0071] Compared with Example 1, the plant polyol in the polymer polyol is replaced by an equal amount of reactive flame retardant modified polyol, and the rest is the same as Example 1, specifically as follows:

[0072] A spray rigid polyurethane foam material for building exterior walls consists of component A and component B. Component A comprises the following raw material components in parts by weight: 71 parts of polymer polyol, 2.7 parts of chain extender, 0.71 parts of foam stabilizer, 0.76 parts of catalyst 1, 1.55 parts of epoxy vinyl ester resin, and 0.35 parts of weathering aid. Component B is polyphenylmethane polyisocyanate.

[0073] Among them, the polymer polyol is a reactive flame retardant modified polyol, which is prepared by the following method: in a reaction kettle, add a small molecule alcohol (ethylene glycol) and N, N-bis (2-hydroxyethyl) aminomethylenephosphonic acid diethyl ester (FRC-6), start stirring, heat at 115 ° C for 2 hours, add catalyst two (tetraethylammonium bromide), keep the temperature at 110 ° C, add epoxy compound (propylene oxide), react for 2 hours, and obtain phosphorus-containing flame retardant polyol. Among them, the weight ratio of small molecule alcohol, FRC-6, epoxy compound, and catalyst two is 65:90:205:1.5.

[0074] In this embodiment, the chain extender is hydroquinone dihydroxyethyl ether (HQEE, CAS No.: 104-38-1); the foam stabilizer is poly (dimethylsiloxane) (CAS No.: 156327-07-0); the catalyst one is 2-hydroxy-NNN-trimethyl-1-propylamine formate (TMR-2, CAS: 62314-25-4); the epoxy vinyl ester resin uses Derakane510 flame retardant epoxy vinyl ester resin from Dow Chemical. The weathering agent is a mixture of a hindered phenol antioxidant and a benzotriazole ultraviolet absorber in a ratio of 2:1, the hindered phenol antioxidant is antioxidant 1010, and the benzotriazole ultraviolet absorber is ultraviolet absorber UV-326. The polyphenylmethane polyisocyanate is Wanhua Chemical PM400.

[0075] Comparative Example 2

[0076] Compared with Example 1, the reactive flame retardant modified polyol in the polymer polyol is replaced by an equal amount of polyether polyol INOVOL R6207 from Shandong Yinuowei New Materials Co., Ltd., and the rest is the same as Example 1, as follows:

[0077] A spray rigid polyurethane foam material for building exterior walls consists of component A and component B. Component A comprises the following raw material components in parts by weight: 71 parts of polymer polyol, 2.7 parts of chain extender, 0.71 parts of foam stabilizer, 0.76 parts of catalyst 1, 1.55 parts of epoxy vinyl ester resin, and 0.35 parts of weathering aid. Component B is polyphenylmethane polyisocyanate.

[0078] The polymer polyol is composed of plant polyol and polyether polyol INOVOL R6207, and the weight ratio of the two is 1:4. In this embodiment, the plant polyol is castor oil polyol, and the modified castor oil polyol with the brand SY750 produced by Shanghai Shuyu Chemical Co., Ltd. is used.

[0079] In this embodiment, the chain extender is hydroquinone dihydroxyethyl ether (HQEE, CAS No.: 104-38-1); the foam stabilizer is poly (dimethylsiloxane) (CAS No.: 156327-07-0); the catalyst one is 2-hydroxy-NNN-trimethyl-1-propylamine formate (TMR-2, CAS: 62314-25-4); the epoxy vinyl ester resin uses Derakane510 flame retardant epoxy vinyl ester resin from Dow Chemical. The weathering agent is a mixture of a hindered phenol antioxidant and a benzotriazole ultraviolet absorber in a ratio of 2:1, the hindered phenol antioxidant is antioxidant 1010, and the benzotriazole ultraviolet absorber is ultraviolet absorber UV-326. The polyphenylmethane polyisocyanate is Wanhua Chemical PM400.

[0080] Comparative Example 3

[0081] Compared with Example 1, epoxy vinyl ester resin is not added, and the rest is the same as Example 1.

[0082] Comparative Example 4

[0083] Compared with Example 1, glycerol is used as the chain extender, and the rest is the same as Example 1.

[0084] Comparative Example 5

[0085] Compared with Example 1, no foam stabilizer is added, and the rest is the same as Example 1.

[0086]

Performance test

[0087] According to the formula of the embodiment and the comparative example, each raw material is added into a stirring kettle, stirred evenly to prepare component A, and when used, component A and component B are prepared in a weight ratio of 1:1.1, sprayed by a high-pressure sprayer, matured for 10 minutes after spraying, and molded to obtain a rigid foam polyurethane material.

[0088] The prepared rigid polyurethane foam material was subjected to performance tests, referring to GB 8624-2012 "Classification of Combustion Performance of Building Materials and Products" and GB 50404-2017 "Technical Specifications for Thermal Insulation and Waterproof Engineering of Rigid Polyurethane Foam". Hygrothermal aging test: The test samples were placed in a hygrothermal aging test chamber (temperature 60°C, relative humidity 90%) for one week to test the dimensional stability of the samples. The results are shown in Table 1.

[0089] Table 1 Test results

[0090]

[0091] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A spray rigid polyurethane foam material for building exterior walls, consisting of component A and component B, characterized in that: The component A comprises the following raw material components in parts by weight: 65-76 parts of polymer polyol, 1.8-3.5 parts of chain extender, 0.55-0.85 parts of foam stabilizer, 0.67-0.85 parts of catalyst 1, 1.2-1.75 parts of epoxy vinyl ester resin, and 0.01-0.5 parts of weathering agent; The component B is polyphenylmethane polyisocyanate.

2. The spray rigid polyurethane foam material for building exterior walls according to claim 1, characterized in that: The polymer polyol is composed of plant polyol and reactive flame retardant modified polyol, and the weight ratio of the plant polyol to the reactive flame retardant modified polyol is 1:3-5.

3. The spray rigid polyurethane foam material for building exterior walls according to claim 2, characterized in that: The plant polyol is castor oil polyol.

4. The spray rigid polyurethane foam material for building exterior walls according to claim 2, characterized in that: The reactive flame-retardant modified polyol is a phosphorus-containing flame-retardant polyol, which is prepared by the following method: adding a small molecule alcohol and N,N-bis(2-hydroxyethyl)aminomethylenephosphonic acid diethyl ester into a reaction kettle, starting stirring, heating at 80-150° C. for 1-3 hours, adding a second catalyst, maintaining the temperature at 100-120° C., adding an epoxy compound, reacting for 1-2 hours, and obtaining the phosphorus-containing flame-retardant polyol.

5. The spray rigid polyurethane foam material for building exterior walls according to claim 4, characterized in that: The weight ratio of the small molecule alcohol, N,N-bis(2-hydroxyethyl)aminomethylenephosphonic acid diethyl ester, epoxy compound and catalyst 2 is 60-70:80-100:200-210:1-2; The small molecule alcohol is selected from one or more of methanol, ethanol, propanol, ethylene glycol, and glycerol; The catalyst is selected from one or more of tetraethylammonium bromide, tetraethylammonium chloride, benzyltrimethylammonium chloride, and dodecyltrimethylammonium chloride; The epoxy compound is selected from one or more of ethylene oxide, propylene oxide and epichlorohydrin.

6. The spray rigid polyurethane foam material for building exterior walls according to claim 1, characterized in that: The chain extender is a diol or diamine compound containing an aromatic ring, and is selected from one or more of hydroquinone dihydroxyethyl ether, metaphenylenediamine, and 4,4'-diaminodiphenylmethane.

7. The spray rigid polyurethane foam material for building exterior walls according to claim 1, characterized in that: The foam stabilizer is an organosilicon foam stabilizer selected from poly(dimethylsiloxane); And / or, the catalyst 1 is formate or potassium acetate of 2-hydroxy-NNN-trimethyl-1-propylamine; And / or, the epoxy vinyl ester resin is Derakane 510 flame retardant epoxy vinyl ester resin produced by Dow Chemical.

8. The spray rigid polyurethane foam material for building exterior walls according to claim 1, characterized in that: The weathering aid is a mixture of a hindered phenol antioxidant and a benzotriazole ultraviolet absorber in a ratio of 2:

1.

9. The spray rigid polyurethane foam material for building exterior walls according to claim 1, characterized in that: The viscosity of the polyphenylmethane polyisocyanate is 300-600 cp, and is preferably at least one of Wanhua Chemical PM400, PM700 and BASF M20S.

10. The method for preparing the spray rigid foam polyurethane material for building exterior walls according to claim 1, characterized in that: The following steps are involved: Preparation of component A: Add polymer polyol, chain extender, foam stabilizer, catalyst 1, epoxy vinyl ester resin and weathering agent into a stirring kettle and stir evenly; When using, mix component A with component B 1: The weight ratio of 1.05-1.15 is prepared on the spot and sprayed by a high-pressure foaming machine.

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