Non-combustible spraying polyurethane material for refrigeration house and preparation method of non-combustible spraying polyurethane material

Abstract

The invention relates to a non-combustible spraying polyurethane material for a refrigeration house and a preparation method thereof, the non-combustible spraying polyurethane material for the refrigeration house is composed of a component A and a component B. The volume ratio of the component A to the component B is 1: 0.9-1.7, the component A is prepared from the following components in parts by weight: 15 to 70 parts of polyether polyol composition, 15 to 70 parts of flame-retardant polyether polyol, 15 to 70 parts of flame-retardant polyester polyol, 20 to 45 parts of flame retardant, 0.5 to 3 parts of foam stabilizer, 0.2 to 2 parts of chemical foaming agent, 10 to 30 parts of physical foaming agent and 6 to 16 parts of catalyst; and the component B is prepared from 123 to 333 parts of polymethylene polyphenyl polyisocyanate. The non-combustible polyurethane foam formed by effectively matching the components such as the polyether polyol II, the polyether polyol III, the polyester polyol, the catalyst and the foaming agent and mixing and spraying with the polymethylene polyphenyl polyisocyanic acid has the characteristic of high flame retardance.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane and relates to a spray polyurethane material, in particular to a non-flammable spray polyurethane material for cold storage and a preparation method thereof. Background Art

[0002] Polyurethane foam is a kind of polymer synthetic material with excellent comprehensive performance, and it is also classified as the fifth largest plastic. Rigid polyurethane foam, also known as rigid polyurethane foam (RPUF), is one of the most important products of polyurethane materials. Compared with other inorganic and organic polymer materials, it not only has low density, good thermal insulation, good energy-saving effect, and green environmental protection, but also is an environmentally friendly thermal insulation material. It is also recognized as the best energy-saving material in the field of thermal insulation in the world, so it is widely used in the field of thermal insulation.

[0003] Polyurethane spraying has been widely promoted and applied in the fields of building exterior walls, cold storage insulation, etc. due to its advantages of convenient construction, high construction efficiency, special-shaped structure spraying, seamless connection, and integrated insulation and waterproofing. However, the general polyurethane foam products on the market have insufficient flame retardancy and can even ignite in the atmospheric environment. The risk factor is extremely high, and fire accidents are prone to occur, causing property losses to the people, and in serious cases, life-threatening. With the increase in the frequency of fires in various countries, governments of various countries have also put forward higher requirements for the flame retardancy of polyurethane insulation materials. The requirements for flame retardancy in the fields of construction, cold storage, etc. are also increasing year by year. The industry urgently needs a non-combustible spray polyurethane material for cold storage.

[0004] The polyurethane insulation materials currently used in the market are all flammable materials, combustible materials or flame-retardant materials. When designed and used, they need to be separated by a fire barrier of at least 15 minutes or other approved non-combustible material coverings (such as fire-retardant paint, color steel plates, gypsum boards, etc.). Summary of the invention

[0005] The purpose of the present invention is to overcome the deficiencies of the prior art and to provide a non-combustible spray polyurethane material for cold storage, which has excellent flame retardant properties and meets the non-combustible polyurethane spray standard.

[0006] The first object of the present invention is to provide a non-combustible spray polyurethane material for cold storage, which is composed of component A and component B, wherein the volume ratio of component A to component B is 1:0.9-1.7.

[0007] The component A comprises, by weight: 15-70 parts of a polyether polyol composition, 15-70 parts of a flame retardant polyether polyol, 15-70 parts of a flame retardant polyester polyol, 20-45 parts of a flame retardant, 0.5-3 parts of a foam leveler, 0.2-2 parts of a chemical foaming agent, 10-30 parts of a physical foaming agent and 6-16 parts of a catalyst; the polyether polyol composition comprises the following components by weight: 5-20 parts of polyether polyol I, 5-35 parts of polyether polyol II and 5-30 parts of polyether polyol III,

[0008] The polyether polyol I is prepared with glycerol as the initiator, propylene oxide as the chain extension, ethylene oxide as the end capping, a viscosity of 500-1500 mPa·s / 25°C, and a hydroxyl value of 30-50 mgKOH / g; the polyether polyol II is prepared with ethylenediamine as the initiator, propylene oxide as the chain extension, a viscosity of 1400-2100 mPa·s / 50°C, and a hydroxyl value of 600-900 mgKOH / g; the polyether polyol III is prepared with sorbitol as the initiator, propylene oxide as the chain extension, ethylene oxide as the end capping, a viscosity of 900-2100 mPa·s / 25°C, and a hydroxyl value of 250-550 mgKOH / g;

[0009] The B component is 123-333 parts of polymethylene polyphenyl polyisocyanate.

[0010] Optimally, the flame retardant polyether polyol has a viscosity of 100-800 mPa·s / 25° C. and a hydroxyl value of 100-120 mgKOH / g.

[0011] Optimally, the flame retardant polyester polyol is a flame retardant polyester polyol based on phthalic anhydride and paraben, with a viscosity of 9000-12000 mPa·s / 25°C and a hydroxyl value of 175-215 mgKOH / g.

[0012] Optimally, the flame retardant is a mixture of one or more selected from tris(chloroisopropyl) phosphate, triethyl phosphate, aluminum hydroxide, magnesium hydroxide, melamine, ammonium polyphosphate and coated red phosphorus.

[0013] Optimally, the foam leveling agent is a non-hydrolyzable silicon-carbon surfactant.

[0014] Furthermore, the foam leveling agent is a mixture of one or more selected from M-88710, M-88716, M8805, M158, L6950, L6920, BL-677, BL580Na, UR-16553 and UR-5940.

[0015] Optimally, the chemical foaming agent is deionized water, and the physical foaming agent is one or a mixture of two selected from pentafluoropropane and chlorotrifluoropropene.

[0016] Optimally, the catalyst is a mixture of one or more selected from organic bismuth, N,N-dimethylethanolamine, PT303, T12, 2040, PC5, PC8 and 75% potassium isooctanoate solution in diethylene glycol K15; preferably, it is a mixture of N,N-dimethylethanolamine, PT303, organic bismuth, T12, 2040 and 75% potassium isooctanoate solution in diethylene glycol K15.

[0017] Optimally, the polymethylene polyphenyl polyisocyanate is a mixture of one or more selected from PM200, PM400, Bayer 44V20, BASF M20S, Dow MR200 and Huntsman 5005.

[0018] Another object of the present invention is to provide a method for preparing the above-mentioned non-combustible spray polyurethane material for cold storage, comprising the following steps:

[0019] (a) weighing the polyether polyol I, the polyether polyol II, the polyether polyol III, the flame retardant polyether polyol, the flame retardant polyester polyol, the flame retardant, the foam leveling agent, the chemical foaming agent, the physical foaming agent and the catalyst in a proportion, adding them into a stirring tank, and stirring and mixing to obtain the component A;

[0020] (b) Weigh the polymethylene polyphenyl polyisocyanate in a formula amount as component B, mix the component A and the component B according to a volume ratio, and mix and foam them at 10° C. to 40° C. using a polyurethane foam sprayer.

[0021] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0022] The non-combustible spray polyurethane material for cold storage of the present invention adopts A component and B component of specific formula for matched use, so that the polyurethane has excellent flame retardant performance, meets the non-combustible polyurethane spray standard, and far exceeds the common polyurethane spray material on the market; specifically: ① the non-combustible polyurethane material can effectively prevent the spread and expansion of flames, and significantly reduce the risk of fire; ② during the combustion process, a protective film can be formed on the surface of the polyurethane material, which effectively prevents the invasion of flames, thereby slowing down the combustion speed; ③ the polyurethane high flame retardant material generates less harmful gases and solid waste during the combustion process, and is environmentally friendly; ④ the non-combustible polyurethane will not significantly affect the physical and mechanical properties of the polyurethane material, such as strength, stiffness and durability, while maintaining high flame retardant properties; ⑤ the non-combustible polyurethane can reduce the density of smoke generated in the event of a fire, improve the visibility of the escape route, and reduce the harm of smoke to the human body. DETAILED DESCRIPTION

[0023] The non-combustible spray polyurethane material for cold storage of the present invention is composed of component A and component B, wherein the volume ratio of component A to component B is 1:0.9-1.7, and the component A comprises, by weight: 15-70 parts (preferably 40-60 parts) of a polyether polyol composition, 15-70 parts (preferably 20-40 parts) of a flame retardant polyether polyol, 15-70 parts (preferably 20-40 parts) of a flame retardant polyester polyol, 20-45 parts (preferably 35-45 parts) of a flame retardant, 0.5-3 parts (preferably 0.5-2 parts) of a uniform foaming agent, and 0.2-2 parts (preferably 0.2 ~0.6 parts), 10-30 parts (preferably 27-30 parts) of physical foaming agent and 6-16 parts (preferably 7-15 parts) of catalyst; the polyether polyol composition comprises the following components in parts by weight: 5-20 parts of polyether polyol I, 5-35 parts of polyether polyol II and 5-30 parts of polyether polyol III; the polyether polyol III is based on sorbitol as an initiator, propylene oxide as a chain extender, ethylene oxide as a terminal, with a viscosity of 900-2100 MPa·s / 25℃ and a hydroxyl value of 250-550 mgKOH / g; the B component is 123-333 parts of polymethylene polyphenyl polyisocyanate. The non-combustible polyurethane foam formed by the effective combination of components such as polyether polyol II, polyether polyol III, polyester polyol, catalyst, and foaming agent and mixed with polymethylene polyphenyl polyisocyanate and spraying has high flame retardant properties. The specific advantages are mainly reflected in the following aspects: ① Non-combustible polyurethane materials can effectively prevent the spread and expansion of flames, significantly reducing the risk of fire; ② During the combustion process, a protective film can be formed on the surface of the polyurethane material, effectively preventing the invasion of flames, thereby slowing down the combustion rate; ③ Polyurethane highly flame retardant materials produce less harmful gases and solid waste during the combustion process, which is environmentally friendly; ④ Non-combustible polyurethane will not significantly affect the physical and mechanical properties of polyurethane materials, such as strength, stiffness and durability, while maintaining high flame retardant properties; ⑤ Non-combustible polyurethane can reduce the density of smoke generated in the event of a fire, improve the visibility of the escape route, and reduce the harm of smoke to the human body.

[0024] The polyether polyol I is based on glycerol as the initiator, propylene oxide as the chain extension, and ethylene oxide as the end cap, with a viscosity of 500-1500MPa·s / 25℃ and a hydroxyl value of 30-50mgKOH / g. The polyether polyol II is based on ethylenediamine as the initiator, propylene oxide as the chain extension, with a viscosity of 1400-2100MPa·s / 50℃ and a hydroxyl value of 600-900mgKOH / g. The flame retardant polyether polyol has a viscosity of 100-800mPa·s / 25℃ and a hydroxyl value of 100-120mgKOH / g. The flame retardant polyester polyol is a flame retardant polyester polyol based on phthalic anhydride and paraben, and is the WS-4210F product of Wanshun Company. The flame retardant is a mixture of one or two of tris(chloroisopropyl) phosphate-TCPP, triethyl phosphate-TEP, aluminum hydroxide-Al(OH)3, magnesium hydroxide, melamine, ammonium polyphosphate (APP), and coated red phosphorus. The foam leveling agent is a non-hydrolyzed silicon-carbon surfactant, which can be a mixture of one or more selected from M-88710, M-88716, M8805, M158, Maitu L6950, Maitu L6920, Maihao BL-677, BL580Na, UR-16553, and UR-5940 of Meside.

[0025] The chemical foaming agent is deionized water, the physical foaming agent is a mixture of one or two of pentafluoropropane and trifluorochloropropylene. The catalyst is a mixture of one or more selected from organic bismuth, N, N-dimethylethanolamine, PT303, T12, 2040, PC5, PC8 and 75% potassium isooctanoate diethylene glycol solution K15; specifically, the catalyst is a mixture of six raw materials: N, N-dimethylethanolamine, PT303, organic bismuth, T12, 2040 and 75% potassium isooctanoate diethylene glycol solution K15. Specifically, the weight ratio of the five catalysts of N,N-dimethylethanolamine, PT303, organic bismuth, T12, 2040 and 75% potassium 2-ethylhexanoate solution K15 is 1-2: 2-4: 0.5-1.5: 0.5-1: 2-4: 1.5-4; N,N-dimethylethanolamine, PT303 and T12 have a faster starting speed, 2040 can avoid the polyurethane reaction at low temperature to produce polyurea, thereby improving the brittleness of the spray foam, and 75% potassium 2-ethylhexanoate solution K15 and organic bismuth improve the maturation of the foam; thus, compounding multiple catalysts in proportion can produce a good synergistic effect, thereby having better construction tolerance. Ammonium polyphosphate (APP), zinc borate and coated red phosphorus can be used as acid sources. Pentaerythritol and sorbitol are used as carbon sources. Urea, melamine and polyamide are used as gas sources. Acid source, carbon source and gas source exist as the three basic elements of intumescent flame retardant, and are added in different proportions according to specific requirements in actual use, using one, two or more of them. In addition, liquid flame retardant can be used at the same time, and the finished polyurethane foam has better flame retardant properties after spraying. The polymethylene polyphenyl polyisocyanate is a mixture of one or more selected from Wanhua PM200 and PM400, Bayer 44V20, BASF M20S, Dow MR200 and Huntsman 5005.

[0026] The preparation method of the non-flammable spray polyurethane material for cold storage comprises the following steps: (a) weighing the polyether polyol I, the polyether polyol II, the polyether polyol III, the flame retardant polyether polyol, the flame retardant polyester polyol, the flame retardant, the foam leveling agent, the chemical foaming agent, the physical foaming agent and the catalyst in proportion, adding them into a stirring tank, stirring and mixing to obtain the component A; (b) weighing the polymethylene polyphenyl polyisocyanate as the component B, mixing the component A and the component B in a volume ratio, and mixing and foaming them in a polyurethane foaming sprayer at 10°C to 40°C.

[0027] The present invention is further described in detail below in conjunction with specific examples, but the present invention is not limited to the following examples. The implementation conditions used in the examples can be further adjusted according to different requirements of specific use, and the implementation conditions not specified are conventional conditions in the industry.

[0028] Example 1

[0029] This embodiment provides a non-combustible spray polyurethane material for cold storage, which is composed of component A and component B (the volume ratio of component A to component B is 1:1);

[0030] Wherein, component A comprises: 50g of polyether polyol composition (comprising 5g of polyether polyol I (F3135), 15g of polyether polyol II (SD403) and 30g of polyether polyol III (SD1035)), 30g of flame retardant polyester polyol WS-4210F, 20g of flame retardant polyether polyol WS-4110, 30g of flame retardant TCPP, 15g of coated red phosphorus (GYTK85), 1g of foaming agent M8805, 11.5g of catalyst (2g of N,N-dimethylethanolamine, 3g of PT303, 0.5g of T12, 3g of 2040 and 3g of K15), 0.5g of deionized water (chemical foaming agent) and 30g of pentafluoropropane (physical foaming agent);

[0031] Component B was 188 g PM200 (purchased from Yantai Wanhua).

[0032] The method for preparing the non-combustible spray polyurethane material for cold storage comprises the following steps: (a) weighing polyether polyol I, polyether polyol II, polyether polyol III, polyester polyol, flame retardant, foam leveling agent, chemical foaming agent, catalyst and physical foaming agent according to mass ratio, and mixing to form component A;

[0033] (b) Weigh polymethylene polyphenyl polyisocyanate as component B; mix component A and component B in a volume ratio of 1:1, and spray the mixture on the surface of building materials at 10° C. to 40° C. using a polyurethane foam sprayer to form foam. No primer spraying is required, and the mixture can be directly sprayed layer by layer.

[0034] Example 2

[0035] The present embodiment provides a non-combustible spray polyurethane material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that: component A includes: 40g of a polyether polyol composition (including 5g of polyether polyol I (F3135), 10g of polyether polyol II (SD403) and 25g of polyether polyol III (SD1035)), 40g of a flame retardant polyester polyol WS-4210F, 20g of a flame retardant polyether polyol WS-4110, 25g of a flame retardant TCPP, 10g of coated red phosphorus, 0.5g of a foaming agent M8805, 7g of a catalyst (1g of N,N-dimethylethanolamine, 2g of PT303, 0.5g of T12, 2g of 2040 and 1.5g of K15), 0.2g of deionized water (chemical foaming agent) and 27g of pentafluoropropane (physical foaming agent); component B is 167g of PM200 (purchased from Yantai Wanhua).

[0036] Example 3

[0037] The present embodiment provides a non-combustible spray polyurethane material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that: component A includes: 60g of a polyether polyol composition (including 10g of polyether polyol I (F3135), 15g of polyether polyol II (SD403) and 35g of polyether polyol III (SD1035)), 20g of a flame retardant polyester polyol WS-4210F, 20g of a flame retardant polyether polyol WS-4110, 35g of a flame retardant TCPP, 10g of coated red phosphorus, 2g of a foaming agent M8805, 15g of a catalyst (2g of N,N-dimethylethanolamine, 4g of PT303, 1g of T12, 4g of 2040 and 4g of K15), 0.6g of deionized water (chemical foaming agent), and 30g of pentafluoropropane (physical foaming agent); component B is 190g of PM200 (purchased from Yantai Wanhua).

[0038] Example 4

[0039] The present embodiment provides a non-combustible spray polyurethane material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that: component A includes: 70g of a polyether polyol composition (including 20g of polyether polyol I (F3135), 15g of polyether polyol II (SD403) and 35g of polyether polyol III (SD1035)), 15g of a flame retardant polyester polyol WS-4210F, 15g of a flame retardant polyether polyol WS-4110, 15g of a flame retardant TCPP, 5g of coated red phosphorus, 0.5g of a foaming agent M8805, 6g of a catalyst (2g of N,N-dimethylethanolamine, 1g of PT303, 1g of T12, 1g of 2040 and 1g of K15), 0.2g of deionized water (chemical foaming agent), and 10g of pentafluoropropane (physical foaming agent); component B is 123g of PM200 (purchased from Yantai Wanhua).

[0040] Example 5

[0041] This embodiment provides a non-combustible spray polyurethane material for cold storage and a preparation method thereof, which is basically the same as that in Example 1. The difference is that component A includes: 15g of polyether polyol composition (including 5g of polyether polyol I (F3135), 5g of poly ether polyol II (SD403) and 5g polyether polyol III (SD1035)), 70g flame retardant polyester polyol WS-4210F, 15g flame retardant polyether polyol WS-4110, flame retardant 30g TCPP, 15g coated red phosphorus, 3g foaming agent M8805, 16g catalyst (4g N, N-dimethylethanolamine, 4g PT303, 4g T12, 2g 2040 and 2g K15), 2g deionized water (chemical foaming agent), 30g pentafluoropropane (physical foaming agent); component B is 333g PM200 (purchased from Yantai Wanhua).

[0042] Example 6

[0043] This embodiment provides a non-combustible spray polyurethane material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that: the polyether polyol composition is 50g, including 5g F3135, 10g SD403 and 35g SD1035.

[0044] Example 7

[0045] This embodiment provides a non-combustible spray polyurethane material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that: 50 g of the polyether polyol composition contains 7 g of F3135, 13 g of SD403 and 30 g of SD1035.

[0046] Example 8

[0047] This embodiment provides a non-combustible spray polyurethane material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that: the flame retardant is 45g, including 20g TCPP, 10g TEP and 15g coated red phosphorus.

[0048] Example 9

[0049] This embodiment provides a non-combustible spray polyurethane material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that: 45g of flame retardant, including 10g of TCPP, 20g of TEP and 15g of coated red phosphorus.

[0050] Example 10

[0051] This embodiment provides a non-combustible spray polyurethane material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that the components of the catalyst are different, including 1.5g N,N-dimethylethanolamine, 2.5g PT303, 1gT12, 3g 2040 and 3g K15.

[0052] Embodiment 11

[0053] This embodiment provides a non-combustible spray polyurethane material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that the components of the catalyst are different, including 1g N,N-dimethylethanolamine, 4g PT303, 1g T12, 3g2040 and 3g K15.

[0054] Example 12

[0055] This embodiment provides a non-combustible spray polyurethane material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that the components of the catalyst are different, including 2g N,N-dimethylethanolamine, 3g PT303, 1g T12, 3.5g 2040 and 2g K15.

[0056] Example 13

[0057] This embodiment provides a non-combustible spray polyurethane material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that the components of the catalyst are different, including 1g N,N-dimethylethanolamine, 3g PT303, 0.8g T12, 3.5g 2040 and 4g K15.

[0058] Embodiment 14

[0059] This embodiment provides a non-combustible spray polyurethane material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that: 0.5g of deionized water and 28g of pentafluoropropane.

[0060] Embodiment 15

[0061] This embodiment provides a non-combustible spray polyurethane material for cold storage and a preparation method thereof, which is basically the same as that in Embodiment 1, except that: 0.6 g of deionized water and 25 g of pentafluoropropane.

[0062] Comparative Example 1

[0063] This example provides a non-combustible spray polyurethane thermal insulation material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that: no polyether polyol I is added, and the polyether polyol composition is 45g (including 15g SD403 and 30g SD1035).

[0064] Comparative Example 2

[0065] This example provides a non-combustible spray polyurethane thermal insulation material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that: no polyether polyol II is added, and the polyether polyol composition is 35g (including 5g F3135 and 30g SD1035).

[0066] Comparative Example 3

[0067] This example provides a non-combustible spray polyurethane thermal insulation material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that: no polyether polyol III is added, and the polyether polyol composition is 20g (including 5g F3135 and 15g SD403).

[0068] Comparative Example 4

[0069] This example provides a non-combustible spray polyurethane thermal insulation material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that: 80g of polyether polyol composition (including 10g F3135, 15g SD403, and 55g SD1035).

[0070] Comparative Example 5

[0071] This example provides a non-combustible spray polyurethane thermal insulation material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that: 10 g of flame retardant (including 10 g of TCPP).

[0072] Comparative Example 6

[0073] This example provides a non-combustible spray polyurethane thermal insulation material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that: 60g of flame retardant (including 60g of TCPP).

[0074] Comparative Example 7

[0075] This example provides a non-combustible spray polyurethane insulation material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that: N,N-dimethylethanolamine is not added, and four catalysts are added in different proportions (including 3g PT303, 0.5g T12, 3g 2040 and 3g K15).

[0076] Comparative Example 8

[0077] This example provides a non-combustible spray polyurethane thermal insulation material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that the components of the catalyst are different, including 2g N,N-dimethylethanolamine, 3g PT303, 3g 2040 and 3g K15.

[0078] Comparative Example 9

[0079] This example provides a non-combustible spray polyurethane insulation material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that the components of the catalyst are different, including 2g N,N-dimethylethanolamine, 3g PT303, 1g T12, 1 part 2040 and 3g K15.

[0080] Comparative Example 10

[0081] This example provides a non-combustible spray polyurethane thermal insulation material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that: 1g of deionized water and 25g of pentafluoropropane.

[0082] Comparative Example 11

[0083] This example provides a non-flammable spray polyurethane thermal insulation material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that no deionized water is added.

[0084] Comparative Example 12

[0085] This example provides a non-combustible spray polyurethane thermal insulation material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that: no coated red phosphorus is added, and 15g of aluminum hydroxide is added.

[0086] Comparative Example 13

[0087] This example provides a non-combustible spray polyurethane thermal insulation material for cold storage and a preparation method thereof, which is basically the same as that in Example 1, except that: no coated red phosphorus is added, and 15g of melamine is added.

[0088] The polyurethane thermal insulation materials in Examples 1-15 and Comparative Examples 1-13 were subjected to performance tests, and the data are listed in Table 1; the specific test standards are as follows: density GB / T 6343-2009, compressive strength GB / T 8813-2008, closed porosity GB / T 10799-2008, thermal conductivity GB / T 10294-2008, bonding strength GB 50404-2007 Appendix B, ISO 5660-1-2015, GBT16172-2007 Test method for heat release rate of building materials and combustion performance grade test GB / T 20284.

[0089] Table 1 Performance data of polyurethane spray foam insulation materials in Examples 1-15 and Comparative Examples 1-13

[0090]

[0091]

[0092] Table 2 Combustion performance data of polyurethane spray foam insulation materials in Examples 1-15 and Comparative Examples 1-13

[0093]

[0094]

[0095] It can be clearly seen from the data of Examples 1-4 and Comparative Examples 1-3 and Table 1 that in the composition of polyether polyols, when the ratio of polyether polyol I, polyether polyol II, polyether polyol III, flame retardant polyester polyol and flame retardant polyether polyol is (5-20): (10-15): (25-35): (10-40): (15-20), all performance parameters meet the actual application requirements. In Comparative Example 1, as the amount of polyether polyol I decreases, the spray foam product begins to become brittle and the adhesion to the substrate becomes very poor. In Comparative Examples 2 and 3, without adding polyether polyol II and polyether polyol III, the foam will shrink.

[0096] It can be clearly seen from the data in Examples 1, 8, 9, Comparative Examples 5, 6 and Table 1 that when the amount of flame retardant added in the formula is too small, the overall flame retardant properties of the spray polyurethane foam deteriorate and cannot meet the design requirements; however, when the amount of flame retardant added is large, the plasticity of the polyurethane foam is significantly enhanced and the foam will shrink.

[0097] It can be clearly seen from the data of Examples 1, 10-13, Comparative Examples 7-9 and Table 1 above that the proportion of the five catalysts added in the polyurethane formula is very important. When the total amount of the added catalyst is too small, there will be abnormal construction phenomena such as side flow, top dripping, poor surface flatness of the foam curing, slow maturation of the foam skin, etc. during the spraying process. From Comparative Example 9, the addition of 2040 has a relatively large effect on the adhesion. From Comparative Example 7 above, when the amount of catalyst added in the formula is too small, not only will the gun tip be blocked during the spraying process, but it will also cause the spraying operation efficiency to decrease and the overall flatness of the foam to deteriorate.

[0098] It can be clearly seen from the data of Examples 1, 14-15, Comparative Examples 10-11 and Table 1 above that the amount of chemical foaming agent added in the formula is also very critical. When the amount of chemical foaming agent water added in the formula is too large, a large amount of urea-bonded structures will be produced under low temperature conditions, the overall brittleness of the foam is relatively large, and debonding will occur (the foam will fall off from the sprayed substrate). The reaction of water (chemical foaming agent) and isocyanate is an exothermic reaction, which will provide energy for the physical foaming agent to foam. When there is no chemical foaming agent, the foaming reaction of the entire polyurethane is unbalanced. The phenomenon of flowing is very likely to occur during the spraying process, and the flatness of the foam will become very poor.

[0099] It can be clearly seen from the data of Example 1, Comparative Examples 12-13, and Tables 1 and 2 above that adding different types of solid flame retardants will have a great impact on the surface ripening and combustion performance tests of the foam. The main reason is that the coated red phosphorus will form a dense carbon layer during the combustion test, combined with the characteristics of the non-combustible polyurethane formula design that will expand at high temperatures, so that the foam as a whole cannot continue to burn, the total amount of heat release is small, and the flame cannot spread horizontally to the edge of the long wing. Among them, the overall performance of the coated red phosphorus is better than that of aluminum hydroxide and melamine.

[0100] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the contents of the present invention and implement them accordingly. They cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A non-combustible spray polyurethane material for cold storage, which consists of component A and component B, wherein the volume ratio of component A to component B is 1:0.9-1.7, and is characterized in that: The component A comprises, by weight: 15-70 parts of a polyether polyol composition, 15-70 parts of a flame retardant polyether polyol, 15-70 parts of a flame retardant polyester polyol, 20-45 parts of a flame retardant, 0.5-3 parts of a foam leveler, 0.2-2 parts of a chemical foaming agent, 10-30 parts of a physical foaming agent and 6-16 parts of a catalyst; the polyether polyol composition comprises the following components by weight: 5-20 parts of polyether polyol I, 5-35 parts of polyether polyol II and 5-30 parts of polyether polyol III, The polyether polyol I is prepared with glycerol as the initiator, propylene oxide as the chain extension, ethylene oxide as the end capping, a viscosity of 500-1500 mPa·s / 25°C, and a hydroxyl value of 30-50 mgKOH / g; the polyether polyol II is prepared with ethylenediamine as the initiator, propylene oxide as the chain extension, a viscosity of 1400-2100 mPa·s / 50°C, and a hydroxyl value of 600-900 mgKOH / g; the polyether polyol III is prepared with sorbitol as the initiator, propylene oxide as the chain extension, ethylene oxide as the end capping, a viscosity of 900-2100 mPa·s / 25°C, and a hydroxyl value of 250-550 mgKOH / g; The B component is 123-333 parts of polymethylene polyphenyl polyisocyanate.

2. The non-combustible spray polyurethane material for cold storage according to claim 1, characterized in that: The flame retardant polyether polyol has a viscosity of 100 to 800 mPa·s / 25° C. and a hydroxyl value of 100 to 120 mgKOH / g.

3. The non-combustible spray polyurethane material for cold storage according to claim 1, characterized in that: The flame retardant polyester polyol is a flame retardant polyester polyol based on phthalic anhydride and paraben, with a viscosity of 9000-12000 mPa·s / 25° C. and a hydroxyl value of 175-215 mgKOH / g.

4. The non-combustible spray polyurethane material for cold storage according to claim 1, characterized in that: The flame retardant is a mixture of one or more selected from tris(chloroisopropyl)phosphate, triethyl phosphate, aluminum hydroxide, magnesium hydroxide, melamine, ammonium polyphosphate and coated red phosphorus.

5. The non-combustible spray polyurethane material for cold storage according to claim 1, characterized in that: The foam leveling agent is a non-hydrolyzable silicon-carbon surfactant.

6. The non-combustible spray polyurethane material for cold storage according to claim 5, characterized in that: The foam leveling agent is a mixture of one or more selected from M-88710, M-88716, M8805, M158, L6950, L6920, BL-677, BL580Na, UR-16553 and UR-5940.

7. The non-combustible spray polyurethane material for cold storage according to claim 1, characterized in that: The chemical foaming agent is deionized water, and the physical foaming agent is one or a mixture of two selected from pentafluoropropane and chlorotrifluoropropylene.

8. The non-combustible spray polyurethane material for cold storage according to claim 1, characterized in that: The catalyst is a mixture of one or more selected from organic bismuth, N,N-dimethylethanolamine, PT303, T12, 2040, PC5, PC8 and 75% potassium isooctanoate solution in diethylene glycol K15; preferably a mixture of N,N-dimethylethanolamine, PT303, organic bismuth, T12, 2040 and 75% potassium isooctanoate solution in diethylene glycol K15.

9. The non-combustible spray polyurethane material for cold storage according to claim 1, characterized in that: The polymethylene polyphenyl polyisocyanate is a mixture of one or more selected from PM200, PM400, Bayer 44V20, BASF M20S, Dow MR200 and Huntsman 5005.

10. The method for preparing the non-combustible spray polyurethane material for cold storage according to any one of claims 1 to 9, characterized in that: The following steps are involved: (a) weighing the polyether polyol I, the polyether polyol II, the polyether polyol III, the flame retardant polyether polyol, the flame retardant polyester polyol, the flame retardant, the foam leveling agent, the chemical foaming agent, the physical foaming agent and the catalyst in a proportion, adding them into a stirring tank, and stirring and mixing to obtain the component A; (b) Weigh the polymethylene polyphenyl polyisocyanate in a formula amount as component B, mix the component A and the component B according to a volume ratio, and mix and foam them at 10° C. to 40° C. using a polyurethane foam sprayer.

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