Marine spraying rigid foam polyurethane material and preparation method thereof

Abstract

The invention relates to a marine spraying rigid foam polyurethane material which is composed of a component A and a component B. The component A comprises the following raw materials in parts by weight: 60-88 parts of polymer polyol, 2-3 parts of a chain extender, 4-7 parts of a flame retardant, 0.5-0.9 part of a foam stabilizer, 0.6-0.9 part of a catalyst and 1-1.5 parts of a silane end-capping agent. And the component B is polyphenyl methane polyisocyanate. Compared with the prior art, the modified polymer polyol, the siloxane modified epoxy resin and the optimized flame retardant are adopted, so that the water resistance, the mechanical property, the flame retardant efficiency and the like of the product are improved.

Description

Technical Field

[0001] The invention relates to the field of engineering materials, in particular to a marine spray rigid foam polyurethane material and a preparation method thereof. Background Art

[0002] At present, small-scale aquaculture fishing boats, river cleaning fishing boats or large and medium-sized ships in the ocean are mostly made of PE, steel, wood and other materials. The fishing boats made of the above materials are heavy and will corrode or rot after being used in water, especially in seawater for a period of time. Wooden fishing boats are prone to wood rot and reduced displacement as the use time increases; PE materials will age and deteriorate after being used under sunlight for a period of time. Spray rigid foam polyurethane material is a polymer synthetic material. In the process of decades of development, its excellent properties have been used in ships. As an excellent thermal insulation and energy-saving material, polyurethane rigid foam has great development potential in ships. It has low thermal conductivity and good thermal performance. It also has the advantages of aging resistance, good chemical stability, excellent moisture and water resistance, temperature resistance and non-melting, and good bonding performance with the base surface. Although spray rigid foam polyurethane material has many advantages mentioned above, for ship use, especially long-term operation in the marine environment, it is necessary to have good waterproof performance, corrosion resistance, wear resistance, and flame retardancy to ensure the stability, durability and safety of the hull structure. Existing marine spray rigid foam polyurethane materials have problems such as insufficient durability and limited waterproof performance. Therefore, marine spray rigid foam polyurethane materials with excellent performance still need to be further developed. Summary of the invention

[0003] The purpose of the present invention is to provide a marine spray rigid foam polyurethane material and a preparation method thereof in order to solve the above problems.

[0004] The purpose of the present invention is achieved through the following technical solutions:

[0005] A marine spray rigid polyurethane foam material, composed of component A and component B, wherein component A comprises the following raw material components in parts by weight: 60-88 parts of polymer polyol, 2-3 parts of chain extender, 4-7 parts of flame retardant, 0.5-0.9 parts of foam stabilizer, 0.6-0.9 parts of catalyst, and 1-1.5 parts of silane end-capping agent;

[0006] The component B is polyphenylmethane polyisocyanate.

[0007] Preferably, the polymer polyol is composed of bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3, and the weight ratio of the bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3 is 6-7:1.8-2.1:0.9-1.2:1.45-1.55.

[0008] Preferably, the weight ratio of the bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3 is 6.5:2:1:1.5.

[0009] Preferably, the bio-based polyol is a bio-based polyol having a functionality of 7.5-9.5 and a hydroxyl value of 390-450 mgKOH / g;

[0010] The polyether polyol 1 is a polyether polyol having a functionality of 4.6-4.8 and a hydroxyl value of 392-420 mgKOH / g;

[0011] The polyether polyol II is a polyether polyol having a functionality of 4.0-4.2 and a hydroxyl value of 370-390 mgKOH / g;

[0012] The polyether polyol tris is a phthalic anhydride polyester polyol with a hydroxyl value of 310-330 mgKOH / g.

[0013] Preferably, the chain extender is at least one of glycerol, dipropylene glycol, 1,3-butylene glycol and trimethylolpropane.

[0014] Preferably, the flame retardant is a mixture of triethyl phosphate (TEP) and tri(2-chloropropyl) phosphate (TCPP), and the mass ratio of triethyl phosphate to tri(2-chloropropyl) phosphate is 1:1.5.

[0015] Preferably, the catalyst is 2-hydroxy-NNN-trimethyl-1-propylamine formate (TMR-2) or potassium acetate (KAc);

[0016] The foam stabilizer is Evonik B8545.

[0017] Preferably, the viscosity of the polyphenylmethane polyisocyanate is 300-600 cp, preferably at least one of Wanhua Chemical PM400, PM700 and BASF M20S.

[0018] Preferably, the silane capping agent is a siloxane-modified epoxy resin, which is prepared by the following method:

[0019] Put the epoxy resin (E44) into the reactor, add the solvent n-butanol, stir until the epoxy resin is completely dissolved, control the temperature to 75-80°C, add 3-isocyanatepropyltrimethoxysilane (CAS No. 15396-00-6), stir and react for 2-3 hours to obtain;

[0020] The weight ratio of the epoxy resin, 3-isocyanate propyltrimethoxysilane and n-butanol is 2:1:4-5.

[0021] A method for preparing a marine spray rigid polyurethane foam material comprises the following steps: preparing component A: adding polymer polyol, chain extender, flame retardant, foam stabilizer, catalyst and silane end-capping agent into a stirring kettle and stirring evenly;

[0022] When in use, component A and component B are prepared in a weight ratio of 1:1.1-1.2 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 compounded polymer polyol, and selects a highly hydrophobic bio-based polyol as the main chain polymer polyol. The bio-based polyol can effectively avoid the influence of water on the foaming reaction, and is helpful to improve water resistance and mechanical properties. The epoxy resin modified by siloxane can improve the bonding strength of polyurethane, effectively avoid hydrolysis or degradation when soaked in water, has excellent water resistance, can meet the use requirements of the immersion environment, and improve water resistance and mechanical properties. The flame retardant TEP significantly improves the flame retardancy of the product foam and has a good flame retardant effect. Adding TEP to the polyurethane material can improve the thermal stability of the polymer. TEP can play a role in catalytic cross-linking and synergistic carbonization during the combustion process of polyurethane, and the flame retardant efficiency is improved after adding TEP. 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 marine spray rigid foam polyurethane material consists of component A and component B, wherein component A comprises the following raw material components in parts by weight: 60-88 parts of polymer polyol, 2-3 parts of chain extender, 4-7 parts of flame retardant, 0.5-0.9 parts of foam stabilizer, 0.6-0.9 parts of catalyst, and 1-1.5 parts of silane end-capping agent; and component B is polyphenylmethane polyisocyanate.

[0027] As a preferred embodiment, the component A comprises the following raw material components in parts by weight: 75.5 parts of polymer polyol, 2.4 parts of chain extender, 5 parts of flame retardant, 0.65 parts of foam stabilizer, 0.77 parts of catalyst, and 1.3 parts of silane capping agent.

[0028] As a preferred embodiment, the polymer polyol is composed of bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3, and the weight ratio of the bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3 is 6-7:1.8-2.1:0.9-1.2:1.45-1.55. Preferably, the weight ratio of the bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3 is 6.5:2:1:1.5.

[0029] As a preferred embodiment, the bio-based polyol is a bio-based polyol with a functionality of 7.5-9.5 and a hydroxyl value of 390-450 mgKOH / g; the polyether polyol 1 is a polyether polyol with a functionality of 4.6-4.8 and a hydroxyl value of 392-420 mgKOH / g; the polyether polyol 2 is a polyether polyol with a functionality of 4.0-4.2 and a hydroxyl value of 370-390 mgKOH / g; the polyether polyol 3 is a phthalic anhydride polyester polyol with a hydroxyl value of 310-330 mgKOH / g.

[0030] As a preferred embodiment, the bio-based polyol adopts the FH-8450 bio-based polyol produced by Zhangjiagang Feihang Technology Co., Ltd., the polyether polyol one is the commercially available brand INOVOL R6001C, the polyether polyol two is the commercially available brand INOVOL R6205, both of which are products of Shandong INOVOL New Materials Co., Ltd., and the polyether polyol three is RAYNOL PS-3152 produced by Qingdao Ruinuo Chemical Co., Ltd.

[0031] As a preferred embodiment, the chain extender is at least one of glycerol, dipropylene glycol, 1,3-butylene glycol and trimethylolpropane.

[0032] As a preferred embodiment, the flame retardant is a mixture of triethyl phosphate (TEP) and tri(2-chloropropyl) phosphate (TCPP), wherein the mass ratio of triethyl phosphate to tri(2-chloropropyl) phosphate is 1:1.5. TEP can significantly improve the flame retardancy of the foam product and has a good flame retardant effect. Adding TEP to the polyurethane material can improve the thermal stability of the polymer. TEP can play a role in catalytic cross-linking and synergistic carbonization during the combustion of polyurethane, and the flame retardant efficiency is improved after adding TEP.

[0033] As a preferred embodiment, the catalyst is 2-hydroxy-NNN-trimethyl-1-propylamine formate (TMR-2) or potassium acetate (KAc); the foam stabilizer is Evonik B8545.

[0034] As a preferred embodiment, the viscosity of the polyphenylmethane polyisocyanate is 300-600 cp, preferably at least one of Wanhua Chemical PM400, PM700 and BASF M20S.

[0035] As a preferred embodiment, the silane capping agent is a siloxane-modified epoxy resin, which is prepared by the following method: putting an epoxy resin (E44) into a reactor, adding a solvent of n-butanol, stirring until the epoxy resin is completely dissolved, controlling the temperature to 75-80°C, adding 3-isocyanatepropyltrimethoxysilane (CAS No. 15396-00-6), and stirring the reaction for 2-3 hours to obtain the obtained product; the weight ratio of the epoxy resin, 3-isocyanatepropyltrimethoxysilane, and n-butanol is 2:1:4-5.

[0036] The siloxane-modified epoxy resin of the present invention can improve the bonding strength of polyurethane, achieve long-term water immersion from its hydrophobic functional groups such as siloxane, effectively avoid hydrolysis or degradation when soaked in water, have excellent water resistance, and can meet the use requirements of water immersion environment. Silicon-containing compounds release highly active terminal hydroxyl groups when hydrolyzed, and the terminal hydroxyl groups themselves can condense to form a three-dimensional network elastomer, so that the polyurethane has high elasticity, low-temperature flexibility, aging resistance, and corrosion resistance; in addition, the siloxane, hydrocarbon group and other hydrophobic groups of the silane end-capping agent improve water immersion resistance.

[0037] A method for preparing a marine spray rigid polyurethane foam material comprises the following steps: preparing component A: adding polymer polyol, chain extender, flame retardant, foam stabilizer, catalyst and silane end-capping agent into a stirring kettle and stirring evenly; when in use, preparing component A and component B in a weight ratio of 1:1.1-1.2 and spraying through a high-pressure foaming machine.

[0038] The following is a detailed description through specific embodiments.

[0039] Example 1

[0040] A marine spray rigid foam polyurethane material consists of component A and component B, wherein component A comprises the following raw material components in parts by weight: 75.5 parts of polymer polyol, 2.4 parts of chain extender, 5 parts of flame retardant, 0.65 parts of foam stabilizer, 0.77 parts of catalyst, and 1.3 parts of silane end-capping agent, and component B is polyphenylmethane polyisocyanate.

[0041] The polymer polyol is composed of bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3, and the weight ratio of bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3 is 6.5:2:1:1.5. The bio-based polyol adopts FH-8450 bio-based polyol of Zhangjiagang Feihang Technology Co., Ltd., polyether polyol 1 is commercially available INOVOL R6001C, polyether polyol 2 is commercially available INOVOL R6205, both of which are products of Shandong Yinuowei New Materials Co., Ltd., and polyether polyol 3 is RAYNOL PS-3152 of Qingdao Ruinuo Chemical Co., Ltd.

[0042] The chain extender is glycerol. The flame retardant is a mixture of triethyl phosphate (TEP) and tri(2-chloropropyl) phosphate (TCPP), and the mass ratio of triethyl phosphate to tri(2-chloropropyl) phosphate is 1:1.5. The catalyst is 2-hydroxy-NNN-trimethyl-1-propylamine formate (TMR-2), CAS: 62314-25-4. The foam stabilizer is Evonik B8545. The polyphenylmethane polyisocyanate is Wanhua Chemical PM400.

[0043] The silane capping agent is a siloxane-modified epoxy resin, which is prepared by the following method: putting the epoxy resin (E44) into a reactor, adding a solvent of n-butanol, stirring until the epoxy resin is completely dissolved, controlling the temperature to 78°C, adding 3-isocyanatepropyltrimethoxysilane (CAS No. 15396-00-6), and stirring and reacting for 3 hours to obtain the obtained product; the weight ratio of the epoxy resin, 3-isocyanatepropyltrimethoxysilane, and n-butanol is 2:1:4.

[0044] Example 2

[0045] A marine spray rigid foam polyurethane material consists of component A and component B, wherein component A comprises the following raw material components in parts by weight: 60.5 parts of polymer polyol, 2 parts of chain extender, 4 parts of flame retardant, 0.51 parts of foam stabilizer, 0.6 parts of catalyst, and 1 part of silane end-capping agent, and component B is polyphenylmethane polyisocyanate.

[0046] The polymer polyol is composed of bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3, and the weight ratio of bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3 is 6:1.8:0.9:1.45. The bio-based polyol adopts FH-8450 bio-based polyol of Zhangjiagang Feihang Technology Co., Ltd., polyether polyol 1 is the commercially available brand INOVOL R6001C, polyether polyol 2 is the commercially available brand INOVOL R6205, both of which are products of Shandong Yinuowei New Materials Co., Ltd., and polyether polyol 3 is RAYNOL PS-3152 of Qingdao Ruinuo Chemical Co., Ltd.

[0047] The chain extender is dipropylene glycol. The flame retardant is a mixture of triethyl phosphate (TEP) and tri(2-chloropropyl) phosphate (TCPP), and the mass ratio of triethyl phosphate to tri(2-chloropropyl) phosphate is 1:1.5. The catalyst is potassium acetate. The foam stabilizer is Evonik B8545. The polyphenylmethane polyisocyanate is BASF M20S.

[0048] The silane capping agent is a siloxane-modified epoxy resin, which is prepared by the following method: putting the epoxy resin (E44) into a reactor, adding a solvent of n-butanol, stirring until the epoxy resin is completely dissolved, controlling the temperature to 75°C, adding 3-isocyanatepropyltrimethoxysilane (CAS No. 15396-00-6), and stirring and reacting for 2 hours to obtain the obtained product; the weight ratio of the epoxy resin, 3-isocyanatepropyltrimethoxysilane, and n-butanol is 2:1:4.

[0049] Example 3

[0050] A marine spray rigid foam polyurethane material consists of component A and component B. Component A comprises the following raw material components in parts by weight: 88 parts of polymer polyol, 3 parts of chain extender, 7 parts of flame retardant, 0.9 parts of foam stabilizer, 0.9 parts of catalyst, and 1.5 parts of silane end-capping agent; component B is polyphenylmethane polyisocyanate.

[0051] The polymer polyol is composed of bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3, and the weight ratio of bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3 is 7:2.1:1.2:1.55. The bio-based polyol adopts FH-8450 bio-based polyol of Zhangjiagang Feihang Technology Co., Ltd., polyether polyol 1 is commercially available INOVOL R6001C, polyether polyol 2 is commercially available INOVOL R6205, both of which are products of Shandong Yinuowei New Materials Co., Ltd., and polyether polyol 3 is RAYNOL PS-3152 of Qingdao Ruinuo Chemical Co., Ltd.

[0052] The chain extender is 1,3-butanediol. The flame retardant is a mixture of triethyl phosphate (TEP) and tri(2-chloropropyl) phosphate (TCPP), and the mass ratio of triethyl phosphate to tri(2-chloropropyl) phosphate is 1:1.5. The catalyst is 2-hydroxy-NNN-trimethyl-1-propylamine formate (TMR-2), CAS: 62314-25-4. The foam stabilizer is Evonik B8545. The polyphenylmethane polyisocyanate is Wanhua Chemical PM700.

[0053] The silane capping agent is a siloxane-modified epoxy resin, which is prepared by the following method: putting the epoxy resin (E44) into a reactor, adding a solvent of n-butanol, stirring until the epoxy resin is completely dissolved, controlling the temperature to 80°C, adding 3-isocyanatepropyltrimethoxysilane (CAS No. 15396-00-6), and stirring and reacting for 2 hours to obtain the obtained product; the weight ratio of the epoxy resin, 3-isocyanatepropyltrimethoxysilane, and n-butanol is 2:1:5.

[0054] Example 4

[0055] A marine spray rigid foam polyurethane material consists of component A and component B. Component A comprises the following raw material components in parts by weight: 70 parts of polymer polyol, 2.6 parts of chain extender, 6 parts of flame retardant, 0.8 parts of foam stabilizer, 0.8 parts of catalyst, and 1.4 parts of silane end-capping agent; component B is polyphenylmethane polyisocyanate.

[0056] The polymer polyol is composed of bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3, and the weight ratio of bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3 is 7:2.1:1.1:1.52. The bio-based polyol adopts the bio-based polyol FH-8450 of Zhangjiagang Feihang Technology Co., Ltd., the polyether polyol 1 is the commercially available brand INOVOL R6001C, and the polyether polyol 2 is the commercially available brand INOVOL R6205, both of which are products of Shandong Yinuowei New Materials Co., Ltd., and the polyether polyol 3 is RAYNOL PS-3152 of Qingdao Ruinuo Chemical Co., Ltd.

[0057] The chain extender is glycerol. The flame retardant is a mixture of triethyl phosphate (TEP) and tri(2-chloropropyl) phosphate (TCPP), and the mass ratio of triethyl phosphate to tri(2-chloropropyl) phosphate is 1:1.5. The catalyst is 2-hydroxy-NNN-trimethyl-1-propylamine formate (TMR-2), CAS: 62314-25-4. The foam stabilizer is Evonik B8545. The polyphenylmethane polyisocyanate is Wanhua Chemical PM700.

[0058] The silane capping agent is a siloxane-modified epoxy resin, which is prepared by the following method: putting the epoxy resin (E44) into a reactor, adding a solvent of n-butanol, stirring until the epoxy resin is completely dissolved, controlling the temperature to 80°C, adding 3-isocyanatepropyltrimethoxysilane (CAS No. 15396-00-6), and stirring and reacting for 2 hours to obtain the obtained product; the weight ratio of the epoxy resin, 3-isocyanatepropyltrimethoxysilane, and n-butanol is 2:1:5.

[0059] Example 5

[0060] A marine spray rigid foam polyurethane material consists of component A and component B. Component A comprises the following raw material components in parts by weight: 82 parts of polymer polyol, 2.8 parts of chain extender, 7 parts of flame retardant, 0.85 parts of foam stabilizer, 0.85 parts of catalyst, and 1.45 parts of silane end-capping agent; component B is polyphenylmethane polyisocyanate.

[0061] The polymer polyol is composed of bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3, and the weight ratio of bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3 is 7:2:1:1.5. The bio-based polyol adopts FH-8450 bio-based polyol of Zhangjiagang Feihang Technology Co., Ltd., polyether polyol 1 is commercially available INOVOL R6001C, polyether polyol 2 is commercially available INOVOL R6205, both of which are products of Shandong Yinuowei New Materials Co., Ltd., and polyether polyol 3 is RAYNOL PS-3152 of Qingdao Ruinuo Chemical Co., Ltd.

[0062] The chain extender is trimethylolpropane. The flame retardant is a mixture of triethyl phosphate (TEP) and tri(2-chloropropyl) phosphate (TCPP), and the mass ratio of triethyl phosphate to tri(2-chloropropyl) phosphate is 1:1.5. The catalyst is potassium acetate (KAc). The foam stabilizer is Evonik B8545. The polyphenylmethane polyisocyanate is BASF M20S.

[0063] The silane capping agent is a siloxane-modified epoxy resin, which is prepared by the following method: putting the epoxy resin (E44) into a reactor, adding a solvent of n-butanol, stirring until the epoxy resin is completely dissolved, controlling the temperature to 75°C, adding 3-isocyanatepropyltrimethoxysilane (CAS No. 15396-00-6), and stirring and reacting for 2 hours to obtain the obtained product; the weight ratio of the epoxy resin, 3-isocyanatepropyltrimethoxysilane, and n-butanol is 2:1:4.

[0064] Example 6

[0065] A marine spray rigid foam polyurethane material consists of component A and component B, wherein component A comprises the following raw material components in parts by weight: 85 parts of polymer polyol, 2.4 parts of chain extender, 5 parts of flame retardant, 0.65 parts of foam stabilizer, 0.75 parts of catalyst, and 1.35 parts of silane end-capping agent, and component B is polyphenylmethane polyisocyanate.

[0066] The polymer polyol is composed of bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3, and the weight ratio of bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3 is 6.5:2:1.1:1.5. The bio-based polyol adopts FH-8450 bio-based polyol of Zhangjiagang Feihang Technology Co., Ltd., polyether polyol 1 is commercially available INOVOL R6001C, polyether polyol 2 is commercially available INOVOL R6205, both of which are products of Shandong Yinuowei New Materials Co., Ltd., and polyether polyol 3 is RAYNOL PS-3152 of Qingdao Ruinuo Chemical Co., Ltd.

[0067] The chain extender is dipropylene glycol. The flame retardant is a mixture of triethyl phosphate (TEP) and tri(2-chloropropyl) phosphate (TCPP), and the mass ratio of triethyl phosphate to tri(2-chloropropyl) phosphate is 1:1.5. The catalyst is potassium acetate (KAc). The foam stabilizer is Evonik B8545. The polyphenylmethane polyisocyanate is BASF M20S.

[0068] The silane capping agent is a siloxane-modified epoxy resin, which is prepared by the following method: putting the epoxy resin (E44) into a reactor, adding a solvent of n-butanol, stirring until the epoxy resin is completely dissolved, controlling the temperature to 78°C, adding 3-isocyanatepropyltrimethoxysilane (CAS No. 15396-00-6), and stirring and reacting for 2 hours to obtain the obtained product; the weight ratio of the epoxy resin, 3-isocyanatepropyltrimethoxysilane, and n-butanol is 2:1:5.

[0069] Comparative Example 1

[0070] Compared with Example 1, the bio-based polyol in the polymer polyol was replaced by an equal amount of polyether polyol INOVOL R6207 from Shandong Yinuowei New Materials Co., Ltd., and the rest was the same as Example 1.

[0071] A marine spray rigid foam polyurethane material consists of component A and component B, wherein component A comprises the following raw material components in parts by weight: 75.5 parts of polymer polyol, 2.4 parts of chain extender, 5 parts of flame retardant, 0.65 parts of foam stabilizer, 0.77 parts of catalyst, and 1.3 parts of silane end-capping agent, and component B is polyphenylmethane polyisocyanate.

[0072] The polymer polyol is composed of INOVOL R6207, polyether polyol 1, polyether polyol 2 and polyether polyol 3, and the weight ratio of INOVOL R6207, polyether polyol 1, polyether polyol 2 and polyether polyol 3 is 6.5:2:1:1.5. Polyether polyol 1 is the commercially available brand INOVOL R6001C, polyether polyol 2 is the commercially available brand INOVOLR6205, both of which are products of Shandong INOVOL New Materials Co., Ltd., and polyether polyol 3 is RAYNOL PS-3152 of Qingdao Ruinuo Chemical Co., Ltd.

[0073] The chain extender is glycerol. The flame retardant is a mixture of triethyl phosphate (TEP) and tri(2-chloropropyl) phosphate (TCPP), and the mass ratio of triethyl phosphate to tri(2-chloropropyl) phosphate is 1:1.5. The catalyst is 2-hydroxy-NNN-trimethyl-1-propylamine formate (TMR-2), CAS: 62314-25-4. The foam stabilizer is Evonik B8545. The polyphenylmethane polyisocyanate is Wanhua Chemical PM400.

[0074] The silane capping agent is a siloxane-modified epoxy resin, which is prepared by the following method: putting the epoxy resin (E44) into a reactor, adding a solvent of n-butanol, stirring until the epoxy resin is completely dissolved, controlling the temperature to 78°C, adding 3-isocyanatepropyltrimethoxysilane (CAS No. 15396-00-6), and stirring and reacting for 3 hours to obtain the obtained product; the weight ratio of the epoxy resin, 3-isocyanatepropyltrimethoxysilane, and n-butanol is 2:1:4.

[0075] Comparative Example 2

[0076] Compared with Example 1, the flame retardant used is tris(2-chloroisopropyl) phosphate flame retardant TCPP, which comes from Zhangjiagang Feihang Technology Co., Ltd., and the rest is the same as Example 1.

[0077] A marine spray rigid foam polyurethane material consists of component A and component B, wherein component A comprises the following raw material components in parts by weight: 75.5 parts of polymer polyol, 2.4 parts of chain extender, 5 parts of flame retardant, 0.65 parts of foam stabilizer, 0.77 parts of catalyst, and 1.3 parts of silane end-capping agent, and component B is polyphenylmethane polyisocyanate.

[0078] The polymer polyol is composed of bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3, and the weight ratio of bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3 is 6.5:2:1:1.5. The bio-based polyol adopts FH-8450 bio-based polyol of Zhangjiagang Feihang Technology Co., Ltd., polyether polyol 1 is commercially available INOVOL R6001C, polyether polyol 2 is commercially available INOVOL R6205, both of which are products of Shandong Yinuowei New Materials Co., Ltd., and polyether polyol 3 is RAYNOL PS-3152 of Qingdao Ruinuo Chemical Co., Ltd.

[0079] The chain extender is glycerol. The flame retardant is tris(2-chloroisopropyl) phosphate flame retardant TCPP, Zhangjiagang Feihang Technology Co., Ltd. The catalyst is 2-hydroxy-NNN-trimethyl-1-propylamine formate (TMR-2), CAS: 62314-25-4. The foam stabilizer is Evonik B8545. The polyphenylmethane polyisocyanate is Wanhua Chemical PM400.

[0080] The silane capping agent is a siloxane-modified epoxy resin, which is prepared by the following method: putting the epoxy resin (E44) into a reactor, adding a solvent of n-butanol, stirring until the epoxy resin is completely dissolved, controlling the temperature to 78°C, adding 3-isocyanatepropyltrimethoxysilane (CAS No. 15396-00-6), and stirring and reacting for 3 hours to obtain the obtained product; the weight ratio of the epoxy resin, 3-isocyanatepropyltrimethoxysilane, and n-butanol is 2:1:4.

[0081] Comparative Example 3

[0082] Compared with Example 1, no silane capping agent is added, and the rest is the same as Example 1.

[0083] A marine spray rigid foam polyurethane material consists of component A and component B, wherein component A comprises the following raw material components in parts by weight: 75.5 parts of polymer polyol, 2.4 parts of chain extender, 5 parts of flame retardant, 0.65 parts of foam stabilizer, and 0.77 parts of catalyst, and component B is polyphenylmethane polyisocyanate.

[0084] The polymer polyol is composed of bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3, and the weight ratio of bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3 is 6.5:2:1:1.5. The bio-based polyol adopts FH-8450 bio-based polyol of Zhangjiagang Feihang Technology Co., Ltd., polyether polyol 1 is commercially available INOVOL R6001C, polyether polyol 2 is commercially available INOVOL R6205, both of which are products of Shandong Yinuowei New Materials Co., Ltd., and polyether polyol 3 is RAYNOL PS-3152 of Qingdao Ruinuo Chemical Co., Ltd.

[0085] The chain extender is glycerol. The flame retardant is tris(2-chloroisopropyl) phosphate flame retardant TCPP, Zhangjiagang Feihang Technology Co., Ltd. The catalyst is 2-hydroxy-NNN-trimethyl-1-propylamine formate (TMR-2), CAS: 62314-25-4. The foam stabilizer is Evonik B8545. The polyphenylmethane polyisocyanate is Wanhua Chemical PM400.

[0086]

Performance test

[0087] According to the formula of the embodiment and the comparative example, each raw material is added into a stirring kettle and stirred evenly to prepare component A. When in use, component A and component B are prepared in a weight ratio of 1:1.05 and sprayed by a high-pressure sprayer. After spraying, the rigid foam polyurethane material is rapidly foamed.

[0088] The prepared rigid polyurethane foam material was cut and sampled, and performance tests were carried out with reference to GB 8624-2012 "Classification of Combustion Performance of Building Materials and Products" and "Technical Specification for Thermal Insulation and Waterproof Engineering of Rigid Polyurethane Foam" GB 50404-2017. The results are shown in Table 1.

[0089] Table 1 Test results

[0090]

[0091]

[0092] 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 marine spray rigid foam polyurethane material, consisting of component A and component B, characterized in that: The component A comprises the following raw material components in parts by weight: 60-88 parts of polymer polyol, 2-3 parts of chain extender, 4-7 parts of flame retardant, 0.5-0.9 parts of foam stabilizer, 0.6-0.9 parts of catalyst, and 1-1.5 parts of silane end-capping agent; The component B is polyphenylmethane polyisocyanate.

2. A marine spray rigid polyurethane foam material according to claim 1, characterized in that: The polymer polyol is composed of bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3, and the weight ratio of the bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3 is 6-7: 1.8-2.1：0.9-1.2：1.45-1.55。 3. A marine spray rigid foam polyurethane material according to claim 2, characterized in that: The weight ratio of the bio-based polyol, polyether polyol 1, polyether polyol 2 and polyether polyol 3 is 6.5:2:1:1.

5.

4. A marine spray rigid polyurethane foam material according to claim 3, characterized in that: The bio-based polyol is a bio-based polyol having a functionality of 7.5-9.5 and a hydroxyl value of 390-450 mgKOH / g; The polyether polyol 1 is a polyether polyol having a functionality of 4.6-4.8 and a hydroxyl value of 392-420 mgKOH / g; The polyether polyol II is a polyether polyol having a functionality of 4.0-4.2 and a hydroxyl value of 370-390 mgKOH / g; The polyether polyol tris is a phthalic anhydride polyester polyol with a hydroxyl value of 310-330 mgKOH / g.

5. The marine spray rigid polyurethane foam material according to claim 1, characterized in that: The chain extender is at least one of glycerol, dipropylene glycol, 1,3-butylene glycol and trimethylolpropane.

6. A marine spray rigid polyurethane foam material according to claim 1, characterized in that: The flame retardant is a mixture of triethyl phosphate (TEP) and tri(2-chloropropyl) phosphate (TCPP), and the mass ratio of triethyl phosphate to tri(2-chloropropyl) phosphate is 1:1.

5.

7. The marine spray rigid polyurethane foam material according to claim 1, characterized in that: The catalyst is 2-hydroxy-NNN-trimethyl-1-propylamine formate (TMR-2) or potassium acetate (KAc); The foam stabilizer is Evonik B8545.

8. The marine spray rigid polyurethane foam material 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.

9. The marine spray rigid polyurethane foam material according to claim 1, characterized in that: The silane capping agent is a siloxane-modified epoxy resin, which is prepared by the following method: Put the epoxy resin (E44) into the reactor, add the solvent n-butanol, stir until the epoxy resin is completely dissolved, control the temperature to 75-80°C, add 3-isocyanatepropyltrimethoxysilane (CAS No. 15396-00-6), stir and react for 2-3 hours to obtain; The weight ratio of the epoxy resin, 3-isocyanate propyltrimethoxysilane and n-butanol is 2:1:4-5.

10. The method for preparing a marine spray rigid polyurethane foam material according to claim 1, characterized in that: The following steps are involved: Preparation of component A: Add polymer polyol, chain extender, flame retardant, foam stabilizer, catalyst, and silane end-capping agent into a stirred tank and stir evenly; When in use, component A and component B are prepared in a weight ratio of 1:1.1-1.2 and sprayed using a high-pressure foaming machine.

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