A spray polyurethane foam composition and its use

Abstract

The application belongs to the field of chemical materials and its production technology, and particularly relates to a spraying type polyurethane hard foam composition and application thereof. The spraying type polyurethane hard foam composition is composed of A material and B material, and the A material and the B material are independently packaged; the A material comprises the following components in parts by weight: plant oil polyol 100 parts; ionic liquid catalyst 0.1-1 parts; foaming agent 1-5 parts; foam stabilizer 1-3 parts; flame retardant 10-20 parts; and the B material is polymeric MDI. The plant oil polyol with a specific hydroxyl value is used as a raw material, the prepared bio-based polyurethane hard foam has good bonding performance and mechanical properties, and meanwhile, has good heat preservation and water insulation effect. The spraying type bio-based polyurethane hard foam prepared by using a new compound and catalytic system has a short reaction time, and can be cured to obtain the spraying type polyurethane hard foam within 2 minutes after spraying and foaming, so that the requirement of on-site construction can be met.

Description

Technical Field

[0001] This invention belongs to the field of chemical materials and their production technology, specifically relating to a sprayable polyurethane rigid foam composition and its application. Background Technology

[0002] Polyurethane is a polymer with repeating urethane segments, produced by the reaction of isocyanates and polyols. Polyurethane products are broadly classified into foamed and non-foamed products. Foamed products include flexible, rigid, and semi-rigid polyurethane foams; non-foamed products include coatings, adhesives, synthetic leather, elastomers, and elastic fibers. Rigid polyurethane foam is an important functional material, widely used in building insulation, pipe insulation, appliance insulation, interior decoration, lightweight building materials, automobile manufacturing, and electronic component manufacturing due to its excellent thermal insulation, good adhesion, high specific strength, and outstanding durability.

[0003] The requirements for thermal insulation and water resistance in railway tunnels are extremely complex and of great significance to my country's railway construction. For example, on the Sichuan-Tibet Railway, in the 1100-kilometer section from Lhasa to Nyingchi alone, the bridge-to-tunnel ratio exceeds 80%, equivalent to digging a tunnel from Beijing to Nanjing. Moreover, all of this is done by excavating through mountains, where the pressure from the mountains creates a large temperature difference between the tunnel interior and the surrounding landscape, often reaching 70 degrees Celsius or even higher, necessitating high thermal insulation performance. Simultaneously, the mountains are prone to water seepage and are alkaline, requiring high water resistance and weather resistance. Furthermore, the complex substrate in the construction environment demands high bonding strength from rigid foam. Additionally, the tunnel's vibration environment and long service life require materials with good seismic resistance and stability. Finally, the remote geographical location and inconvenient transportation of the tunnels, coupled with the limited internal space, necessitate convenient material storage, transportation, and construction, ideally allowing for on-site spraying and forming.

[0004] Traditional polyurethanes prepared from petrochemical polyols typically exhibit low adhesion, making them unsuitable for the complex substrate environment of tunnels. Furthermore, they can create voids, impacting the thermal and waterproof performance of rigid foam. In contrast, plant-based polyols can enhance product performance by introducing specific functional groups. For example, introducing polyhydroxyl groups can create a cross-linked structure, improving material stability and weather resistance, increasing closed-cell ratio, and optimizing thermal and waterproof performance; while suspension chains can enhance damping properties and optimize seismic resistance. However, current formulations and catalytic systems for spray-applied polyurethanes are designed for petrochemical polyols and are not suitable for plant-based polyols. Therefore, there is an urgent need to develop compound systems suitable for plant-based polyols, enabling rapid reactions to meet on-site construction requirements. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to address the shortcomings of the prior art by providing a sprayable rigid polyurethane foam, its preparation method and application.

[0006] Invention concept: In order to ensure that the sprayable bio-based rigid foam can meet the thermal insulation and waterproofing requirements of railway tunnels while having excellent mechanical properties, a formula suitable for plant oil polyols was developed, which enables polyurethane to react, foam and harden quickly, meet the requirements of on-site construction, and at the same time have excellent thermal insulation, waterproofing and mechanical properties.

[0007] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows:

[0008] This invention discloses a sprayable polyurethane rigid foam composition, which is composed of component A and component B, and component A and component B are packaged separately.

[0009] Material A comprises the following components in parts by weight:

[0010] 100 parts of vegetable oil polyols;

[0011] 0.1 to 1 part of ionic liquid catalyst;

[0012] 1-5 parts of foaming agent;

[0013] 1-3 parts foam stabilizer;

[0014] 10-20 parts flame retardant;

[0015] Material B is polymeric MDI;

[0016] Preferably, material A comprises the following components in parts by weight:

[0017] 100 parts of vegetable oil polyols;

[0018] 0.2–0.6 parts of ionic liquid catalyst;

[0019] 3 parts foaming agent;

[0020] 2 parts foam stabilizer;

[0021] 15 parts flame retardant;

[0022] Material B is polymeric MDI;

[0023] Material A contains neither crosslinking agent nor water; material B contains neither crosslinking agent nor water.

[0024] Among the crosslinking agents commonly used in this technical field are glycerol, trimethylolpropane, pentaerythritol, and diethanolamine.

[0025] In some embodiments, the vegetable oil polyol is any one or a combination of several of olive oil polyol, peanut oil polyol, rapeseed oil polyol, cottonseed oil polyol, soybean oil polyol, coconut oil polyol, palm oil polyol, sesame oil polyol, corn oil polyol, and sunflower seed oil polyol, preferably soybean oil polyol; the vegetable oil polyol has a hydroxyl value of 300-500 mg KOH / g.

[0026] The plant oil polyol is prepared according to existing technology (Chinese patent application number 201310247746.8).

[0027] In some embodiments, the ionic liquid catalyst is a pyridine-type ionic liquid catalyst, an imidazole-type ionic liquid catalyst, or a long-chain aliphatic amine-type ionic liquid catalyst; the anion of the ionic liquid catalyst is a Brønsted base; the Brønsted base is dicyandiamide, hexafluorophosphate, boron tetrafluoride, or bis(trifluoromethanesulfonyl)imide, preferably dicyandiamide; the cation of the ionic liquid catalyst is preferably any one of the cations shown in the following structures:

[0028]

[0029] Further preferred

[0030] In some embodiments, the foaming agent is any one or a combination of two of physical foaming agents and chemical foaming agents; preferably, the foaming agent is a physical foaming agent; more preferably, the foaming agent is dichlorofluoroethane, trichlorofluoromethane, or trichlorotrifluoroethane; even more preferably, the foaming agent is dichlorofluoroethane.

[0031] In some embodiments, the foam stabilizer is an organosilicon foam stabilizer; preferably, the foam stabilizer is polyurethane rigid foam silicone oil AK-158, AK-8805 polyurethane foam stabilizer, or Demei Shichuang silicone oil AK8803; more preferably, the foam stabilizer is Demei Shichuang silicone oil AK8803.

[0032] In some embodiments, the flame retardant is any one or a combination of several of the following: tributyl phosphate, tris(2-ethylhexyl) phosphate, tris(2-chloroethyl) phosphate, tris(2,3-dichloropropyl) phosphate, tris(2,3-dibromopropyl) phosphate, Pyrol99, toluene-diphenyl phosphate, tricresyl phosphate, triphenyl phosphate, (2-ethylhexyl)-diphenyl phosphate, bis(4-hydroxyphenyl)phenylphosphine oxide, and casein; preferably, the flame retardant is Pyrol99.

[0033] In some embodiments, the -NCO content in the polymeric MDI is 30-35 wt%.

[0034] The application of the above-mentioned sprayable rigid polyurethane foam composition in the preparation of sprayable rigid polyurethane foam is also within the scope of protection of this invention.

[0035] Specifically, component A and component B are added to the mixing chamber of the spraying machine and stirred at 50-80°C and 200-300 rpm. After mixing, the mixture is sprayed and foamed, and cured within 2 minutes to obtain sprayed polyurethane rigid foam.

[0036] Specifically, preferably, material A and material B are added to the mixing chamber of the spraying machine and stirred at 60-70°C and 200-300 rpm. After mixing, the mixture is sprayed and foamed, and cured within 2 minutes after spraying to obtain sprayed polyurethane rigid foam.

[0037] Specifically, the molar ratio of the hydroxyl groups in the vegetable oil polyol in material A to the -NCO in the polymeric MDI in material B is 1:1.1 to 1.3, preferably 1:1.2.

[0038] The application of the above-mentioned sprayable polyurethane rigid foam composition in the preparation of tunnel insulation materials is also within the scope of protection of this invention.

[0039] Beneficial effects:

[0040] This invention uses plant oil polyols with specific hydroxyl values ​​as raw materials to prepare bio-based rigid polyurethane foam with good adhesion and mechanical properties, as well as excellent thermal insulation and waterproofing. Employing a novel compounding and catalytic system, the resulting spray-applied bio-based rigid polyurethane foam exhibits a short reaction time, curing within 2 minutes after spraying and foaming, thus meeting the requirements of on-site construction. Detailed Implementation

[0041] The present invention can be better understood from the following embodiments. However, those skilled in the art will readily understand that the descriptions in the embodiments are for illustrative purposes only and should not, and will not, limit the invention as detailed in the claims.

[0042] The vegetable oil polyols used in this embodiment were prepared according to existing technology (Chinese patent application number 201310247746.8).

[0043] The polymeric MDI used in the embodiments of this invention was purchased from Yantai Wanhua Polyurethane Co., Ltd.

[0044] The relevant determination methods for the prepared vegetable oil polyols and polyurethane materials of this invention are as follows:

[0045] (1) The closed-cell rate was determined according to GB / T 10799-2008.

[0046] (2) The compressive strength was determined according to GB / T 8813-2008.

[0047] (3) The oxygen index was determined according to GB / T 2406-1993.

[0048] (4) The combustion test of the monomer was determined according to GB / T 20284-2006.

[0049] (5) Determine the combustion performance according to GB 8624-2012.

[0050] (6) The combustion behavior was determined according to GB / T 2406.2-2009.

[0051] (7) Flammability test according to GB / T 8626-2007.

[0052] (8) The bond strength, tensile strength and impermeability of sprayed rigid polyurethane were determined according to GB 50404-2017.

[0053] (9) The thermal insulation performance of sprayed rigid polyurethane was determined according to GB / T 10294-2008.

[0054] Example 1

[0055] 100g of soybean oil polyol (hydroxyl value 312mg KOH / g) was mixed evenly with 0.5g of imidazole-type ionic liquid catalyst (anion is dicyandiamide, cationic is CB-5), 3g of foaming agent monofluorodichloroethane, 2g of foam stabilizer Demeishichuang silicone oil AK8803, and 15g of flame retardant Pyrol99 to form component A; component B consisted of 88g of polymeric MDI with a -NCO content of 32wt%. Components A and B were added to the mixing chamber of a spraying machine and stirred at 60-70℃ and 200-300rpm. After mixing, the mixture was sprayed onto the board for on-site foaming. After curing, spray-applied rigid polyurethane foam was obtained.

[0056] Example 2

[0057] 100g of soybean oil polyol (hydroxyl value 383mg KOH / g) was mixed evenly with 0.5g of imidazole-type ionic liquid catalyst (anion is dicyandiamide, cationic is CB-5), 3g of foaming agent monofluorodichloroethane, 2g of foam stabilizer Demeishichuang silicone oil AK8803, and 15g of flame retardant Pyrol99 to form component A; component B consisted of 108g of polymeric MDI with a -NCO content of 32wt%. Components A and B were added to the mixing chamber of a spraying machine and stirred at 60-70℃ and 200-300rpm. After mixing, the mixture was sprayed onto the board for on-site foaming. After curing, spray-applied rigid polyurethane foam was obtained.

[0058] Example 3

[0059] 100g of soybean oil polyol (hydroxyl value 427mg KOH / g) was mixed evenly with 0.5g of imidazole-type ionic liquid catalyst (anion is dicyandiamide, cationic is CB-5), 3g of foaming agent monofluorodichloroethane, 2g of foam stabilizer Demeishichuang silicone oil AK8803, and 15g of flame retardant Pyrol99 to form component A; component B was 120g of polymeric MDI with a -NCO content of 32wt%. Components A and B were added to the mixing chamber of a spraying machine and stirred at 60-70℃ and 200-300rpm. After mixing, the mixture was sprayed onto the board for on-site foaming. After curing, spray-applied rigid polyurethane foam was obtained.

[0060] Example 4

[0061] 100g of soybean oil polyol (hydroxyl value 489mg KOH / g) was mixed evenly with 0.5g of imidazole-type ionic liquid catalyst (anion is dicyandiamide, cationic is CB-5), 3g of foaming agent monofluorodichloroethane, 2g of foam stabilizer Demeishichuang silicone oil AK8803, and 15g of flame retardant Pyrol99 to form component A; component B consisted of 137g of polymeric MDI with a -NCO content of 32wt%. Components A and B were added to the mixing chamber of a spraying machine and stirred at 60-70℃ and 200-300rpm. After mixing, the mixture was sprayed onto the board for on-site foaming. After curing, spray-applied rigid polyurethane foam was obtained.

[0062] Comparative Example 1

[0063] 100g of soybean oil polyol (hydroxyl value 312mg KOH / g) was mixed evenly with 0.5g of imidazole-type ionic liquid catalyst (anion is dicyandiamide, cationic is CB-5), 3g of foaming agent monofluorodichloroethane, 2g of foam stabilizer Demeishichuang silicone oil AK8803, and 15g of flame retardant Pyrol99 to form component A; component B was 80g of polymeric MDI with a -NCO content of 32wt%. Components A and B were added to the mixing chamber of a spraying machine and stirred at 60-70℃ and 200-300rpm. After mixing, the mixture was sprayed onto the board for on-site foaming. After curing, spray-applied rigid polyurethane foam was obtained.

[0064] Comparative Example 2

[0065] 100g of soybean oil polyol (hydroxyl value 383mg KOH / g) was mixed evenly with 0.5g of imidazole-type ionic liquid catalyst (anion is dicyandiamide, cationic is CB-5), 3g of foaming agent monofluorodichloroethane, 2g of foam stabilizer Demeishichuang silicone oil AK8803, and 15g of flame retardant Pyrol99 to form component A; component B consisted of 134g of polymeric MDI with a -NCO content of 32wt%. Components A and B were added to the mixing chamber of a spraying machine and stirred at 60-70℃ and 200-300rpm. After mixing, the mixture was sprayed onto the board for on-site foaming. After curing, spray-applied rigid polyurethane foam was obtained.

[0066] Comparative Example 3

[0067] 100g of soybean oil polyol (hydroxyl value 427mg KOH / g) was mixed evenly with 0.5g of imidazole-type ionic liquid catalyst (anion is dicyandiamide, cationic is CB-5), 3g of foaming agent monofluorodichloroethane, 2g of foam stabilizer Demeishichuang silicone oil AK8803, and 5g of flame retardant Pyrol99 to form component A; component B was 120g of polymeric MDI with a -NCO content of 32wt%. Components A and B were added to the mixing chamber of a spraying machine and stirred at 60-70℃ and 200-300rpm. After mixing, the mixture was sprayed onto the board for on-site foaming. After curing, spray-applied rigid polyurethane foam was obtained.

[0068] Comparative Example 4

[0069] 100g of soybean oil polyol (hydroxyl value 489mg KOH / g) was mixed evenly with 0.5g of imidazole-type ionic liquid catalyst (anion is dicyandiamide, cationic is CB-5), 3g of foaming agent monofluorodichloroethane, 2g of foam stabilizer Demeishichuang silicone oil AK8803, and 30g of flame retardant Pyrol99 to form component A; component B was 137g of polymeric MDI with a -NCO content of 32wt%. Components A and B were added to the mixing chamber of a spraying machine and stirred at 60-70℃ and 200-300rpm. After mixing, the mixture was sprayed onto the board for on-site foaming. After curing, spray-applied rigid polyurethane foam was obtained.

[0070] Comparative Example 5

[0071] 100g of soybean oil polyol (hydroxyl value 383mg KOH / g) was mixed evenly with 0.5g of triethylamine, 3g of foaming agent monofluorodichloroethane, 2g of foam stabilizer Demeishichuang silicone oil AK8803, and 15g of flame retardant Pyrol99 to form component A; component B consisted of 108g of polymeric MDI with a -NCO content of 32wt%. Components A and B were added to the mixing chamber of a spraying machine and stirred at 60-70℃ and 200-300rpm. After mixing, the mixture was sprayed onto the board for on-site foaming. After curing, spray-applied rigid polyurethane foam was obtained.

[0072] Example 5: Performance Characterization of Vegetable Oil-Based Spray-Applied Rigid Polyurethane Foam

[0073] The performance indicators of the vegetable oil-based sprayable polyurethane rigid foams prepared in Examples 1-4 and Comparative Examples 1-5 are shown in Table 1.

[0074] Table 1 Performance indicators of spray-applied polyurethane rigid foams prepared in Examples 1-4 and Comparative Examples 1-5

[0075]

[0076]

[0077] Table 1 shows that during the preparation of spray-coated rigid polyurethane foam, (1) adding too much flame retardant will result in insufficient mechanical properties of the spray-coated rigid polyurethane foam (Example 4 vs Comparative Example 4); (2) adding too little flame retardant will result in poor flame retardant effect of the spray-coated rigid polyurethane foam (Example 3 vs Comparative Example 3); (3) the ratio of component A to component B will affect the mechanical properties of the rigid foam (Example 1 vs Comparative Example 1, Example 2 vs Comparative Example 2); (4) the type of catalyst will affect the reaction time and the performance of the generated rigid foam (Example 2 vs Comparative Example 5).

[0078] This invention provides a sprayable polyurethane rigid foam composition and its application, along with a method and approach. Many methods and approaches exist for implementing this technical solution; the above description is merely a preferred embodiment of the invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of this invention, and these improvements and modifications should also be considered within the scope of protection of this invention. All components not explicitly stated in this embodiment can be implemented using existing technologies.

Claims

1. A sprayable polyurethane rigid foam composition, characterized in that, The spray-applied rigid polyurethane foam composition consists of component A and component B, which are packaged separately. Material A comprises the following components in parts by weight: 100 parts of vegetable oil polyols; 0.1 to 1 part of ionic liquid catalyst; 1-5 parts of foaming agent; 1-3 parts foam stabilizer; 10-20 parts flame retardant; Material B is polymeric MDI; Wherein, material A does not contain crosslinking agent and water; material B does not contain crosslinking agent and water; The plant oil polyol has a hydroxyl value of 300~500 mg KOH / g; The ionic liquid catalyst is an imidazole-type ionic liquid catalyst; the cation of the ionic liquid catalyst is... The anion of the ionic liquid catalyst is dicyandiamide. The flame retardant is Pyrol99; The -NCO content in the polymeric MDI is 30~35 wt%; The molar ratio of the hydroxyl groups in the vegetable oil polyol in component A to the -NCO in the polymeric MDI in component B is 1:1.

2.

2. The sprayable rigid polyurethane foam composition according to claim 1, characterized in that, Material A comprises the following components in parts by weight: 100 parts of vegetable oil polyols; 0.2~0.6 parts of ionic liquid catalyst; 3 parts foaming agent; 2 parts foam stabilizer; 15 parts flame retardant; Material B is polymeric MDI; Material A contains neither crosslinking agent nor water; material B contains neither crosslinking agent nor water.

3. The sprayable rigid polyurethane foam composition according to claim 1 or 2, characterized in that, The plant oil polyols are any one or a combination of several of the following: olive oil polyols, peanut oil polyols, rapeseed oil polyols, cottonseed oil polyols, soybean oil polyols, coconut oil polyols, palm oil polyols, sesame oil polyols, corn oil polyols, and sunflower seed oil polyols.

4. The sprayable rigid polyurethane foam composition according to claim 1 or 2, characterized in that, The plant oil polyol is soybean oil polyol.

5. The sprayable rigid polyurethane foam composition according to claim 1 or 2, characterized in that, The foaming agent is any one or a combination of two of physical foaming agents and chemical foaming agents; the foam stabilizer is an organosilicon foam stabilizer.

6. The use of the sprayable polyurethane rigid foam composition according to any one of claims 1 to 5 in the preparation of sprayable polyurethane rigid foam.

7. The application according to claim 6, characterized in that, Add component A and component B to the mixing chamber of the spraying machine, and spray at 50-80°C. o C. Stir at a speed of 200~300 rpm, mix and then spray to foam. After spraying, cure within 2 minutes to obtain spray-applied rigid polyurethane foam.

8. The use of the sprayable polyurethane rigid foam composition according to any one of claims 1 to 5 in the preparation of tunnel insulation materials.

Images