Polyurethane spraying foam material as well as preparation method and application thereof

Abstract

The invention discloses a polyurethane spraying foam material as well as a preparation method and application thereof. The polyurethane spraying foam material comprises a component A and a component B in a ratio of 1: (1-1.03), the component A comprises 45-50 parts of flame-retardant polyester polyol, 6-8 parts of high-functionality polyether polyol, 20-25 parts of a flame retardant, 0.5-1.5 parts of a foam stabilizer, 4-6 parts of a catalyst, 15-17 parts of a physical foaming agent, 0.2-0.3 part of color paste and 0.1-0.3 part of water; and the component B comprises polymethyl polyphenyl polyisocyanate and modified isocyanate in a weight ratio of (8-9): 1. The flame-retardant polyester polyol is combined with the flame retardant, so that the flame-retardant property is enhanced, and the flame-retardant grade reaches B1 grade; the high-functionality polyether polyol, the washing flame retardant, the low-odor catalyst, the reaction type catalyst and the foaming agent are matched, so that the odor is less than 3.0, the uniformity and compactness of the flame-retardant covering layer are promoted, and the flame-retardant effect is further improved; the density is 45-55kg / m < 3 >, the heat conductivity is less than 0.023 W / mK at 25 DEG C, the heat insulation effect is good, the compression strength is more than 260kPa, the dimensional stability is less than 1% at-20 DEG C / 80 DEG C, the toughness is high, and the impact resistance is good.

Description

Technical Field

[0001] The invention relates to a polyurethane material, in particular to a polyurethane spray foam material and a preparation method and application thereof. Background Art

[0002] Polyurethane rigid foam is a synthetic material with thermal insulation and waterproof functions. It has extremely low thermal conductivity, good sound insulation and air insulation, excellent adhesion, waterproof and moisture-proof and durability. It is widely used in thermal insulation, refrigeration and freezing equipment, wall or pipe insulation, tank insulation and other fields. However, polyurethane rigid foam itself is a polymer flammable material. As an indispensable building decoration material, it is widely used. In some major fire accident investigations, polyurethane foam has played a role in fueling the occurrence and development of fires. Once it encounters a spark, the fire spreads rapidly and causes irreparable casualties. Compared with similar products, polyurethane foam has excellent and irreplaceable performance. It is impossible to completely avoid its application in related industries. It can only prevent safety accidents by improving its performance and strengthening the use specifications. By adding flame retardants, polyurethane foam can reduce its flammability and become a flame-retardant self-extinguishing material. With the continuous development of the construction industry and the increasing living standards, people have higher and higher requirements for the safety, comfort and health of the living environment. The flame retardant properties of existing polyurethane rigid foam plastics are average, and they cannot effectively prevent the spread of fire in the face of large fire attacks. At the same time, polyurethane spray products have a strong odor. During the construction process, use or living process, toxic and harmful gases are volatilized for a long time and in large quantities, causing serious damage to people's respiratory and nervous systems. Every year, the number of cases caused by the use of unqualified building materials increases year by year. These problems have seriously affected the healthy development of polyurethane rigid foam plastics in the construction industry and threatened people's life and property safety. Summary of the invention

[0003] Purpose of the invention: The purpose of the present invention is to improve the flame retardant properties of polyurethane spray foam and reduce the volatilization of toxic and harmful gases, and to provide a polyurethane spray foam material; another purpose of the present invention is to provide a method for preparing the material; another purpose of the present invention is to provide the application of the material in polyurethane rigid foam materials.

[0004] Technical solution: The polyurethane spray foam material of the present invention is composed of component A and component B in a weight ratio of 1:1 to 1.03, measured in parts by weight; the component A comprises: 45 to 50 parts of flame retardant polyester polyol, 6 to 8 parts of high-functional polyether polyol, 20 to 25 parts of flame retardant, 0.5 to 1.5 parts of foam stabilizer, 4 to 6 parts of catalyst, 15 to 17 parts of physical foaming agent, 0.2 to 0.3 parts of color paste and 0.1 to 0.3 parts of water; the component B comprises polymethyl polyphenyl polyisocyanate and modified isocyanate, and the weight ratio thereof is 8 to 9:1.

[0005] Furthermore, the flame retardant polyester polyol has an average molecular weight of 600-700, a hydroxyl value of 200-250 mgKON / g, a functionality of 3, and is selected from HF-8730. The high-functional polyether polyol is a polyether polyol with ethylenediamine or toluene diamine as an initiator, with a molecular weight of 500-750, a hydroxyl value of 500-750 mgKOH / g, a functionality of 4, and is selected from at least one of NJ-403 or TD405. The flame retardant polyester polyol introduces flame retardant elements into the molecular structure containing a relatively high benzene ring, which can greatly improve the flame retardant properties of the foam and improve the high temperature resistance of the foam. It is then combined with the polyether polyol to participate in the chemical reaction during the foam generation process, link to the foam material, form a permanent flame retardant effect, and can significantly reduce the amount of flame retardant.

[0006] Furthermore, the flame retardant is a phosphate flame retardant, selected from at least one of water-washed tris(chloropropyl) phosphate TCPP, tris(2-chloroethyl) phosphate TCEP, and tris(dichloropropyl) phosphate TDCPP. Compared with the volatility, irritation and toxicity of non-water-washed flame retardants, water-washed flame retardants are selected to reduce the volatile odor of the foam material. When the three flame retardants encounter high temperatures, they will release non-combustible gases to dilute the combustible gases and prevent further development of combustion. Among them, water-washed tris(chloropropyl) phosphate TCPP and tris(dichloropropyl) phosphate TDCPP have high flame retardant properties and good volatility, good oil resistance and hydrolysis resistance, and are more likely to form glass or foam when heated and mixed with other components to make the mixture more uniform, and form a uniform covering layer when encountering high temperatures to prevent flame retardancy. Tris(2-chloroethyl)phosphate TCEP has good water solubility, reduces the surface tension of other components and the viscosity of the system, and makes it easier to evenly mix glassy or foamy water-washed tris(chloropropyl)phosphate TCPP and tris(dichloropropyl)phosphate TDCPP into the foam material when mixed with other components, further promoting the uniformity of the flame retardant layer when encountering high temperature, thereby further improving the flame retardant effect and ensuring that the polyurethane foam has excellent atomization performance. At the same time, the three flame retardants can improve the flexibility of polyurethane foam materials and improve their impact strength.

[0007] Further, the foam stabilizer is a non-hydrolyzable silicon surfactant or a polysiloxane surfactant, selected from at least one of L6900, B8545, or DC193. Silicon surfactants have good interfacial activity and emulsification properties, low surface tension, and good permeability, and can penetrate deeper into other components more quickly, promoting the glassy or foamy form of water-washed tris(chloropropyl) phosphate TCPP and tris(dichloropropyl) phosphate TDCPP formed by component A when mixed at high temperatures to be more stable, and promoting its rapid mixing into the depth of the polyurethane foam material. When the flame retardant in the finished product after the polyurethane foam material is sprayed is more uniform, the flame retardant covering layer formed is also more uniform and dense, thereby improving the flame retardant effect.

[0008] Furthermore, the catalyst is selected from low-odor amine catalysts or metal catalysts, selected from tetramethyldipropylenetriamine PC15, dimethylethanolamine DMEA, N,N,N ， -Trimethyl-N ， - At least four of hydroxyethyl bisaminoethyl ether ZF-10, tris(dimethylaminopropyl)hexahydrotriazine PC41, potassium isooctanoate K15 or dibutyltin dimethicone T12. ZF-10 and PC41 are highly efficient reactive foaming catalysts that promote rapid foaming and solidification of polyols and isocyanates in sprayers; PC41 is a highly active trimerization catalyst for polyurethane rigid foams with excellent foaming / gelling ability, which can promote the copolymerization of flame-retardant polyester polyols with polyether polyols, multiple methyl polyphenyl polyisocyanates and modified isocyanates; PC15 is a low-odor reactive catalyst that promotes flame-retardant polyester polyols and high-functional polyether polyols to participate in chemical reactions and link with multiple methyl polyphenyl polyisocyanates and modified isocyanates during the foam generation process. The three catalysts promote rapid mixing and uniform reaction of various components to form foams at the initial stage of the reaction. The catalytic performance of T12 is exerted relatively slowly. It is soluble in various organic biomass and has certain lubricity and foam stability in the process of forming foam spraying. At the same time, it prevents the foam from solidifying too early to form more closed cells and insufficient reaction, which affects the performance of the finished product. It delays the curing time of polyurethane to make its reaction more complete and the filling effect during the construction process is better, which increases the dimensional stability and makes it less likely to deform.

[0009] Furthermore, the physical blowing agent is selected from at least one of 1,1,1,3,3-pentafluoropropane HFC 245fa and monofluorodichloropropane HFC-141B.

[0010] Furthermore, the polymethyl polyphenyl polyisocyanate is selected from at least one of M20S and PM-200; the modified isocyanate is CNI-1210. Compared with ordinary isocyanates, the modified isocyanate contains active groups in its molecular structure, which makes it have stronger adhesion, hardness, heat resistance, chemical resistance, waterproof performance and flame retardant performance, improves the impact resistance of the polyurethane spray material, and further improves the flame retardant performance of the polyurethane spray material.

[0011] The present invention also provides a method for preparing the above-mentioned polyurethane spray foam material, comprising the following steps:

[0012] (1) Stir and mix the reagents of component A in parts by weight;

[0013] (2) Stir and mix the reagents of component B by weight;

[0014] (3) Component A and component B are uniformly mixed according to a weight ratio, and atomized and foamed to obtain a polyurethane spray foam material.

[0015] Furthermore, by adjusting the pressure of the high-pressure sprayer to 1.5-2.5 Pa and the temperature to 45°C±5°C for uniform mixing, atomization and foaming are rapidly formed and matured to obtain a highly flame-retardant and ultra-low odor polyurethane material.

[0016] The invention also provides application of the polyurethane spray foam material in polyurethane rigid foam material.

[0017] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: 1. By using flame-retardant polyester polyols in combination with flame retardants, the flame retardant properties of polyurethane materials are greatly enhanced, the flame retardant grade can reach B1, and the safety performance is greatly improved; 2. By using high-official polyether polyols, water-washable flame retardants, low-odor catalysts, reactive catalysts and foaming agents in a reasonable combination, the odor of the prepared polyurethane material is below 3.0, while promoting the uniformity and compactness of the flame retardant covering layer, further improving the flame retardant effect; 3. The density of the polyurethane material is 45-55kg / m 3 , thermal conductivity <0.023W / mK@25℃, good thermal insulation effect; 4. The compressive strength of polyurethane material is >260kPa, dimensional stability <1%@-20℃ / 80℃, high toughness and good impact resistance, which improves the protective performance of polyurethane materials. DETAILED DESCRIPTION

[0018] The technical solution of the present invention is further described below in conjunction with the examples. The raw materials used in the examples are shown in Table 1, and the pure water meets the quality specifications of grade 3 water in GB / T 6682-2016.

[0019] Table 1 List of raw materials

[0020]

[0021] The preparation method of the polyurethane spray foam material of the embodiment and the comparative example comprises the following steps:

[0022] (1) Stir and mix the reagents of component A in parts by weight;

[0023] (2) Stir and mix the reagents of component B by weight;

[0024] (3) Component A and component B are uniformly mixed according to the weight ratio, and the pressure of the high-pressure sprayer is adjusted to 1.5-2.5 Pa and the temperature is adjusted to 45°C ± 5°C for uniform mixing, and the atomization foaming is rapidly formed and matured to obtain a highly flame-retardant and ultra-low odor polyurethane material.

[0025] Table 2 Weight parts of each component raw material in the embodiments and comparative examples

[0026]

[0027] Table 2 shows the components and proportions (parts by weight) of Examples 1 to 3 and Comparative Examples 1 to 6.

[0028] Comparative Example 1: Based on Example 2, the flame retardant polyester polyol HF-8730 was replaced with ordinary polyester polyol PS-3152, and the remaining steps were the same.

[0029] Comparative Example 2: Based on Example 2, the flame retardant polyester polyol HF-8730 was partially replaced with ordinary polyester polyol SKR-240B, and the remaining steps were the same.

[0030] Comparative Example 3: Based on Example 2, catalysts PC15, K15, T12 and ZF-10 were all replaced by PC5, A33, TMR-2 and PC41, and the remaining steps were the same.

[0031] Comparative Example 4: Based on Example 2, all flame retardants were replaced with a flame retardant TDCPP, and the remaining steps were the same.

[0032] Comparative Example 5: Based on Example 2, all flame retardants were replaced with non-TDCPP flame retardants, and the remaining steps were the same.

[0033] Comparative Example 6: Based on Example 2, all modified isocyanates were replaced with polymethyl polyphenyl polyisocyanate, and the remaining steps were the same.

[0034] The prepared high flame retardant and ultra-low odor polyurethane material was sprayed in an environment of 10-35°C, relative humidity less than 80%, and wind speed not exceeding 5m / s. The physical property test data of the prepared high flame retardant and ultra-low odor polyurethane spray material are shown in Table 3.

[0035] Table 3 Performance test data of embodiments and comparative examples

[0036]

[0037] Compared with Examples 1 to 3, Example 2 has the best flame retardant effect and the lowest odor level, mainly because the flame retardant polyester polyol and the high-functional polyether polyol participate in the chemical reaction during the foam generation process, link to the foam material, and form a permanent flame retardant effect, which can significantly reduce the amount of flame retardant, and reduce the generation of volatile gases while improving the flame retardant effect, thereby improving the environmental friendliness of polyurethane foam materials, improving people's comfort during construction or living, and reducing harm to human health. Compared with ordinary isocyanates, modified isocyanates contain active groups in their molecular structure, which makes them have stronger adhesion, hardness, heat resistance, chemical resistance, waterproof performance and flame retardant performance, improve the flame retardant performance of polyurethane spray materials, and improve the impact resistance of polyurethane spray materials. The three flame retardants are used in combination, and while each plays its own role, tris(2-chloroethyl) phosphate ester TCEP can promote the glassy or foamy water-washed tris(chloropropyl) phosphate ester TCPP and tris(dichloropropyl) phosphate ester TDCPP to be more easily and evenly mixed into the foam material, making the formed covering flame retardant layer uniform, thereby further improving the flame retardant effect. At the same time, the three flame retardants can improve the flexibility of polyurethane foam materials and further improve their impact strength.

[0038] Comparative Examples 1 and 2 replace all or part of the flame-retardant polyester polyol HF-8730 with ordinary polyester polyol PS-3152 on the basis of Example 2, and the flame retardant performance and compressive strength thereof are significantly reduced. This is mainly because HF-8730 is trifunctional, and its main component is tris(hydroxyethyl)isocyanurate THEIC, which is a multifunctional compound with a cage-type triazine ring structure, introduces flame retardant elements, has high flame retardancy, and is easily covalently bonded with high-functional polyether polyols to participate in the formation of foam, forming a permanent flame retardant effect.

[0039] Comparative Example 3 replaces all catalysts PC15, K15, T12 and ZF-10 with PC5, A33, TMR-2 and PC41 on the basis of Example 2. The odor is much stronger than that of the example, and it is impossible to take into account both flame retardant performance and environmentally friendly performance.

[0040] Comparative Examples 4 and 5 use only one flame retardant, TDCPP has poor solubility and high system viscosity, resulting in poor atomization performance and poor thermal conductivity; while using TCEP alone, on the one hand, affects the storage stability of the combined material, and on the other hand, cannot effectively form a flame retardant coating on its surface, resulting in poor flame retardant performance.

[0041] Comparative Example 6 replaces all modified isocyanates with polymethyl polyphenyl polyisocyanates based on Example 2, and the flame retardant performance is poor. The polyester modification of isocyanate promotes the mixing uniformity and adhesion with component A, further improves the flame retardant performance, and improves the impact resistance.

Claims

1. A polyurethane spray foam material, measured by weight, characterized in that: The invention is composed of component A and component B in a weight ratio of 1:1 to 1.03; the component A comprises: 45 to 50 parts of flame retardant polyester polyol, 6 to 8 parts of high-functional polyether polyol, 20 to 25 parts of flame retardant, 0.5 to 1.5 parts of foam stabilizer, 4 to 6 parts of catalyst, 15 to 17 parts of physical foaming agent, 0.2 to 0.3 parts of color paste and 0.1 to 0.3 parts of water; the component B comprises polymethyl polyphenyl polyisocyanate and modified isocyanate in a weight ratio of 8 to 9:

1.

2. The polyurethane spray foam material according to claim 1, characterized in that: The flame retardant polyester polyol has an average molecular weight of 600-700, a hydroxyl value of 200-250 mgKON / g, a functionality of 3, and is HF-8730; the high-functional polyether polyol is a polyether polyol using ethylenediamine or toluenediamine as an initiator, has a molecular weight of 500-750, a hydroxyl value of 500-750 mgKOH / g, a functionality of 4, and is selected from at least one of NJ-403 or TD405.

3. The polyurethane spray foam material according to claim 1, characterized in that: The flame retardant is a phosphate flame retardant, which is selected from at least one of water-washed tris(chloropropyl) phosphate TCPP, tris(2-chloroethyl) phosphate TCEP, and tris(dichloropropyl) phosphate TDCPP.

4. The polyurethane spray foam material according to claim 1, characterized in that: The foam stabilizer is a non-hydrolyzable silicon surfactant or a polysiloxane surfactant, selected from at least one of L6900, B8545, or DC193.

5. The polyurethane spray foam material according to claim 1, characterized in that: The catalyst is selected from low-odor amine catalysts or metal catalysts, selected from tetramethyl dipropylene triamine PC15, dimethyl ethanolamine DMEA, N, N, N ， -Trimethyl-N ， - At least four of hydroxyethyl bisaminoethyl ether ZF-10, tris(dimethylaminopropyl)hexahydrotriazine PC41, potassium isooctanoate K15, dibutyltin dilaurate T12 or bis-(2-dimethylaminoethyl) ether ZF-20.

6. The polyurethane spray foam material according to claim 1, characterized in that: The physical foaming agent is selected from at least one of 1,1,1,3,3-pentafluoropropane HFC 245fa and monofluorodichloropropane HFC-141B.

7. The polyurethane spray foam material according to claim 1, characterized in that: The polymethyl polyphenyl polyisocyanate is selected from at least one of M20S and PM-200.

8. The polyurethane spray foam material according to claim 1, characterized in that: The modified isocyanate is CNI-1210.

9. A method for preparing the polyurethane spray foam material according to any one of claims 1 to 8, characterized in that: The steps include: (1) Stir and mix the reagents of component A in parts by weight; (2) Stir and mix the reagents of component B by weight; (3) Component A and component B are uniformly mixed according to a weight ratio, and atomized and foamed to obtain a polyurethane spray foam material.

10. Use of the polyurethane spray foam material according to any one of claims 1 to 8 in polyurethane rigid foam materials.

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