Bi-component polyurethane light foam as well as preparation method and application thereof

Abstract

The invention relates to bi-component polyurethane light foam as well as a preparation method and application thereof. The bi-component polyurethane light foam mainly solves the problems of high density, poor flame retardance and poor flame-retardant stability of automotive polyurethane light foam in the prior art. According to the technical scheme, the bi-component polyurethane light foam material is adopted and comprises a component A and a component B, the weight part ratio of the component A to the component B is 100: (110-220), the component A comprises the following components in parts by weight: 20-40 parts of polyether polyol I, 20-40 parts of polyether polyol II, 20-40 parts of open-cell polyether polyol, 10-20 parts of tri (dipropylene glycol) phosphite ester and 1.5-2.2 parts of a foam stabilizer, and the component B comprises the following components in parts by weight: 10-20 parts of polyether polyol I, 20-40 parts of polyether polyol II, 20-40 parts of open-cell polyether polyol II, 10-20 parts of tri (dipropylene glycol) phosphite ester and 1.5-2.2 parts of a foam stabilizer; 0.5 to 0.9 part of a combined catalyst and 8.5 to 14 parts of water; the component B is a composition of modified isocyanate and a tetrabromophthalic anhydride derivative in a weight part ratio of 100: (2.5-5). According to the technical scheme, the problems are well solved, and the method can be applied to industrial application of automobile roofs.

Description

Technical Field

[0001] The invention relates to a two-component polyurethane lightweight foam and a preparation method and application thereof. Background Art

[0002] Traditional automotive acoustic pads are mostly made of felt, fiberglass, etc., that is, felt / fiberglass + black non-woven fabrics, etc. are made by molding and punching, and often have pungent odors, floating cotton wool, and high density. Now, non-woven fabrics + glue + lightweight foam + glue + non-woven fabrics / aluminum are usually used, and the lightweight foam is lightweight polyurethane foam, which has the advantages of low density and easy molding. Pads with excellent acoustic performance need to reflect sound absorption and excellent sound insulation. Sound absorption refers to the absorption of radiated noise in the car, and sound insulation refers to the isolation of noise from external noise sources transmitted into the car. In addition, certain flame retardant properties are required. The method commonly used at present is to add solid flame retardants or phosphorus-containing compounds, especially organic phosphorus compounds, which are widely used flame retardants. Organic phosphorus flame retardants are mainly based on phosphates, phosphonates or phosphites. Known phosphorus-containing flame retardants, such as triethyl phosphate (TEP) or diethyl ethylphosphonate (DEEP), for example, can cause the discharge of plastics, thereby producing an unpleasant odor. In addition, non-reactive liquid flame retardants also have the disadvantage of easy migration, which, over time, can cause the disadvantage of decreased flame retardancy. This hinders the use of the flame retardant in the preparation of polyurethane foam for enclosed spaces such as automobile passenger compartments. Solid flame retardants such as expanded graphite can easily block the injection pipe and the gun tip when the low-pressure foaming agent is foamed. Therefore, it is imperative to develop a lightweight foam that does not contain a solid flame retardant or a volatile liquid flame retardant such as a phosphorus-containing compound.

[0003] Chinese patent application CN103910854A discloses a low-density flame-retardant semi-rigid polyurethane foam and a preparation method thereof. The foam obtained is a flame-retardant semi-rigid polyurethane foam with a high open-cell rate of ≥90%, which partially meets the Volkswagen PV3937 requirements. However, the Volkswagen flame-retardant standard has been updated to TL1010-2008, which has more stringent requirements. There is no subsequent patent related to the flame retardancy of the low-density flame-retardant semi-rigid polyurethane foam. In addition, the invention uses 20 to 40 parts of halogenated phosphate esters such as TCPP and other flame retardants. This type of flame retardant has a strong odor and is highly volatile, affecting the interior environment of the vehicle, and the sound absorption performance of the foam is not mentioned.

[0004] CN110982030A discloses a one-step continuous production method for preparing lightweight polyurethane semi-rigid foam. The formula contains a combined polyether, a combined isocyanate, and related additives. The combined polyether ratio is as follows by mass: polyether polyol composition: 80-90 parts; flame retardant: 10-20 parts; cell opener: 2-10 parts; chain extender: 5-10 parts. The foam produced by this method has the advantages of low density and finer pores, but uses phosphate flame retardants, which are volatile and have a strong odor, and do not meet the environmental protection requirements for the development of automotive interiors. In addition, the content does not mention the flame retardant properties of the foam.

[0005] CN116874721A adopts a low-density porous material, which is composed of components A, B, C and D. In terms of weight ratio, A:B:C:D=100:85-250:0.5-10:10-55; component A, in terms of weight ratio, comprises: 20-60 parts of polyether polyol A, 20-50 parts of polyether polyol B, 0.5-11 parts of open-cell polyether polyol, 0.2-2.5 parts of foam stabilizer, and 3-18 parts of water; component B is isocyanate; component C is a combination of a small molecule compound and a catalyst; component D is a combination of an intumescent flame retardant material and a porous nano material in a weight ratio of 1:1-10; the expansion ratio of the intumescent flame retardant material is greater than 50; the particle size of the porous nano material is ≥3000 mesh, and the specific surface area is greater than 10000cm 2 / g and the technical solution for its preparation have effectively solved the problems of high density, poor sound absorption and poor flame retardancy of automotive polyurethane porous materials existing in the prior art, but its flame retardancy is not high, only meeting the A0 level and failing to meet the requirement of oxygen index ≥ 28.2%. Summary of the invention

[0006] One of the technical problems to be solved by the present invention is that the prior art has the problem of high density, poor flame retardancy and poor flame retardant stability of lightweight polyurethane foam for vehicles, and provides a two-component lightweight polyurethane foam having the advantages of low density, good flame retardant performance and good flame retardant stability.

[0007] The second technical problem to be solved by the present invention is to provide a method for preparing a two-component polyurethane lightweight foam corresponding to the first technical problem to be solved.

[0008] The third technical problem to be solved by the present invention is to provide an application of a two-component polyurethane lightweight foam corresponding to the first technical problem to be solved.

[0009] In order to solve one of the above technical problems, the technical solution provided by the present invention is as follows: a two-component polyurethane lightweight foam composition, consisting of component A and component B, wherein component A and component B are calculated in a weight ratio of 100:110-220, wherein, in weight ratio, component A: polyether polyol I is 20-40 parts, polyether polyol II is 20-40 parts, open-cell polyether polyol is 20-40 parts, tri(dipropylene glycol) phosphite is 10-20 parts, foam stabilizer is 1.5-2.2 parts, combined catalyst is 0.5-0.9 parts, and water is 8.5-14 parts; component B is a composition of modified isocyanate and tetrabromophthalic anhydride derivative in a weight ratio of 100:2.5-5. The polyether polyol I is prepared by polymerization of ethylene oxide and propylene oxide with glycerol as the initiator, with a functionality of 3, a molecular weight of 5000-7000, and a hydroxyl value of 26-30 mgKOH / g; the polyether polyol II is prepared by polymerization of propylene oxide with glycerol as the initiator, with a functionality of 3, a molecular weight of 900-1100, and a hydroxyl value of 163-172 mgKOH / g, and has a relatively suitable support; the open-cell polyether polyol is prepared by polymerization of sorbitol and The propylene glycol is used as an initiator, which is polymerized from ethylene oxide and propylene oxide, has a functionality of 4, a molecular weight of 7000-9000, a hydroxyl value of 25-40 mgKOH / g, and an EO content of 65%-80%. The tri(dipropylene glycol) phosphite is a phosphorus-containing polyol flame retardant, has a phosphorus content of 7.2%, and a hydroxyl value of 395 mgKOH / g. The component B is prepolymerized from isocyanate and a tetrabromophthalic anhydride derivative, and has an isocyanate group content of 24-27%.

[0010] In the above technical solution, the tri(dipropylene glycol) phosphite in component A is a phosphorus-containing polyol flame retardant, selected from at least one of Weston430 and P430.

[0011] In the above technical solution, the foam stabilizer in component A is selected from at least one of AK-8805, B8002, and L580.

[0012] In the above technical scheme, the combined catalyst in component A is composed of catalyst A and catalyst B, the weight ratio of catalyst A to catalyst B is 1:0.2-0.6, catalyst A is selected from at least one of A1, ZF-10, and NE-300, and catalyst B is selected from at least one of A33, NE-1070, and NE-210.

[0013] In the above technical scheme, the isocyanate in component B is selected from at least one of pure MDI, crude MDI, PM200, M20S, 5005, carbonized diamine-modified MDI, MDI-50 or TDI, and the tetrabromophthalic anhydride derivative is selected from at least one of firemaster BZ-54 and BZ-54HP.

[0014] To solve the second technical problem, the technical solution adopted by the present invention is as follows: a method for preparing a two-component low-density polyurethane lightweight foam composition comprises the following steps:

[0015] (1) Preparation of component A: Add in a container, in order by weight: 20-40 parts of polyether polyol I, 20-40 parts of polyether polyol II, 20-40 parts of open-cell polyether polyol, 10-20 parts of tri(dipropylene glycol) phosphite, 1.5-2.2 parts of foam stabilizer, 0.5-0.9 parts of combined catalyst, and 8.5-14 parts of water, and stir the components thoroughly;

[0016] (2) Preparation of component B: adding isocyanate to a reaction kettle, stirring and evacuating, controlling the temperature at 60-80° C., and after nitrogen replacement, adding dropwise a flame-retardant polytetrabromophthalic anhydride derivative ester, wherein the isocyanate and the flame-retardant polyester are in a weight ratio of 100:2.5-5, and the reaction time is about 160-200 min;

[0017] (3) Control the ambient temperature to 19-22° C., add component C to component B and mix quickly, then add component A and stir quickly for 15-25 seconds. After stirring evenly, immediately pour into a foaming box for foaming to obtain the product.

[0018] In order to solve the third of the above technical problems, the technical solution adopted by the present invention is as follows: application of a two-component low-density polyurethane lightweight foam composition in a bus roof.

[0019] By adopting the technical scheme of the present invention, a preparation method of a composition of a two-component polyurethane lightweight foam can be prepared, and the advantages of the technical scheme are as follows: first, tri(dipropylene glycol)phosphite is a phosphorus-containing polyol flame retardant, and its phosphorus content is 7.2%, and its hydroxyl value is 395 mgKOH / g. It is a phosphorus-containing and hydroxyl-containing reactive flame retardant, has good flame retardancy, is not easy to migrate, and has a long flame retardant effect; second, tetrabromophthalic anhydride derivatives and isocyanates are prepolymerized, which can form a large number of benzene ring structures on the one hand, and also introduce a large number of flame retardant bromine elements, which can greatly improve the flame retardant performance; directly participate in the reaction and become the main constituent material of the foam, and will not migrate, and the flame retardant effect is maintained for a long time; third, the formula design does not adopt the commonly used method of adding solid flame retardants, which will cause the viscosity of the composite material to be large on the one hand, and on the other hand, the solid flame retardant cannot be used for foaming in a low-pressure or high-pressure foaming machine, otherwise it will block the pipeline; and non-reactive phosphorus-containing compounds, especially organic phosphorus compounds, which are widely used flame retardants, are not used. Organic phosphorus flame retardants are mainly based on phosphates, phosphonates or phosphites. Known phosphorus-containing flame retardants, such as triethyl phosphate (TEP) or diethyl ethylphosphonate (DEEP), for example, can cause the emission of plastics, thereby producing an unpleasant odor. Fourth, the polyether polyol II in component A is selected to use propylene oxide as an initiator with a functionality of 3, a molecular weight of 900-1100, and a hydroxyl value of 163-172 mgKOH / g. It has a relatively suitable support and can provide the foam with better foam strength and toughness. The two-component polyurethane lightweight foam obtained by the present invention not only has a low density (8.4-15.3 kg / m 3 ), and the flame retardancy (LOI is 22.1-24.2%) and flame retardancy stability are very good, and good technical effects have been achieved. DETAILED DESCRIPTION

[0020] The present invention is further described below in conjunction with specific embodiments. The described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments.

[0021] Table 1 List of raw materials

[0022]

[0023]

[0024] Example 1

[0025] (1) Preparation of component A: In a container, add 30 parts of polyether polyol I, 30 parts of polyether polyol II, 20 parts of open-cell polyether polyol, 0.8 parts of foam stabilizer AK-8805, 1.0 parts of foam stabilizer B8002, 0.5 parts of catalyst I: ZF-10, 0.2 parts of catalyst II: NE-1070, 10 parts of tri(dipropylene glycol) phosphite, and 11 parts of water in order by weight, and stir the components thoroughly;

[0026] (2) Preparation of component B: 200 parts of isocyanate were added to a reaction kettle, stirred and evacuated, the temperature was controlled at 60-80°C, and after nitrogen replacement, 10 parts of P430 were added dropwise and reacted for about 180 minutes;

[0027] (3) Control the ambient temperature to 19-22° C., add component C to component B and mix quickly, then add component A and stir quickly for 15-25 seconds. After stirring evenly, immediately pour into a foaming box for foaming to obtain the product.

[0028] Embodiments 2 to 8

[0029] Examples 2 to 8 are carried out according to the steps in Example 1, except that the reaction raw materials and raw material ratios in the foaming formula are different, as shown in Table 2; the performance index data of the obtained two-component polyurethane lightweight foam are shown in Tables 4 and 5.

[0030] Table 2 Weight parts of each component in the foaming formula of two-component polyurethane lightweight foam in Examples 1 to 8

[0031]

[0032]

[0033] Comparative Examples 1 to 5

[0034] (1) Prepare the raw materials according to the weight proportions of the components in Table 3;

[0035] (2) Preparation of component A: Add the weighed components in the container in order according to the weight proportions in step (1), stir for 15 seconds, the material temperature is 20° C., and mix thoroughly;

[0036] (3) Controlling the ambient temperature to 20°C, quickly mixing component A with component B and component C, and immediately pouring them into a foaming box for foaming after stirring evenly, to obtain a polyurethane lightweight foam material, the performance index data of which are shown in Table 4.

[0037] Table 3 Weight parts of each component in the foaming formula of the polyurethane lightweight foam of Comparative Examples 1 to 5

[0038]

[0039] Table 4 Performance test data of polyurethane lightweight foam of Examples 1 to 8 and Comparative Examples 1 to 5

[0040]

[0041]

[0042] Note: The flame retardant stability is characterized by the LOI after aging and the flame retardant performance after aging, that is, the trend of the flame retardant performance of polyurethane foam changing over time. (The larger the LOI, the better, and the smaller the horizontal combustion value, the better)

[0043] The test method for the performance in Table 4 is as follows:

[0044] Density: GB / T 6343-2009;

[0045] Compression strength: GB / T 8813-2020;

[0046] Elongation at break: GB / T 6344-2008;

[0047] LOI(%): Tested in accordance with GB / T 2406.2;

[0048] Flame retardant performance: According to Volkswagen TL1010-2008, the general requirement is that the burning rate is <100mm / min, and the flame retardant performance test meets the standard requirements. If the burning rate is >100mm / min, the flame retardant performance test does not meet the standard requirements.

[0049] LOI after aging (%): baked in oven at 80°C for 21 days, tested according to GB / T 2406.2;

[0050] Flame retardant properties after aging: baked in oven at 80°C for 21 days, in accordance with Volkswagen TL1010-2008 standard.

[0051] It can be seen from Table 4 that the two-component polyurethane lightweight foams prepared in Examples 1 to 8 of the present invention have a density of 8.4 to 15.3 kg / m 3 ) is less than the density of the comparative example (9.2~16.4kg / m 3 ), the compressive strength (12.7-25.9 KPa), elongation at break (18.1-25.6%) and LOI (22.1-24.2%) are still better than those of the embodiments; the flame retardant properties of the polyurethane lightweight foam after aging in the embodiments of the present invention are not much changed compared with the original ones, and can be used in industrial applications of automobile roofs.

Claims

1. A two-component polyurethane lightweight foam composition, consisting of component A and component B, wherein component A and component B are calculated in a weight ratio of 100:110-220, wherein: In terms of weight ratio, component A includes 20 to 40 parts of polyether polyol I, 20 to 40 parts of polyether polyol II, 20 to 40 parts of open-cell polyether polyol, 10 to 20 parts of tri(dipropylene glycol) phosphite, 1.5 to 2.2 parts of foam stabilizer, 0.5 to 0.9 parts of combined catalyst, and 8.5 to 14 parts of water; component B is a composition of modified isocyanate and tetrabromophthalic anhydride derivative in a weight ratio of 100:2.5 to 5. The polyether polyol I is prepared by polymerization of ethylene oxide and propylene oxide with glycerol as the initiator, with a functionality of 3, a molecular weight of 5000-7000, and a hydroxyl value of 26-30 mgKOH / g; the polyether polyol II is prepared by polymerization of propylene oxide with glycerol as the initiator, with a functionality of 3, a molecular weight of 900-1100, and a hydroxyl value of 163-172 mgKOH / g, and has a relatively suitable support; the open-cell polyether polyol is prepared by polymerization of sorbitol and The propylene glycol is used as an initiator, which is polymerized from ethylene oxide and propylene oxide, has a functionality of 4, a molecular weight of 7000-9000, a hydroxyl value of 25-40 mgKOH / g, and an EO content of 65%-80%. The tri(dipropylene glycol) phosphite is a phosphorus-containing polyol flame retardant, has a phosphorus content of 7.2%, and a hydroxyl value of 395 mgKOH / g. The component B is prepolymerized from isocyanate and a tetrabromophthalic anhydride derivative, and has an isocyanate group content of 24-27%.

2. A two-component polyurethane lightweight foam composition according to claim 1, characterized in that: The tri(dipropylene glycol) phosphite is a phosphorus-containing polyol flame retardant, selected from at least one of Weston430 and P430.

3. A two-component polyurethane lightweight foam composition according to claim 1, characterized in that: The foam stabilizer is selected from at least one of AK-8805, B8002 and L580.

4. A two-component polyurethane lightweight foam composition according to claim 1, characterized in that: The combined catalyst is composed of catalyst A and catalyst B, the weight ratio of catalyst A to catalyst B is 1:0.2-0.6, catalyst A is selected from at least one of A1, ZF-10, and NE-300, and catalyst B is selected from at least one of A33, NE-1070, and NE-210.

5. The two-component polyurethane lightweight foam composition according to claim 1, characterized in that: The isocyanate in component B is selected from at least one of pure MDI, crude MDI, PM200, M20S, 5005, carbonized diamine-modified MDI, MDI-50 or TDI, and the tetrabromophthalic anhydride derivative is selected from at least one of firemaster BZ-54 and BZ-54HP.

6. A method for preparing a two-component polyurethane lightweight foam composition according to claim 1, comprising the following steps: (1) preparing component A: adding in a container, in order by weight, 20 to 40 parts of polyether polyol I, 20 to 40 parts of polyether polyol II, 20 to 40 parts of open-cell polyether polyol, 10 to 20 parts of tri(dipropylene glycol) phosphite, 1.5 to 2.2 parts of foam stabilizer, 0.5 to 0.9 parts of combined catalyst, and 8.5 to 14 parts of water, and stirring the components thoroughly; (2) Preparation of component B: adding isocyanate to a reaction kettle, stirring and evacuating, controlling the temperature at 60-80° C., and after nitrogen replacement, adding dropwise a flame-retardant polytetrabromophthalic anhydride derivative ester, wherein the isocyanate and the flame-retardant polyester are in a weight ratio of 100:2.5-5, and the reaction time is about 160-200 min; (3) Control the ambient temperature to 19-22° C., add component C to component B and mix quickly, then add component A and stir quickly for 15-25 seconds. After stirring evenly, immediately pour into a foaming box for foaming to obtain the product.

7. Use of the two-component polyurethane lightweight foam according to claim 1 in automobile ceilings.

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