Two-component polyurethane composition, polyurethane foam material and preparation method

Abstract

The invention belongs to the technical field of polyurethane materials, particularly relates to a two-component polyurethane composition and a washable anti-yellowing polyurethane foam material prepared from the two-component polyurethane composition, and further discloses a preparation method of the two-component polyurethane composition. The bi-component polyurethane composition comprises an independent component A and an independent component B. The component A comprises polyether polyol, a random polymer of hexafluorobutyl methacrylate (HFBMA) and 2-hydroxyethyl methacrylate (HEMA), a cross-linking agent, a foaming agent, a foam stabilizer and a catalyst. And the component B comprises isocyanate. According to the double-component polyurethane composition disclosed by the invention, on the basis of a traditional polyurethane synthesis system, a polymer obtained by copolymerizing hexafluorobutyl methacrylate and 2-hydroxyethyl methacrylate is used as a modifier; the polyurethane material prepared from the polyurethane composition has the advantages of washable yellowing resistance, excellent tensile strength, tear strength and elongation at break, and certain weatherability.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane materials, and in particular relates to a two-component polyurethane composition and a washable and yellowing-resistant polyurethane foam material prepared therefrom, and further discloses a preparation method thereof. Background Art

[0002] Polyurethane synthetic materials are a widely used polymer material. In order to improve or enhance the performance of polyurethane, people prepare high-performance polyurethane composite materials by adding special functional materials to the foaming system, such as low temperature resistance, shape memory, washability, etc. According to the different performance of additives in the foaming system, polyurethane foam composite materials with different functions can be obtained and distributed to different application scenarios. For example, the current inflatable slow-rebound sponge is widely used in seats, sofas, mattresses, pillows and other fields due to its extremely high comfort.

[0003] However, most memory foam pillows are prone to yellowing and cannot be washed. During long-term use, they are prone to produce odor. In the long run, polyurethane pillows will not only fail to bring a comfortable experience, but will affect people's usage experience.

[0004] The current mainstream polyurethane slow-rebound sponge mainly uses polyether with high EO content, but it itself has the problem of swelling after washing, decreased physical properties, and easy rupture of the sponge. Although reducing the EO content will improve the swelling performance of the sponge, it will greatly reduce its reaction activity, resulting in a worse feel of the sponge. Summary of the invention

[0005] To this end, the technical problem to be solved by the present invention is to provide a two-component polyurethane composition, in which HFBMA-co-HEMA polymer is introduced to reduce the swelling of polyurethane foam material by utilizing its hydrophobic property, and fluorine itself has good weather resistance, and the addition of hexafluorobutyl methacrylate can also improve the problem of yellowing of the polyurethane material itself;

[0006] The second technical problem to be solved by the present invention is to provide a water-washable and yellowing-resistant polyurethane foam material, which has the advantages of being water-washable and yellowing-resistant, and has excellent mechanical properties and can be repeatedly washed with water;

[0007] The third technical problem to be solved by the present invention is to provide a method for preparing a water-washable and yellowing-resistant polyurethane foam material.

[0008] In order to solve the above technical problems, the present invention discloses a two-component polyurethane composition, comprising independent component A and component B; wherein:

[0009] The A component includes the following raw material components in parts by weight:

[0010] Polyether polyol 45-110 parts by weight;

[0011] 5-10 parts by weight of HFBMA-co-HEMA polymer;

[0012] A blowing agent, the amount of which accounts for 1.5-3wt% of the total amount of the polyether polyol and the HFBMA-co-HEMA polymer;

[0013] A cross-linking agent, the amount of which accounts for 0.5-2wt% of the total amount of the polyether polyol and the HFBMA-co-HEMA polymer;

[0014] A foam stabilizer, the amount of which accounts for 0.5-2wt% of the total amount of the polyether polyol and the HFBMA-co-HEMA polymer;

[0015] A catalyst, the amount of which accounts for 0.1-2wt% of the total amount of the polyether polyol and the HFBMA-co-HEMA polymer;

[0016] The B component includes the following raw material components in parts by weight:

[0017] Isocyanate 50-80 parts by weight.

[0018] Specifically, in the two-component polyurethane composition, the HFBMA-co-HEMA polymer is a polymer of hexafluorobutyl methacrylate and 2-hydroxyethyl methacrylate, and has the following structure:

[0019]

[0020] Preferably, the molecular weight of the HFBMA-co-HEMA polymer is 1000-4000.

[0021] Specifically, the preparation method of the two-component polyurethane composition and the HFBMA-co-HEMA polymer comprises: under a protective atmosphere, using hexafluorobutyl methacrylate (HFBMA) and 2-hydroxyethyl methacrylate (HEMA) as raw materials, adding a chain transfer agent and an initiator, dissolving them in an organic solvent for polymerization reaction, collecting the reactants and removing the organic solvent, thereby obtaining;

[0022] Preferably, the molar ratio of hexafluorobutyl methacrylate to 2-hydroxyethyl methacrylate is 6-15:1;

[0023] Preferably, the chain transfer agent comprises dodecyl mercaptan;

[0024] Preferably, the amount of the chain transfer agent added is 2.0-3.0 wt % of the total amount of hexafluorobutyl methacrylate (HFBMA) and 2-hydroxyethyl methacrylate (HEMA);

[0025] Preferably, the initiator comprises AIBN;

[0026] Preferably, the amount of the initiator added is 0.1-0.3 wt % of the total amount of the hexafluorobutyl methacrylate (HFBMA) and 2-hydroxyethyl methacrylate (HEMA);

[0027] Preferably, the polymerization reaction temperature is 60-70°C and the polymerization reaction time is 3-5h;

[0028] Preferably, the organic solvent comprises anhydrous ethanol.

[0029] Specifically, in the two-component polyurethane composition, the polyether polyol includes at least one of polyether polyol A, polyether polyol B or polyether polyol C; wherein,

[0030] The polyether polyol A has a weight average molecular weight of 3000-5000, a functionality of 2-4, and an ethylene oxide content of 60-85wt% based on the total mass of propylene oxide and ethylene oxide as 100%;

[0031] The polyether polyol B has a weight average molecular weight of 2000-4000, a functionality of 2-4, and a propylene oxide content of 60-95wt% based on the total mass of propylene oxide and ethylene oxide as 100%;

[0032] The weight average molecular weight of the polyether polyol C is 500-1500, the functionality is 2-4, and the content of propylene oxide is 90-100 wt % based on the total mass of propylene oxide and ethylene oxide being 100 wt %.

[0033] Specifically, in the two-component polyurethane composition, the polyether polyol includes a mixture of polyether polyol A, polyether polyol B or polyether polyol C;

[0034] Preferably, the mass ratio of the polyether polyol A, polyether polyol B and polyether polyol C is 20-50:5-20:20-40.

[0035] Specifically, in the two-component polyurethane composition:

[0036] The foaming agent includes one of water, dichloromethane or cyclopentane; and / or,

[0037] The cross-linking agent includes at least one of alcohol or amine small molecule compounds with a functionality of 2-4, preferably one or a mixture of diethanolamine, triethanolamine, and glycerol;

[0038] The foam stabilizer comprises a polysiloxane-olefin oxide block copolymer; and / or,

[0039] The catalyst comprises at least one of an amine catalyst or an organometallic catalyst; and / or,

[0040] The isocyanate includes at least one of isocyanate monomers, polyisocyanates or isocyanate prepolymers; preferably one or a mixture of urethane-modified MDI, polymeric MDI, 4,4-MDI, 2,4-MDI, carbodiimide-modified MDI, TDI or IPDI.

[0041] The invention also discloses the use of the two-component polyurethane composition for preparing a water-washable and yellowing-resistant polyurethane foam material.

[0042] The invention also discloses a water-washable and yellowing-resistant polyurethane foam material, the preparation raw materials of which include the two-component polyurethane composition.

[0043] The present invention also discloses a method for preparing the washable yellowing-resistant polyurethane foam material, comprising the following steps:

[0044] (1) respectively preparing the ingredients according to the selected raw materials and the metering ratio to obtain the component A and the component B for standby use;

[0045] (2) Mix the component A and the component B at 20-30° C. and pour into a mold for forming. After the mold is opened, the mixture is allowed to stand.

[0046] Specifically, the preparation method of the washable yellowing-resistant polyurethane foam material is as follows:

[0047] The mixing step includes adding the B component to the A component and rapidly stirring for 3-6 seconds; and / or,

[0048] The time of the forming step is 5-7 minutes; and / or,

[0049] The time of the standing step is 12-24 hours; and / or,

[0050] The method further comprises the step of preparing the HFBMA-co-HEMA polymer.

[0051] The two-component polyurethane composition of the present invention comprises independent component A and component B, wherein component A comprises polyether polyol, random polymer of hexafluorobutyl methacrylate (HFBMA) and 2-hydroxyethyl methacrylate (HEMA), crosslinking agent, foaming agent, foam stabilizer, and catalyst; and component B comprises isocyanate. The two-component polyurethane composition of the present invention, based on the traditional polyurethane synthesis system, uses the polymer obtained by copolymerization of hexafluorobutyl methacrylate and 2-hydroxyethyl methacrylate as a modifier, and the polyurethane material prepared by the polyurethane composition has water washability, yellowing resistance, excellent tensile strength, tear strength, elongation at break, and certain weather resistance.

[0052] The polyurethane foam material of the present invention, based on the traditional polyurethane synthesis system, uses the polymer obtained by copolymerization of hexafluorobutyl methacrylate and 2-hydroxyethyl methacrylate as a modifier, introduces HFBMA-co-HEMA polymer into the polyurethane molecular chain, utilizes its internal polyester structure to provide excellent mechanical properties, utilizes its internal fluorine to bring better hydrophobic properties, and at the same time, it is grafted into the polyurethane long chain as a side chain, and due to the good weather resistance of fluorine itself, the polyurethane material can have better yellowing resistance. Compared with the polyurethane material system using hexafluorobutyl methacrylate and 2-hydroxyethyl methacrylate monomers alone, the polyurethane foam material of the present invention can effectively improve the water washing and yellowing resistance of the polyurethane foam material, and at the same time has excellent mechanical properties, can be repeatedly washed, is particularly suitable for household polyurethane pillows, is convenient to clean, and is more hygienic.

[0053] The polyurethane composition and polyurethane foam material of the present invention further optimize the polyether polyol system, use high EO polyether in combination with high PO polyether, improve the hydrophobicity of the foam and reduce the swelling ratio of the sponge while ensuring the reaction activity. DETAILED DESCRIPTION

[0054] The present invention provides a polyurethane composition modified by a polymer of hexafluorobutyl methacrylate and 2-hydroxyethyl methacrylate in order to prepare a washable and yellowing-resistant polyurethane foam material, and specifically relates to a two-component polyurethane composition, comprising an independent component A and a component B; wherein:

[0055] The A component includes the following raw material components in parts by weight:

[0056] Polyether polyol 45-110 parts by weight;

[0057] 5-10 parts by weight of HFBMA-co-HEMA polymer;

[0058] A blowing agent, the amount of which accounts for 1.5-3wt% of the total amount of the polyether polyol and the HFBMA-co-HEMA polymer;

[0059] A cross-linking agent, the amount of which accounts for 0.5-2wt% of the total amount of the polyether polyol and the HFBMA-co-HEMA polymer;

[0060] A foam stabilizer, the amount of which accounts for 0.5-2wt% of the total amount of the polyether polyol and the HFBMA-co-HEMA polymer;

[0061] A catalyst, the amount of which accounts for 0.1-2wt% of the total amount of the polyether polyol and the HFBMA-co-HEMA polymer;

[0062] The B component includes the following raw material components in parts by weight:

[0063] Isocyanate 50-80 parts by weight.

[0064] As a preferred solution, the present invention specifically provides a two-component polyurethane composition, comprising independent component A and component B; wherein,

[0065] The A component includes the following raw material components in parts by weight:

[0066] Polyether polyol A 20-50 parts by weight;

[0067] Polyether polyol B 5-20 parts by weight;

[0068] Polyether polyol C 20-40 parts by weight;

[0069] 5-10 parts by weight of HFBMA-co-HEMA polymer;

[0070] A blowing agent, the amount of which accounts for 1.5-3wt% of the total amount of the polyether polyol and the HFBMA-co-HEMA polymer;

[0071] A cross-linking agent, the amount of which accounts for 0.5-2wt% of the total amount of the polyether polyol and the HFBMA-co-HEMA polymer;

[0072] A foam stabilizer, the amount of which accounts for 0.5-2wt% of the total amount of the polyether polyol and the HFBMA-co-HEMA polymer;

[0073] A catalyst, the amount of which accounts for 0.1-2wt% of the total amount of the polyether polyol and the HFBMA-co-HEMA polymer;

[0074] The B component includes the following raw material components in parts by weight:

[0075] Isocyanate 50-80 parts by weight.

[0076] As an operative method, in the two-component polyurethane composition of the present invention:

[0077] The weight average molecular weight of the polyether polyol A is 3000-5000, the functionality is 2-4, and the content of ethylene oxide is 60-85wt% based on the total mass of propylene oxide and ethylene oxide as 100%; preferably, a polyether polyol with a higher EO content is selected as an exemplary raw material. In the following examples of the present invention, the polyether polyol produced by Wanhua Chemical Co., Ltd. is used. F3140 is an example raw material for polyether polyol A;

[0078] The weight average molecular weight of the polyether polyol B is 2000-4000, the functionality is 2-4, and the content of propylene oxide is 60-95wt% based on the total mass of propylene oxide and ethylene oxide as 100%; preferably, a polyether polyol with a high PO content is selected as an exemplary raw material. In the following examples of the present invention, the polyether polyol produced by Wanhua Chemical Co., Ltd. is used. F3156 is an example raw material for polyether polyol B;

[0079] The weight average molecular weight of the polyether polyol C is 500-1500, the functionality is 2-4, and the content of propylene oxide is 90-100wt% based on the total mass of propylene oxide and ethylene oxide as 100%; as an exemplary raw material selection, the present invention uses the polyether polyol C produced by Wanhua Chemical Co., Ltd. in the following examples. S3007 is an example raw material for polyether polyol C.

[0080] As an operative method, in the two-component polyurethane composition of the present invention:

[0081] The foaming agent comprises at least one of water, dichloromethane or cyclopentane, preferably deionized water; and / or,

[0082] The cross-linking agent includes at least one of alcohol or amine small molecule compounds with a functionality of 2-4, preferably one or a mixture of diethanolamine, triethanolamine, and glycerol, more preferably diethanolamine;

[0083] The foam stabilizer includes a polysiloxane-olefin oxide block copolymer, and B8002 produced by Evonik Degussa is used as an example raw material in the following embodiments of the present invention; and / or,

[0084] The catalyst includes a class of additives that can catalyze the reaction between isocyanate groups and active hydrogen atoms, examples of which include but are not limited to amine catalysts, organic metal catalysts, etc. Such catalysts can be used alone or in combination. As an exemplary raw material, preferably produced by Wanhua Chemical Co., Ltd. KC100; and / or,

[0085] The isocyanate includes at least one of an isocyanate monomer, a polyisocyanate or an isocyanate prepolymer; preferably one or a mixture of urethane-modified MDI, polymeric MDI, 4,4-MDI, 2,4-MDI, carbodiimide-modified MDI, TDI or IPDI, as an exemplary raw material, preferably produced by Wanhua Chemical 8629.

[0086] As an operative method, in the two-component polyurethane composition of the present invention, the HFBMA-co-HEMA polymer is a polymer of hexafluorobutyl methacrylate and 2-hydroxyethyl methacrylate, and has the following structure:

[0087]

[0088] Preferably, the molecular weight of the HFBMA-co-HEMA polymer is 1000-4000.

[0089] As an operative mode, in the two-component polyurethane composition of the present invention, the preparation method of the HFBMA-co-HEMA polymer comprises: under a protective atmosphere, using hexafluorobutyl methacrylate (HFBMA) and 2-hydroxyethyl methacrylate (HEMA) as raw materials, adding a chain transfer agent and an initiator, dissolving them in an organic solvent for polymerization reaction, collecting the reactants and removing the organic solvent, and obtaining the HFBMA-co-HEMA polymer; the specific reaction formula is as follows:

[0090]

[0091] Preferably, the molar ratio of hexafluorobutyl methacrylate to 2-hydroxyethyl methacrylate is 6-15:1:1;

[0092] Preferably, the chain transfer agent comprises dodecyl mercaptan;

[0093] Preferably, the amount of the chain transfer agent added can be used according to the conventional dosage in the art. As an exemplary embodiment, the amount of the chain transfer agent added can be selected to account for 2.0-3.0wt% of the total amount of hexafluorobutyl methacrylate (HFBMA) and 2-hydroxyethyl methacrylate (HEMA);

[0094] Preferably, the initiator comprises AIBN;

[0095] Preferably, the amount of the initiator added can be used according to the conventional dosage in the art. As an exemplary embodiment, the amount of the initiator added can be selected to account for 0.1-0.3wt% of the total amount of hexafluorobutyl methacrylate (HFBMA) and 2-hydroxyethyl methacrylate (HEMA);

[0096] Preferably, the polymerization reaction temperature is 60-70°C and the polymerization reaction time is 3-5h;

[0097] Preferably, the organic solvent comprises anhydrous ethanol.

[0098] The present invention also provides use of the two-component polyurethane composition for preparing a water-washable, yellowing-resistant polyurethane foam material.

[0099] The invention also discloses a water-washable and yellowing-resistant polyurethane foam material, the preparation raw materials of which include the two-component polyurethane composition.

[0100] The present invention also discloses a method for preparing the washable yellowing-resistant polyurethane foam material, comprising the following steps:

[0101] (1) preparing the ingredients according to the selected raw materials and the metering ratio to obtain the A component and the B component for standby use; namely, adding the polyether polyol A, polyether polyol B, polyether polyol C and HFBMA-co-HEMA polymer in metering units into a reaction kettle for stirring and mixing, adding the foaming agent, foam stabilizer and catalyst in metering units in turn, stirring at room temperature to obtain the A component, and taking the B component for standby use;

[0102] (2) Mix the component A and the component B at 20-30° C. and pour into a mold for forming. After the mold is opened, the mixture is allowed to stand.

[0103] Specifically, the preparation method of the washable yellowing-resistant polyurethane foam material is as follows:

[0104] The mixing step includes adding the B component to the A component and rapidly stirring for 3-6 seconds; and / or,

[0105] The time of the forming step is 5-7 minutes; and / or,

[0106] The time of the standing step is 12-24 hours; and / or,

[0107] The method further comprises the step of preparing the HFBMA-co-HEMA polymer.

[0108] The technical solution of the present invention is described in conjunction with the following implementation examples.

[0109] Preparation Example

[0110] This preparation example is used to prepare HFBMA-co-HEMA polymer, that is, hexafluorobutyl methacrylate (HFBMA) and 2-hydroxyethyl methacrylate (HEMA) are used as raw materials, and hexafluorobutyl methacrylate and 2-hydroxyethyl methacrylate polymers with different addition amounts and different block ratios are used to improve the hydrophobic and antioxidant properties of the polyurethane material, so as to obtain a water-washable and yellowing-resistant polyurethane material.

[0111] Hexafluorobutyl methacrylate and 2-hydroxyethyl methacrylate from Shanghai Aladdin Biochemical Technology Co., Ltd. were taken separately, and the inhibitors therein were removed by passing through an alkaline Al2O3 chromatography column. The obtained monomers were added to activated molecular sieves and sealed and stored in a refrigerator.

[0112] Weigh the measured monomers of hexafluorobutyl methacrylate (HFBMA) and 2-hydroxyethyl methacrylate (HEMA), dissolve the chain transfer agent (dodecyl mercaptan) and initiator (AIBN) in anhydrous ethanol solvent, deoxygenate for 0.5 h with N2, and then carry out polymerization reaction in an oil bath at a constant temperature of 65°C for 4 h under N2 protection.

[0113] After the reaction, the three-necked flask was placed in an ice-water bath for cooling, and then vacuum-evaporated at about 50° C. to remove all ethanol solvents to obtain a colloidal liquid polymer of hexafluorobutyl methacrylate and 2-hydroxyethyl methacrylate P (HFBMA-co-HEMA).

[0114] In each preparation example of the present invention, the molar ratio of hexafluorobutyl methacrylate (HFBMA) and 2-hydroxyethyl methacrylate (HEMA) is adjusted to obtain polymers with different block ratios. The specific raw material ratios and block ratios of the prepared copolymers are shown in Table 1 below, which are respectively recorded as P1-P5 according to the different block ratios of the copolymers.

[0115] Table 1 Synthesis of copolymers with different block ratios

[0116]

[0117] The HFBMA-co-HEMA copolymer obtained in this preparation example is used to prepare the desired water-washable and yellowing-resistant polyurethane foam material.

[0118] Example

[0119] In the following examples of the present invention, the desired polyurethane foam material is prepared by using the HFBMA-co-HEMA copolymer prepared in the above preparation examples as a raw material.

[0120] In the following embodiments of the present invention, the raw material composition of the polyurethane foam material provided includes independent component A and component B; wherein,

[0121] The component A comprises the following raw material components: polyether polyol A, polyether polyol B, polyether polyol C, HFBMA-co-HEMA polymer, foaming agent, cross-linking agent, foam stabilizer, and catalyst;

[0122] The B component includes the following raw material components: isocyanate.

[0123] In the following examples of the present invention, the specific composition and ratio of the raw materials selected in each example are shown in Table 2 below.

[0124] In the following embodiments of the present invention, the method for preparing the polyurethane foam material comprises the following steps:

[0125] (1) Ingredients: polyether polyol A, polyether polyol B, polyether polyol C and HFBMA-co-HEMA polymers (P1-P6) with different copolymer block ratios are sequentially added into a stirring kettle according to the formula amounts in Table 2 below and stirred. After uniform stirring, a cross-linking agent, a catalyst, a foam stabilizer and a foaming agent are added in the formula amounts and stirred sufficiently at room temperature to obtain component A; a selected amount of isocyanate is separately taken for standby use;

[0126] (2) Preparation of polyurethane samples: The material temperatures of the above-mentioned components A and B are controlled at 25°C respectively, and the component B is added into the evenly mixed component A according to the measurement unit. The mixture is rapidly stirred for 5 seconds and poured into a mold. The mold is opened after 6 minutes, and the foam is left to stand for 18 hours to obtain a washable and yellowing-resistant polyurethane material.

[0127] Table 2 Washable sponge raw material formula

[0128]

[0129]

[0130] Comparative Example 1

[0131] The raw material composition of the polyurethane foam material prepared in this comparative example includes independent component A and component B; wherein,

[0132] The A component includes the following raw material components: polyether polyol A ( F3140) 55 parts by weight, polyether polyol B ( F3156) 15 parts by weight, polyether polyol C ( S3007) 30 parts by weight, foaming agent (deionized water) 2.5 parts by weight, crosslinking agent (diethanolamine) 0.5 parts by weight, foam stabilizer (B8002) 1.5 parts by weight, catalyst ( KC100) 2 parts by weight;

[0133] The B component includes the following raw material components: isocyanate ( 8629)66 parts by weight.

[0134] The preparation method of the polyurethane foam material in this comparative example is the same as that of the aforementioned embodiment, the only difference being that the HFBMA-co-HEMA polymer is not added.

[0135] Comparative Example 2

[0136] The raw material composition for preparing the polyurethane foam material in this comparative example is the same as that in Example 7, except that the HFBMA-co-HEMA polymer is not added, but an equal amount of hexafluorobutyl methacrylate (HFBMA) is added.

[0137] Comparative Example 3

[0138] The raw material composition for preparing the polyurethane foam material in this comparative example is the same as that in Example 7, except that the HFBMA-co-HEMA polymer is not added, but an equal amount of 2-hydroxyethyl methacrylate (HEMA) is added.

[0139] Comparative Example 4

[0140] The raw material composition for preparing the polyurethane foam material in this comparative example is the same as that in Example 7, the only difference is that the HFBMA-co-HEMA polymer is not added, and equal amounts of hexafluorobutyl methacrylate (HFBMA) and 2-hydroxyethyl methacrylate (HEMA) are directly added according to the raw material ratio for preparing the HFBMA-co-HEMA polymer.

[0141] Experimental example

[0142] The polyurethane foam materials prepared in the above Examples 1-16 and Comparative Examples 1-4 were respectively subjected to corresponding performance tests, and the specific test indicators and test methods are as follows:

[0143] Tensile strength test: The tensile strength was measured according to the standard method of GB / T6344-2008.

[0144] Tear strength test: Tear strength was measured according to the standard method of GB / T10808-2006;

[0145] Elongation at break test: Determination of tensile strength according to the standard method specified in GB / T6344-2008;

[0146] Indentation hardness test (CLD): Determine the hardness according to the standard method of GB / T10807-2006 (indentation method);

[0147] Swelling degree test: Soak a 20cm×20cm×5cm sample in water at 25°C. After washing, spin dry the sample and measure its volume. The swelling degree is the ratio of the volume of the sponge after washing to the volume of the sponge before washing multiplied by 100%;

[0148] Washing test: at 25°C, a washable sponge prepared in each embodiment was placed in a commercially available pillowcase and washed in a heavy-load cycle in a commercially available washing machine. After washing, the washable sponge was taken out and dried in an air oven at 60°C to constant weight, and then various performance tests were performed;

[0149] Yellowing test: Under the conditions of 65°C and 65% constant humidity, observe the yellowing of the sponge sample.

[0150] The test results of the washable sponges prepared in Examples 1-16 of the present invention and Comparative Examples 1-4 are shown in Table 3 below.

[0151] Table 3 Washable sponge test results

[0152]

[0153] It can be seen that the polyurethane foam material system of the present invention can effectively improve the yellowing resistance of the sponge, reduce the swelling degree of the sponge after washing, and improve the phenomenon of the decrease in physical properties of the sponge after washing by adding the copolymer of hexafluorobutyl methacrylate and 2-hydroxyethyl methacrylate; at the same time, by adjusting the block ratio of the copolymer of hexafluorobutyl methacrylate and 2-hydroxyethyl methacrylate, its yellowing resistance and swelling degree after washing can be further optimized.

[0154] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the invention.

Claims

1. A two-component polyurethane composition, characterized in that: It comprises independent component A and component B; wherein, The A component includes the following raw material components in parts by weight: Polyether polyol 45-110 parts by weight; 5-10 parts by weight of HFBMA-co-HEMA polymer; A blowing agent, the amount of which accounts for 1.5-3wt% of the total amount of the polyether polyol and the HFBMA-co-HEMA polymer; A cross-linking agent, the amount of which accounts for 0.5-2wt% of the total amount of the polyether polyol and the HFBMA-co-HEMA polymer; A foam stabilizer, the amount of which accounts for 0.5-2wt% of the total amount of the polyether polyol and the HFBMA-co-HEMA polymer; A catalyst, the amount of which accounts for 0.1-2wt% of the total amount of the polyether polyol and the HFBMA-co-HEMA polymer; The B component includes the following raw material components in parts by weight: Isocyanate 50-80 parts by weight.

2. The two-component polyurethane composition according to claim 1, characterized in that: The HFBMA-co-HEMA polymer is a polymer of hexafluorobutyl methacrylate and 2-hydroxyethyl methacrylate, and has the following structure: Preferably, the molecular weight of the HFBMA-co-HEMA polymer is 1000-4000.

3. The two-component polyurethane composition according to claim 1 or 2, characterized in that: The preparation method of the HFBMA-co-HEMA polymer comprises: under a protective atmosphere, using hexafluorobutyl methacrylate and 2-hydroxyethyl methacrylate as raw materials, adding a chain transfer agent and an initiator, dissolving them in an organic solvent for polymerization reaction, collecting the reactants and removing the organic solvent to obtain the HFBMA-co-HEMA polymer; Preferably, the molar ratio of hexafluorobutyl methacrylate to 2-hydroxyethyl methacrylate is 6-15:1; Preferably, the chain transfer agent comprises dodecyl mercaptan; Preferably, the amount of the chain transfer agent added is 2.0-3.0 wt % of the total amount of the hexafluorobutyl methacrylate and the 2-hydroxyethyl methacrylate; Preferably, the initiator comprises AIBN; Preferably, the amount of the initiator added is 0.1-0.3 wt % of the total amount of the hexafluorobutyl methacrylate and the 2-hydroxyethyl methacrylate; Preferably, the polymerization reaction temperature is 60-70°C and the polymerization reaction time is 3-5h; Preferably, the organic solvent comprises anhydrous ethanol.

4. The two-component polyurethane composition according to any one of claims 1 to 3, characterized in that: The polyether polyol comprises at least one of polyether polyol A, polyether polyol B or polyether polyol C; wherein, The polyether polyol A has a weight average molecular weight of 3000-5000, a functionality of 2-4, and an ethylene oxide content of 60-85wt% based on the total mass of propylene oxide and ethylene oxide as 100%; The polyether polyol B has a weight average molecular weight of 2000-4000, a functionality of 2-4, and a propylene oxide content of 60-95wt% based on the total mass of propylene oxide and ethylene oxide as 100%; The weight average molecular weight of the polyether polyol C is 500-1500, the functionality is 2-4, and the content of propylene oxide is 90-100 wt % based on the total mass of propylene oxide and ethylene oxide being 100 wt %.

5. The two-component polyurethane composition according to claim 4, characterized in that: The polyether polyol comprises a mixture of polyether polyol A, polyether polyol B or polyether polyol C; Preferably, the mass ratio of the polyether polyol A, polyether polyol B and polyether polyol C is 20-50:5-20:20-40.

6. The two-component polyurethane composition according to any one of claims 1 to 5, characterized in that: The foaming agent includes one of water, dichloromethane or cyclopentane; and / or, The cross-linking agent includes at least one of alcohol or amine small molecule compounds with a functionality of 2-4, preferably one or a mixture of diethanolamine, triethanolamine, and glycerol; The foam stabilizer comprises a polysiloxane-olefin oxide block copolymer; and / or, The catalyst comprises at least one of an amine catalyst or an organometallic catalyst; and / or, The isocyanate includes at least one of isocyanate monomers, polyisocyanates or isocyanate prepolymers; preferably one or a mixture of urethane-modified MDI, polymeric MDI, 4,4-MDI, 2,4-MDI, carbodiimide-modified MDI, TDI or IPDI.

7. Use of the two-component polyurethane composition according to any one of claims 1 to 6 for preparing a water-washable, yellowing-resistant polyurethane foam material.

8. A washable yellowing-resistant polyurethane foam material, characterized in that: The raw materials for preparing the polyurethane composition include the two-component polyurethane composition described in any one of claims 1 to 6.

9. A method for preparing the washable yellowing-resistant polyurethane foam material as claimed in claim 8, characterized in that: The steps include: (1) respectively preparing the ingredients according to the selected raw materials and the metering ratio to obtain the component A and the component B for standby use; (2) Mix the component A and the component B at 20-30° C. and pour into a mold for forming. After the mold is opened, the mixture is allowed to stand.

10. The method for preparing the washable yellowing-resistant polyurethane foam material according to claim 9, characterized in that: The mixing step includes adding the B component to the A component and rapidly stirring for 3-6 seconds; and / or, The time of the forming step is 5-7 minutes; and / or, The time of the standing step is 12-24 hours; and / or, The method further comprises the step of preparing the HFBMA-co-HEMA polymer.

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