Polyether polyol and preparation method thereof, polyurethane foam and preparation method thereof

Abstract

The present invention belongs to the technical field of viscoelastic polyurethane foam, and in particular relates to a polyether polyol and a preparation method thereof, a polyurethane foam and a preparation method thereof; the raw material components of the viscoelastic polyurethane foam include a component A and a component B; component A is an isocyanate-reactive component, and component B is an isocyanate; wherein the NCO content of the isocyanate is 18 to 35 wt%; the isocyanate-reactive component includes a polyether polyol composition and a foaming agent, and the polyether polyol composition includes at least one highly active polyether polyol A1; the present invention can reduce the VOC content and odor of the viscoelastic polyurethane foam, obtain a viscoelastic foam with an adjustable loss factor, and has excellent mechanical properties, while meeting normal production process efficiency.

Description

Technical Field

[0001] The present invention belongs to the technical field of viscoelastic polyurethane foam, and in particular relates to a polyether polyol and a preparation method thereof, and polyurethane foam and a preparation method thereof. Background Art

[0002] Due to its superior physical properties and processing flexibility, polyurethane foam is widely used in transportation vehicles such as automobiles, high-speed trains, and aircraft. The damping properties of viscoelastic polyurethane foam give it excellent tactile properties and sound insulation and noise reduction effects, making it commonly used in the production of automotive acoustic components and furniture mattresses.

[0003] In recent years, manufacturers in both the automotive and home furnishing industries have imposed stricter requirements on their foam suppliers, particularly regarding the volatile organic compound (VOC) content and odor requirements for polyurethane foam. According to national standard GB18586-2001, a more stringent definition of VOC is adopted: a general term for volatile organic compounds with a melting point below room temperature and a boiling point between 50°C and 260°C. VOCs, which are irritating and have some toxicity, primarily include aldehydes, amines, benzene compounds, and low-molecular-weight alcohols. VOCs and odors primarily originate from catalysts, polyethers, silicone oils, and other small and medium-molecular-weight alcohols in the system, with catalysts and polyethers being the dominant sources. In addition, the technical solutions adopted by traditional viscoelastic polyurethane foams are mostly the composite use of low molecular weight polyether polyols and high molecular weight polyether polyols (polyether polyols with a weight average molecular weight of less than 1000 are classified as low molecular weight polyether polyols, and polyether polyols with a weight average molecular weight greater than or equal to 2000 are classified as high molecular weight polyether polyols). Due to the composition of low molecular weight polyether polyols, the resulting polyurethane foam has a strong odor, a high VOC, and slightly poor mechanical properties such as tensile strength and tearing.

[0004] Chinese patent document CN104149455A discloses a slow-rebound polyurethane composite material for automobiles with a high damping loss factor and sound insulation performance. The method includes a method for preparing a slow-rebound foam. However, the introduction of an amine catalyst causes the resulting slow-rebound polyurethane composite material to have a pungent odor and potential VOC source risks. Furthermore, the technical solution uses a slow-rebound polyether polyol 2000D with a molecular weight of 700, resulting in poor mechanical properties such as tensile and tearing properties.

[0005] Chinese patent document CN109021193A discloses a highly breathable viscoelastic polyurethane foam based on an MDI system and a preparation method thereof. The foam uses a polyether monool with a functionality of 1 and a low molecular weight polyether polyol. However, the foam also suffers from problems such as a strong odor, high VOC content, and slightly poor mechanical properties such as stretching and tearing.

[0006] Chinese patent document CN104031235A discloses a method for preparing viscoelastic polyurethane sound-absorbing foam, which uses a polyether polyol component with a high ethylene oxide content. However, this component is not the main component and still needs to be used in combination with a low molecular weight polyether polyol. Research on odor and VOC indicators is not involved.

[0007] Therefore, a viscoelastic polyurethane foam technology solution using a highly active polyether polyol system is needed to study how to reduce the VOC and odor of the viscoelastic polyurethane foam while obtaining a viscoelastic foam with an adjustable loss factor and excellent mechanical properties while meeting normal production process efficiency. Summary of the Invention

[0008] The object of the present invention is to provide a polyether polyol and a preparation method thereof, a polyurethane foam and a preparation method thereof, in order to address some technical problems existing in conventional viscoelastic polyurethane foams. The present invention can reduce the amount of catalyst used or eliminate the use of a catalyst while simultaneously regulating the influence of the ethylene oxide content in the polyether polyol on the damping performance of the product, thereby breaking away from the modification method using conventional low-molecular-weight slow-rebound polyether polyols. This fundamentally reduces the VOC and odor of the viscoelastic polyurethane foam, while obtaining a viscoelastic foam with an adjustable loss factor, superior mechanical properties, and the ability to meet normal production process efficiency.

[0009] In order to achieve the above object, the present invention provides the following technical solutions:

[0010] In a first aspect, a highly active polyether polyol A1 is provided, wherein the highly active polyether polyol A1 is a product obtained by ring-opening polymerization of an alkylene oxide compound as an initiator and a polymerization monomer; wherein

[0011] The initiator comprises at least one or more polyamines having a tertiary or secondary amine group at one end and a primary amine group at the other end, and optionally comprises other small molecule amine compounds (such as triethanolamine, diethylenetriamine and other amine small molecules), and / or small molecule polyols (such as ethylene glycol, glycerol, trimethylolpropane, tetrapentanol and sucrose);

[0012] The functionality of the highly active polyether polyol A1 is 2-5 (e.g., 2.5, 3, 3.5, 4, 4.5), preferably 2-4. In the present invention, the type of initiator used in the highly active polyether polyol A1 and the mixing ratio of the components in the initiator determine the functionality of the highly active polyether polyol A1.

[0013] According to the polyether polyol A1 provided by the present invention, in some embodiments, the polyamine containing a tertiary or secondary amine group at one end and a primary amine group at the other end has a specific structure as shown below:

[0014] (I),

[0015] (II),

[0016] (III),

[0017] (IV),

[0018] (V),

[0019] (VI),

[0020] (VII);

[0021] Among them, R1, R2, R3, R5, R6, R7, R8, R9, R 10 、R 11 、R 12 and R 13 Each independently represents one or more of -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-;

[0022] R4 is one or more of -CH3, -CH2CH3, -CH2CH2CH3, and -CH2CH2CH2CH3.

[0023] In some embodiments, the polyamine containing a tertiary or secondary amine group at one end and a primary amine group at the other end is selected from 3-dimethylaminopropylamine and / or N,N-dimethyldipropylenetriamine (i.e., shown in formula (I) and formula (IV)).

[0024] In the structure of the polyamine initiator containing a tertiary or secondary amine group at one end and a primary amine group at the other end, one end of the molecule contains a secondary / primary amine group. After the N atom in the amine group acts as an initiator and polymerizes with a polymerizable monomer, a polyether polyol with a tertiary amine group at one end is formed. The steric hindrance of the terminal N atom is small, and the high activity of its lone pair electrons is maintained. This enables the polyamine initiator to function as a catalyst while eliminating the need for an amine catalyst, thereby avoiding the generation of VOCs and odors by the amine catalyst, and thereby reducing the VOC content of the final product, the polyurethane foam.

[0025] According to the polyether polyol A1 provided by the present invention, in some embodiments, if the initiator is a mixture of a polyamine containing a tertiary or secondary amine group at one end and a primary amine group at the other end and other small molecule amine compounds (such as triethanolamine, diethylenetriamine, etc.), in the mixture, the molar ratio of the two can be (2-8): (8-2); or, if the initiator is a polyamine containing a tertiary or secondary amine group at one end and a primary amine group at the other end and a small molecule polyol (such as ethylene glycol, glycerol, trimethylolpropane, tetrapentanol and sucrose), in the mixture, the molar ratio of the two can be (2-8): (8-2).

[0026] According to the polyether polyol A1 provided by the present invention, in some embodiments, the alkylene oxide compound is ethylene oxide, or a mixture of ethylene oxide and at least one of propylene oxide and butylene oxide, preferably a mixture of ethylene oxide and propylene oxide.

[0027] In some embodiments, the ethylene oxide content in the highly active polyether polyol A1 is ≥40 wt % (e.g., 42 wt %, 45 wt %, 50 wt %, 55 wt %, 60 wt %, 65 wt %, 70 wt %, 75 wt %, 80 wt %, 85 wt %), preferably 40 wt % to 90 wt %.

[0028] The high content of ethylene oxide in the highly active polyether polyol A1 makes the system rich in -CH2-CH2-O- chain segments, which have high regularity. Compared with the oxygen in the ether bond of the structure obtained from propylene oxide, it is not interfered by the side methyl group, has greater polarity and better crystallinity, so that the obtained polyurethane product has excellent damping effect. The damping ratio of the viscoelastic polyurethane foam obtained from the system can be regulated by controlling the content of ethylene oxide in the polyether polyol A1. The addition of a high-content ethylene oxide component during the polymerization process can effectively reduce the side reactions caused by the isomerization of propylene oxide in the system, reduce the unsaturation of the obtained polyether polyol, thereby improving the stability and quality of the polyether polyol, and further reducing the odor and VOC of the obtained polyurethane foam. The use of a high ethylene oxide content makes the primary hydroxyl content of the obtained polyether polyol higher, thereby ensuring the high activity of the polyether polyol. In addition, due to the high hydrophilicity of ethylene oxide, it is beneficial to the stability of the aqueous foaming system.

[0029] According to the polyether polyol A1 provided by the present invention, in the ring-opening polymerization reaction, the molar ratio of the initiator to the alkylene oxide compound is 1:k, and k can be selected from integers of 1 to 400 (for example, 2, 4, 5, 6, 8, 10, 20, 40, 50, 80, 100, 120, 150, 180, 200, 220, 250, 300, 350, 380); the molar ratio of the initiator to ethylene oxide and propylene oxide is 1:m:n, wherein m and n can each independently be selected from integers of 0 to 200 (for example, 2, 4, 5, 6, 8, 10, 20, 40, 50, 80, 100, 120, 150, 160, 180), and m and n cannot be 0 at the same time.

[0030] According to the polyether polyol A1 provided by the present invention, in some embodiments, the hydroxyl value of the highly active polyether polyol A1 is 22-112 mgKOH / g (for example, 23 mgKOH / g, 25 mgKOH / g, 28 mgKOH / g, 30 mgKOH / g, 35 mgKOH / g, 40 mgKOH / g, 50 mgKOH / g, 55 mgKOH / g, 60 mgKOH / g, 80 mgKOH / g, 90 mgKOH / g, 100 mgKOH / g, 105 mgKOH / g), preferably 28-56 mgKOH / g; the primary hydroxyl content is ≥65% (for example, 68%, 70%, 72%, 75%, 80%, 82%, 84%, 85%, 88%, 90%), preferably ≥80%.

[0031] In some embodiments, the viscosity of the highly active polyether polyol A1 is in the range of 800-2500 mPa·s (e.g., 820 mPa·s, 850 mPa·s, 900 mPa·s, 1000 mPa·s, 1100 mPa·s, 1200 mPa·s, 1400 mPa·s, 1500 mPa·s, 1600 mPa·s, 1800 mPa·s, 2000 mPa·s, 2200 mPa·s, 3000 mPa·s, 3500 mPa·s, 3600 mPa·s, 3700 mPa·s, 3800 mPa·s, 3900 mPa·s, 4000 mPa·s, 4100 mPa·s, 4200 mPa·s, 4300 mPa·s, 4400 mPa·s, 4500 mPa·s, 4600 mPa·s, 4700 mPa·s, 4800 mPa·s, 4900 mPa·s, 5000 mPa·s, 5100 mPa·s, 5200 mPa·s, 5300 mPa·s, 5400 mPa·s, 5500 mPa·s, 5600 mPa·s, 5700 mPa·s, 5800 mPa·s, 5900 mPa·s, 6000 mPa·s, 6100 mPa·s, 6200 mPa·s, 6300 mPa·s, 6400 mPa·s, 6500 mPa·s, 6600 mPa·s, 6700 mPa·s, 6800 mPa·s, 690 Pa·s, 2400mPa·s), may be within the range of 900-1200mPa·s, may be within the range of 1000-1500mPa·s, may be within the range of 1200-2000mPa·s, may be within the range of 2000-2300mPa·s, may be within the range of 1000-2400mPa·s, may be within the range of 1500-2400mPa·s, may be within the range of 1800-2400mPa·s.

[0032] In some embodiments, the molecular weight of the highly active polyether polyol A1 is in the range of 3500-8000 (e.g., 3600, 4000, 4200, 4500, 4800, 5000, 5400, 5500, 6000, 6500, 7000, 7500, 7900).

[0033] In a second aspect, a method for preparing the highly active polyether polyol A1 as described above is provided, comprising the following steps:

[0034] S1: Add the initiator and catalyst into the reactor, heat the system, and introduce the alkylene oxide compound to carry out the reaction;

[0035] S2: Adjust the system temperature, then introduce the alkylene oxide compound and continue the reaction;

[0036] S3: The reaction material obtained in step S3 is transferred to a refining kettle, and then acid solution is added thereto for neutralization, followed by dehydration and filtration to obtain a highly active polyether polyol.

[0037] According to the preparation method of polyether polyol provided by the present invention, in some embodiments, in step S1, the catalyst is one or more of an alkali metal catalyst, an inorganic base, an organic base, and a phosphazene catalyst, preferably selected from one or more of sodium metal, sodium hydroxide, potassium hydroxide, potassium tert-butoxide, phosphinothioate, nitrile acid, and phosphate ester; the added amount of the catalyst is 0.02-0.8 wt% (for example, 0.03 wt%, 0.04 wt%, 0.08 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.5 wt%, 0.6 wt%) of the total amount of the initiator and the alkylene oxide compound, preferably 0.05-0.4 wt%.

[0038] In some embodiments, in step S1, the system temperature is 85-110°C (e.g., 90°C, 95°C, 100°C, 105°C), and the system pressure is lower than 0.5 MPaG (e.g., 0.4 MPaG and below, 0.3 MPaG and below);

[0039] In some embodiments, in step S1, the alkylene oxide compound introduced is a mixture of propylene oxide and ethylene oxide, and the addition cycle of the alkylene oxide compound is 5-10 hours (for example, 6 hours, 8 hours, 9 hours); the reaction time is 0.5-2 hours (for example, 1 hour, 1.5 hours).

[0040] According to the method for preparing polyether polyol provided by the present invention, in some embodiments, in step S2, the system temperature is adjusted to 110-130° C. (e.g., 115° C., 120° C., 125° C.), and the system pressure is lower than 0.5 MPaG (e.g., 0.4 MPaG and below, 0.3 MPaG and below);

[0041] In some embodiments, in step S2, the added alkylene oxide compound is ethylene oxide, and the addition cycle of the alkylene oxide compound is 1-3 hours (for example, 1.5 hours, 2 hours, 2.5 hours); the reaction time is 0.5-2 hours (for example, 1 hour, 1.5 hours).

[0042] In the present invention, there is no particular limitation on the amount of the alkylene oxide compound added in step S1 and the amount of the alkylene oxide compound added in step S2, as long as the content of ethylene oxide in the finally obtained high-activity polyether polyol is ensured to be ≥40 wt%.

[0043] According to the method for preparing polyether polyol provided by the present invention, in some embodiments, in step S3, the acid solution is selected from one or more of a phosphoric acid aqueous solution, a sulfuric acid aqueous solution, an acetic acid aqueous solution, and a hydrochloric acid aqueous solution, preferably a phosphoric acid aqueous solution and / or a hydrochloric acid aqueous solution;

[0044] In some embodiments, during the neutralization process, the pH value of the system is adjusted to 4-7 by adding an amount of acid solution.

[0045] In some embodiments, in step S3, the water content in the reactant is reduced to <500 ppm by the dehydration, for example, below 450 ppm, below 400 ppm, below 300 ppm, below 200 ppm, below 100 ppm, below 50 ppm, below 20 ppm, below 10 ppm, below 5 ppm.

[0046] In a third aspect, a viscoelastic polyurethane foam is provided, wherein the raw material components thereof include: component A and component B; component A is an isocyanate reactive component, and component B is an isocyanate; wherein,

[0047] The NCO content of the isocyanate is 18 to 35 wt% (e.g., 20 wt%, 24 wt%, 25 wt%, 28 wt%, 30 wt%, 34 wt%), preferably 22 to 32 wt%;

[0048] The isocyanate-reactive component includes a polyether polyol composition and a foaming agent, wherein the polyether polyol composition includes at least one of the highly active polyether polyol A1 as described above or the highly active polyether polyol A1 prepared by the preparation method as described above.

[0049] In some embodiments of the viscoelastic polyurethane foam provided by the present invention, the isocyanate is selected from one or more of polyphenylmethane polyisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, and a polyol-modified isocyanate prepolymer; preferably, the isocyanate is a mixture of polyphenylmethane polyisocyanate, 4,4-diphenylmethane diisocyanate, and a polyol-modified isocyanate prepolymer. The polyphenylmethane polyisocyanate may be a mixture of polyphenylmethane polyisocyanates having a functionality greater than or equal to 3.

[0050] According to the viscoelastic polyurethane foam provided by the present invention, in some embodiments, the polyether polyol composition further comprises polyether polyol A2 (the polyether polyol A2 may be prepared using ordinary glycerol or other polyamines other than the one containing a tertiary or secondary amine group at one end and a primary amine group at the other end as an initiator);

[0051] In some embodiments, the polyether polyol A2 has an average functionality of 3 to 5 (e.g., 4), a hydroxyl value of 24 to 42 mgKOH / g (e.g., 25 mgKOH / g, 28 mgKOH / g, 30 mgKOH / g, 32 mgKOH / g, 34 mgKOH / g, 35 mgKOH / g, 38 mgKOH / g, 40 mgKOH / g); and a molecular weight of 3200-6000.

[0052] In some embodiments, the polyether polyol A2 is a product obtained by ring-opening polymerization using a small molecule alcohol or a small molecule amine with a functionality of 3-5 as an initiator and an alkylene oxide compound as a polymerization monomer; wherein the alkylene oxide compound is a mixture of ethylene oxide and propylene oxide, and the content of ethylene oxide is 20~40wt% (for example, 22wt%, 24wt%, 25wt%, 28wt%, 30wt%, 32wt%, 34wt%, 35wt%, 38wt%); based on the weight of the polyether polyol A2, the primary hydroxyl content is ≥80%, for example, 82wt%, 84wt%, 85wt%, 90wt% (calculated based on the amount of primary hydroxyl groups and secondary hydroxyl groups).

[0053] According to the viscoelastic polyurethane foam provided by the present invention, in some embodiments, the foaming agent is selected from one or more of water, CO2, dichlorofluoroethane, butane, n-pentane, cyclopentane and isopentane, preferably water.

[0054] According to the viscoelastic polyurethane foam provided by the present invention, in some embodiments, the amount of each component in the isocyanate reactive component is as follows:

[0055] Highly active polyether polyol A1, 60-100 parts by mass, for example, 62 parts by mass, 65 parts by mass, 68 parts by mass, 70 parts by mass, 75 parts by mass, 80 parts by mass, 85 parts by mass, 90 parts by mass, 95 parts by mass;

[0056] Polyether polyol A2, 0-40 parts by mass, for example, 1 part by mass, 2 parts by mass, 4 parts by mass, 5 parts by mass, 10 parts by mass, 12 parts by mass, 15 parts by mass, 20 parts by mass, 25 parts by mass, 30 parts by mass, 35 parts by mass, 38 parts by mass;

[0057] The foaming agent is 3 to 6 parts by mass, for example, 3.5 parts by mass, 4 parts by mass, 4.5 parts by mass, 5 parts by mass, and 5.5 parts by mass; wherein the amount of the foaming agent is based on 100 parts of the total amount of the highly active polyether polyol A1 and the polyether polyol A2.

[0058] In some embodiments, the isocyanate-reactive component may further include auxiliary agents. These auxiliary agents may be known additives and adjuvants. For example, commonly used additives in polyurethane flexible foam include foam stabilizers, surfactants, and crosslinkers. To aid molding and other functional benefits, auxiliary agents such as catalysts, chain extenders, cell openers, flame retardants, colorants, and other fillers may also be added. The amounts of these additives and adjuvants used are conventional in the art and will not be elaborated here.

[0059] In the technical solution of the present invention, the isocyanate-reactive component can be used in combination with a surfactant and a cross-linking agent; wherein the surfactant can be a foam stabilizer, such as a polysiloxane-polyalkylene oxide block copolymer, to stabilize or adjust the cells of the foam plastic, preferably Evonik B8734LF2 as an example; the cross-linking agent is a trihydric or polyhydric alcohol or amine commonly used in polyurethane foam products, preferably triethanolamine or diethanolamine as examples.

[0060] The surfactant can be present in an amount of 0-1 part by weight (e.g., 0.1 part, 0.2 part, 0.4 part, 0.5 part, or 0.8 part); the cross-linking agent can be present in an amount of 0-1 part by weight (e.g., 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, or 0.8 part). The amounts of the surfactant and cross-linking agent used are based on 100 parts of the total amount of the highly active polyether polyol A1 and the polyether polyol A2.

[0061] According to the viscoelastic polyurethane foam provided by the present invention, in some embodiments, the mass ratio of the component A to the component B is 100:(30~70), for example, 100:35, 100:40, 100:45, 100:50, 100:55, 100:60, 100:65, 100:68, preferably 100:(45~65).

[0062] In a fourth aspect, there is provided a method for preparing the viscoelastic polyurethane foam as described above, comprising the steps of:

[0063] (1) uniformly mixing the raw materials of the isocyanate reactive component to obtain the component A;

[0064] (2) At 20-40°C (e.g., 25°C, 30°C, 35°C), the obtained component A and the component B are fully mixed and stirred, and then quickly injected into a mold for foaming. After 60-100 seconds (e.g., 65 seconds, 70 seconds, 75 seconds, 80 seconds, 85 seconds, 90 seconds, 95 seconds), the mold is opened to obtain the polyurethane foam; wherein the temperature of the mold is 50-80°C (e.g., 55°C, 60°C, 65°C, 70°C, 75°C).

[0065] In the preparation steps of the viscoelastic polyurethane foam, any specific preparation parameters and processes not described in detail may be those commonly used by those skilled in the art.

[0066] The polyurethane foam obtained by the preparation method has a molding density of 50 to 80 kg / m 3 , suitable for foaming molding in molds at 50-80℃, with high production efficiency.

[0067] In a fifth aspect, there is provided a use of the viscoelastic polyurethane foam as described above or the viscoelastic polyurethane foam prepared by the preparation method as described above in the preparation of high-resilience polyurethane soft foam (such as automotive parts, furniture mattresses, etc.).

[0068] In the present invention, the specific operation and process conditions for the use of the viscoelastic polyurethane foam in high-resilience polyurethane soft foam can be conventionally selected in the art and will not be described in detail here.

[0069] The viscoelastic polyurethane foam of the present invention can be used, for example, in the preparation of interior products such as automotive carpets and front panels.

[0070] The beneficial effects of the technical solution of the present invention are at least:

[0071] The present invention uses highly active polyether polyols. By improving the raw material composition, a highly active polyether can be obtained. The viscoelastic polyurethane foam prepared using the polyether polyol as a raw material has controllable damping, excellent low VOC and odor characteristics, and low density and rapid properties. It is suitable for the production process requirements of parts for automobiles, home furnishings, etc., and further improves the health and comfort of end users. That is, the present invention can reduce the VOC and odor of the viscoelastic polyurethane foam while obtaining a viscoelastic foam with an adjustable loss factor, excellent mechanical properties, and can meet the normal production process efficiency. DETAILED DESCRIPTION

[0072] In order to understand the technical features and content of the present invention in detail, the preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described in the examples, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments described herein. Where specific conditions are not specified in the examples, they are carried out according to conventional conditions or conditions recommended by the manufacturer.

[0073] In the following examples and comparative examples, the sources of some reagents or raw materials used, unless the manufacturer is specified, are conventional products that can be purchased commercially.

[0074] Among them, some of the raw materials used in each embodiment and comparative example are described as follows:

[0075] Highly active polyether polyol A1-1 is obtained by ring-opening polymerization using the polyamine compound shown in structure 1 as an initiator, propylene oxide and ethylene oxide as polymerization monomers, and ethylene oxide as end-capping. The ethylene oxide content is 60 wt %, the primary hydroxyl content is 87%, the hydroxyl value is 28 mgKOH / g, and the viscosity (25°C) is 2050-2350 mPa·s.

[0076] , structure 1, i.e., 3-dimethylaminopropylamine, was purchased from Aladdin;

[0077] The preparation method of highly active polyether polyol A1-1 comprises the following steps:

[0078] 1) Add 102.18 g (1 mol) of 3-dimethylaminopropylamine and potassium hydroxide (the amount used is equivalent to 0.2 wt% of the total mass of 3-dimethylaminopropylamine, propylene oxide, and ethylene oxide) to a self-priming reactor; seal the reactor and replace it with nitrogen three times. When the reactor temperature reaches 65°C, evacuate the reactor for 1 hour, heat the reactor to 110°C and control the pressure below 0.5 MPa, add 1700 g of propylene oxide and 1700 g of ethylene oxide, and complete the addition within 5 hours. Perform aging reaction until the pressure no longer decreases;

[0079] 2) Adjust the system temperature to 120°C, control the system pressure below 0.4 MPa, add 780 g of ethylene oxide, and complete the addition within 2 hours. Continue the aging reaction until the pressure no longer decreases;

[0080] 3) The reaction mass obtained in step S3 was transferred to a refining kettle and cooled to 75-80°C for 1 hour to remove monomers. Aqueous hydrochloric acid was then added to the resulting product for neutralization, and the pH of the system was adjusted to approximately 7. Water (reduced to <500 ppm) and unreacted hydrochloric acid were then removed. The product was filtered and discharged to obtain highly active polyether polyol A1-1. The product was then measured for parameters such as primary hydroxyl content, hydroxyl value, and viscosity.

[0081] Highly active polyether polyol A1-2 is obtained by ring-opening polymerization using a mixture of the polyamine compound shown in Structure 1 above and diethylenetriamine as a mixed initiator, propylene oxide and ethylene oxide as polymerization monomers, and ethylene oxide as end-capping. The ethylene oxide content is 90 wt %, the primary hydroxyl content is 91%, the hydroxyl value is 34 mgKOH / g, and the viscosity (25°C) is 1850-2150 mPa·s.

[0082] Diethylenetriamine, purchased from Aladdin;

[0083] The preparation method of highly active polyether polyol A1-2 comprises the following steps:

[0084] 1) Add 61.3 g (0.6 mol) of 3-dimethylaminopropylamine, 41.24 g (0.4 mol) of diethylenetriamine, and a phosphazene composite catalyst (the amount used is equivalent to 0.05 wt% of the total mass of 3-dimethylaminopropylamine, diethylenetriamine, propylene oxide, and ethylene oxide, and the composition of the phosphazene composite catalyst is a 1:1 mass ratio of phosphazene to potassium hydroxide) to a self-priming reactor; seal the reactor, replace the atmosphere with nitrogen three times, heat the reactor to 70°C, evacuate the reactor for 1 hour, heat the reactor to 110°C and control the pressure below 0.4 MPa, add 1100 g of ethylene oxide, and complete the addition within 1 hour; then add 500 g of propylene oxide and 2100 g of ethylene oxide, and complete the addition within 4 hours; and perform an aging reaction until the pressure no longer decreases;

[0085] 2) Adjust the system temperature to 125°C, control the system pressure below 0.3 MPa, add 1500 g of ethylene oxide, and complete the addition within 2 hours. Continue the aging reaction until the pressure no longer decreases;

[0086] 3) The reaction mass obtained in step S3 was transferred to a refining kettle. The mass was cooled to 75-80°C for 1 hour to remove monomers. Aqueous hydrochloric acid was then added to the resulting product for neutralization, and the pH of the system was adjusted to approximately 7. Water (reduced to <500 ppm) and unreacted hydrochloric acid were then removed. The product was filtered and discharged to obtain highly active polyether polyol A1-2. The product was then measured for parameters such as primary hydroxyl content, hydroxyl value, and viscosity.

[0087] Highly active polyether polyol A1-3 is obtained by ring-opening polymerization using the polyamine compound shown in structure 2 as an initiator, propylene oxide and ethylene oxide as polymerization monomers, and ethylene oxide as an end-capping agent, wherein the ethylene oxide content is 40wt%, the primary hydroxyl content is 84%, the hydroxyl value is 35mgKOH / g, and the viscosity (25°C) is 900-1100 mPa·s;

[0088] , structure 2, i.e., N,N-dimethyldipropylenetriamine, was purchased from Aladdin;

[0089] The preparation method of highly active polyether polyol A1-3 comprises the following steps:

[0090] 1) Add 159.3 g (1 mol) of N,N-dimethyldipropylenetriamine and a phosphazene composite catalyst (the amount used is equivalent to 0.05 wt% of the total mass of N,N-dimethyldipropylenetriamine, propylene oxide, and ethylene oxide, and the composition of the phosphazene composite catalyst is a 2:1 mass ratio of phosphazene to potassium hydroxide) to a self-priming reactor; seal the reactor and replace it with nitrogen three times. When the reactor temperature reaches 90°C, evacuate the reactor for 1 hour, heat the reactor to 110°C, control the pressure below 0.4 MPa, add 2890 g of propylene oxide and 950 g of ethylene oxide, and complete the addition within 5 hours. Perform an aging reaction until the pressure no longer decreases;

[0091] 2) Adjust the system temperature to 130°C, control the system pressure below 0.3 MPa, add 980 g of ethylene oxide, and complete the addition within 2 hours. Continue the aging reaction until the pressure no longer decreases;

[0092] 3) The reaction mass obtained in step S3 was transferred to a refining kettle. The mass was cooled to 75-80°C for 1 hour to remove monomers. Aqueous hydrochloric acid was then added to the resulting product for neutralization, and the pH of the system was adjusted to approximately 7. Water (reduced to <500 ppm) and unreacted hydrochloric acid were then removed. The product was filtered and discharged to obtain highly active polyether polyol A1-3. The product was then measured for parameters such as primary hydroxyl content, hydroxyl value, and viscosity.

[0093] Highly active polyether polyol A1-4 is obtained by ring-opening polymerization using the polyamine compound shown in structure 2 as an initiator, propylene oxide and ethylene oxide as polymerization monomers, and ethylene oxide as end-capping. The ethylene oxide content is 60 wt %, the primary hydroxyl content is 88%, the hydroxyl value is 35 mgKOH / g, and the viscosity (25°C) is 1250-1450 mPa·s.

[0094] The preparation method of highly active polyether polyol A1-4 comprises the following steps:

[0095] 1) Add 159.3 g (1 mol) of N,N-dimethyldipropylenetriamine and a phosphazene composite catalyst to a self-priming reactor (the amount is equivalent to 0.05 wt% of the total mass of N,N-dimethyldipropylenetriamine, propylene oxide, and ethylene oxide, and the composition of the phosphazene composite catalyst is a mass ratio of phosphazene to potassium hydroxide of 2:1); close the reactor, replace the atmosphere with nitrogen three times, and when the reactor temperature reaches 90°C, evacuate the reactor for 1 hour. Then, heat the reactor to 110°C while controlling the pressure below 0.4 MPa, add 950 g of ethylene oxide, and complete the addition within 1 hour. Continue to add 1900 g of propylene oxide and 950 g of ethylene oxide, and complete the addition within 4 hours. Perform an aging reaction until the pressure no longer decreases.

[0096] 2) Adjust the system temperature to 130°C, control the system pressure below 0.3 MPa, add 980 g of ethylene oxide, and complete the addition within 2 hours. Continue the aging reaction until the pressure no longer decreases;

[0097] 3) The reaction mass obtained in step S3 was transferred to a refining kettle. The mass was cooled to 75-80°C for 1 hour to remove monomers. Aqueous hydrochloric acid was then added to the resulting product for neutralization, and the pH of the system was adjusted to approximately 7. Water (reduced to <500 ppm) and unreacted hydrochloric acid were then removed. The product was filtered and discharged to obtain highly active polyether polyol A1-4. The product was then measured for parameters such as primary hydroxyl content, hydroxyl value, and viscosity.

[0098] Highly active polyether polyol A1-5 is obtained by ring-opening polymerization using the polyamine compound shown in structure 2 as an initiator, propylene oxide and ethylene oxide as polymerization monomers, and ethylene oxide as end-capping. The ethylene oxide content is 80 wt %, the primary hydroxyl content is 90%, the hydroxyl value is 36 mgKOH / g, and the viscosity (25°C) is 1950-2250 mPa·s.

[0099] The preparation method for highly active polyether polyol A1-5 is similar to that for highly active polyether polyol A1-4, except that the amounts of ethylene oxide and propylene oxide are adjusted in steps 2) and 3) based on the ethylene oxide content. In step S2, the amounts of ethylene oxide and propylene oxide are 2000 g and 900 g, respectively, and in step S3, the amount of ethylene oxide is 1650 g. The remaining steps are identical to those for the preparation of highly active polyether polyol A1-4, yielding highly active polyether polyol A1-5. The resulting product is then tested for parameters such as primary hydroxyl content, hydroxyl value, and viscosity.

[0100] Polyether polyol A2-1, glycerol as an initiator, propylene oxide and ethylene oxide as polymerization monomers, and ethylene oxide end-capping, wherein the ethylene oxide content is 23wt%, the primary hydroxyl content is 85%, and the hydroxyl value is 28mgKOH / g; the molecular weight is 6000;

[0101] Polyether polyol A2-2, trimethylolpropane as an initiator, propylene oxide and ethylene oxide as polymerization monomers, and ethylene oxide end-capping, wherein the ethylene oxide content is 35wt%, the primary hydroxyl content is 88%, and the hydroxyl value is 34mgKOH / g; the molecular weight is 4950;

[0102] Polyether polyol A2-3, glycerol as the initiator, propylene oxide as the polymerization monomer, hydroxyl value of 240mgKOH / g;

[0103] Polyether polyol A2-4, triethanolamine as an initiator, propylene oxide and ethylene oxide as polymerization monomers, and ethylene oxide end-capping, wherein the ethylene oxide content is 23wt%, the primary hydroxyl content is 87%, and the hydroxyl value is 33mgKOH / g;

[0104] Polyether polyol A2-5, triethylenediamine as an initiator, propylene oxide and ethylene oxide as polymerization monomers, and ethylene oxide end-capping, wherein the ethylene oxide content is 21wt%, the primary hydroxyl content is 86%, and the hydroxyl value is 36mgKOH / g;

[0105] Surfactant: Evonik B8734LF2;

[0106] Cross-linking agent 1: triethanolamine;

[0107] Cross-linker 2: diethanolamine;

[0108] Isocyanate B1, a mixture of polyphenylmethane polyisocyanate, 4,4-diphenylmethane diisocyanate and polyol-modified isocyanate prepolymer, with an NCO content of 30%;

[0109] Isocyanate B2, a mixture of polyphenylmethane polyisocyanate, 4,4-diphenylmethane diisocyanate, and a polyol-modified isocyanate prepolymer, with an NCO content of 22%;

[0110] Isocyanate B3, a mixture of polyphenylmethane polyisocyanate, 4,4-diphenylmethane diisocyanate, and a polyol-modified isocyanate prepolymer, with an NCO content of 32%;

[0111] Catalyst 1: Huntsman, dimethylaminopropylamine;

[0112] Catalyst 2: Huntsman, N,N-dimethyl-N,N-bis(2-hydroxypropyl)-1,3-propanediamine.

[0113] Performance tests of the polyurethane foams prepared in various embodiments and comparative examples:

[0114] (1) Hydroxyl value: Tested in accordance with GB / T12008.3-1989 "Determination of hydroxyl value in polyether polyols";

[0115] (2) Viscosity: Tested in accordance with GB / T12008.7-2010 "Plastic polyether polyols - Part 7: Determination of viscosity";

[0116] (3) Foam density: The test is carried out in accordance with ISO845 standard;

[0117] (4) Odor and VOC evaluation standards: BMW cubic warehouse test method, GS97014-3:2022 (VOC) GS97014-4:2021 (Odour);

[0118] (5) Loss factor test: obtained by testing using a dynamic Young's modulus and loss factor tester.

[0119] Please see Table 1 and Table 2 for the test results.

[0120] [Examples 1-12]

[0121] The preparation steps of viscoelastic polyurethane foam are as follows:

[0122] The raw material components include: component A and component B; the formula thereof is as shown in Table 1;

[0123] According to the dosage shown in Table 1, the raw materials of the isocyanate-reactive component were uniformly mixed at 25°C to obtain component A. Then, the obtained component A was thoroughly stirred and mixed with component B at 25°C according to the dosage shown in Table 1, and then quickly injected into a mold at a mold temperature of 65°C for reaction foaming. After 120 seconds, the mold was opened and the foam was removed (the gel time needed to be less than 70 seconds) to obtain polyurethane foam.

[0124] [Comparative Examples 1-5]

[0125] The preparation steps of viscoelastic polyurethane foam are as follows:

[0126] The raw material components include: component A and component B; the formula thereof is as shown in Table 2;

[0127] According to the dosage shown in Table 2, the raw materials of the isocyanate-reactive component were uniformly mixed at 25°C to obtain component A. Then, the obtained component A was thoroughly stirred and mixed with component B at 25°C according to the dosage shown in Table 1, and then rapidly injected into a mold at a mold temperature of 65°C for reaction foaming. After 120 seconds, the mold was opened and the foam was removed (the gel time needed to be less than 70 seconds) to prepare a polyurethane foam.

[0128] Among them, no catalyst was added to the formulation system of Comparative Example 1 and Comparative Examples 4-5, and the polyurethane foam could not be formed, that is, the foam could not be formed normally; therefore, the product performance test of Comparative Examples 1 and Comparative Examples 4-5 could not be carried out.

[0129] In Tables 1 and 2, the raw material components are calculated in parts by mass.

[0130] Table 1

[0131]

[0132] Table 2

[0133]

[0134] The data from the examples show that, by adopting the technical solution of the present invention, the polyurethane foam formula can achieve rapid maturation even without the use of a catalyst. At the same time, by controlling the EO segment content in the system, the damping properties of the product can be regulated, ultimately achieving the preparation of a low-odor, low-VOC damping foam.

[0135] Comparison of Comparative Examples 1-2 with the Examples shows that in Comparative Example 1, when the highly active polyether selected in the present technical solution was not used and no catalyst was added to the formula, the foam could not be formed normally; in Comparative Example 2, when the highly active polyether selected in the present technical solution was not used and a catalyst was added to the formula, although the foam could be formed normally, the odor and VOC content were both high;

[0136] Compared with the examples, Comparative Example 3 is a traditional technical solution for slow rebound foam, which requires the addition of a catalyst and the use of a low molecular weight polyol in the formula, but the odor and VOC content of the obtained foam are both high;

[0137] Comparative Example 4 shows that when the amount ratio of the active polyether polyol used in the non-present technical solution is within the ratio range, the polyether reaction activity will be adversely affected, and foam molding cannot be guaranteed when no catalyst is added to the formula; Comparative Example 5 shows that when the amine initiator non-present technical solution is used to prepare the polyether polyol, the reaction activity of the obtained polyether polyol is adversely affected, and foam molding cannot be guaranteed under the condition of no catalyst in the formula.

[0138] While various embodiments of the present invention have been described above, the above description is intended to be illustrative, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the spirit of the present invention.

Claims

1. A highly active polyether polyol A1, characterized in that: The highly active polyether polyol A1 is a product obtained by ring-opening polymerization of an alkylene oxide compound as an initiator and a polymerization monomer; wherein The initiator comprises at least one or more polyamines having a tertiary or secondary amine group at one end and a primary amine group at the other end, and optionally further comprises other small molecule amine compounds and / or small molecule polyols; The functionality of the highly active polyether polyol A1 is 2-5; The alkylene oxide compound is ethylene oxide, or a mixture of ethylene oxide and at least one of propylene oxide and butylene oxide; In the highly active polyether polyol A1, the content of ethylene oxide is 40 wt%-90 wt%; the hydroxyl value of the highly active polyether polyol A1 is 22-112 mgKOH / g; and the primary hydroxyl content is ≥65%.

2. The polyether polyol A1 according to claim 1, characterized in that The polyamine having a tertiary or secondary amine group at one end and a primary amine group at the other end has a specific structure as shown below: Among them, R1, R2, R3, R5, R6, R7, R8, R9, R 10 、R 11 、R 12 and R 13 Each independently represents one or more of -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-; R4 is one or more of -CH3, -CH2CH3, -CH2CH2CH3, and -CH2CH2CH2CH3.

3. The polyether polyol A1 according to claim 1, characterized in that The viscosity of the highly active polyether polyol A1 is in the range of 800-2500 mPa·s.

4. The method for preparing the highly active polyether polyol A1 according to any one of claims 1 to 3, wherein: The following steps are involved: S1: Add the initiator and catalyst into the reactor, heat the system, and introduce the alkylene oxide compound to carry out the reaction; S2: Adjust the system temperature, then introduce the alkylene oxide compound and continue the reaction; S3: The reaction material obtained in step S3 is transferred to a refining kettle, and then acid solution is added thereto for neutralization, followed by dehydration and filtration to obtain a highly active polyether polyol.

5. The preparation method according to claim 4, characterized in that In step S1, the catalyst is one or more of an alkali metal catalyst, an inorganic base, an organic base, and a phosphazene catalyst; In step S1, the system temperature is 85-110°C and the system pressure is lower than 0.5 MPaG; In step S1, the alkylene oxide compound introduced is a mixture of propylene oxide and ethylene oxide, and the addition cycle of the alkylene oxide compound is 5-10 hours; In step S2, the system temperature is adjusted to 110-130°C and the system pressure is lower than 0.5 MPaG; In step S2, the added alkylene oxide compound is ethylene oxide, and the addition period of the alkylene oxide compound is 1-3 hours; In step S3, the acid solution is selected from one or more of a phosphoric acid aqueous solution, a sulfuric acid aqueous solution, an acetic acid aqueous solution and a hydrochloric acid aqueous solution.

6. A viscoelastic polyurethane foam, characterized in that The raw material components include: component A and component B; component A is an isocyanate reactive component, and component B is an isocyanate; wherein the NCO content of the isocyanate is 18 to 35 wt%; The isocyanate-reactive component includes a polyether polyol composition and a foaming agent, wherein the polyether polyol composition includes at least one highly active polyether polyol A1 according to any one of claims 1 to 3 or a highly active polyether polyol A1 prepared by the preparation method according to any one of claims 4 to 5.

7. The viscoelastic polyurethane foam according to claim 6, characterized in that The isocyanate is selected from one or more of polyphenylmethane polyisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate and polyol-modified isocyanate prepolymer.

8. The viscoelastic polyurethane foam according to claim 6, wherein The polyether polyol composition further comprises polyether polyol A2; The polyether polyol A2 has an average functionality of 3 to 5 and a hydroxyl value of 24 to 42 mgKOH / g. The polyether polyol A2 is a product obtained by ring-opening polymerization using a small molecule alcohol or a small molecule amine with a functionality of 3 to 5 as an initiator and an alkylene oxide compound as a polymerization monomer. The alkylene oxide compound is a mixture of ethylene oxide and propylene oxide, and the content of ethylene oxide is 20 to 40 wt%. Based on the weight of the polyether polyol A2, the primary hydroxyl content is ≥80%.

9. The viscoelastic polyurethane foam according to claim 8, characterized in that The foaming agent is selected from one or more of water, CO2, dichlorofluoroethane, butane, n-pentane, cyclopentane and isopentane; The amounts of the components in the isocyanate reactive component are as follows: Highly active polyether polyol A1, 60-100 parts by mass; Polyether polyol A2, 0-40 parts by mass; Foaming agent, 3 to 6 parts by mass.

10. The viscoelastic polyurethane foam according to claim 6, wherein The mass ratio of the component A to the component B is 100:(30-70).

11. The method for preparing the viscoelastic polyurethane foam according to any one of claims 6 to 10, characterized in that: The steps include: (1) uniformly mixing the raw materials of the isocyanate-reactive component to obtain the A component; (2) After fully mixing and stirring the obtained component A and the component B at 20-40°C, the mixture is rapidly injected into a mold for foaming. After 60-100 seconds, the mold is opened to obtain the polyurethane foam; wherein the temperature of the mold is 50-80°C.

12. Use of the viscoelastic polyurethane foam according to any one of claims 6 to 10 or the viscoelastic polyurethane foam prepared by the preparation method according to claim 11 in preparing high-resilience polyurethane soft foam.

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