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

Abstract

The invention belongs to the technical field of viscoelastic polyurethane foam, and particularly relates to polyether polyol and a preparation method thereof as well as polyurethane foam and a preparation method thereof. The viscoelastic polyurethane foam comprises the following raw material components: a component A and a component B, the component A is an isocyanate reactive component, and the component B is isocyanate; wherein the content of NCO (isocyanate) in the isocyanate is 18-35 wt%; the isocyanate reactive component comprises a polyether polyol composition and a foaming agent, and the polyether polyol composition comprises at least one high-activity polyether polyol A1; according to the invention, the VOC content and odor of the viscoelastic polyurethane foam can be reduced, the viscoelastic foam with adjustable loss factors can be obtained, the viscoelastic foam has excellent mechanical properties, and the normal production process efficiency can be met at the same time.

Description

Technical Field

[0001] The invention belongs to the technical field of viscoelastic polyurethane foam, and in particular relates to a polyether polyol and a preparation method thereof, and a 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 vehicles such as automobiles, high-speed trains, and airplanes. The damping properties of viscoelastic polyurethane foam give it a good touch and sound insulation and noise reduction effect, and it is usually used in the preparation of automotive acoustic components and furniture mattresses.

[0003] In recent years, both automotive and home furnishing industry manufacturers have made more stringent demands on their foam suppliers, especially the standards for the volatile organic compound (VOC) content and odor of polyurethane foam. According to the national standard GB18586-2001, a more stringent definition of VOC is selected, that is, the general term for organic volatiles with a melting point below room temperature and a boiling point between 50 and 260°C. VOC means organic volatiles, which are irritating and toxic, mainly including aldehydes, amines, benzene compounds, and low-molecular alcohols. VOC and odor mainly come from catalysts, polyethers, silicone oils and other small and medium-molecular alcohols in the system, among which catalysts and polyethers dominate. 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 obtained polyurethane foams have more odor, higher VOC, and slightly poorer mechanical properties such as stretching and tearing.

[0004] Chinese patent document CN104149455A discloses a slow-rebound polyurethane composite material for automobiles with high damping loss factor and sound insulation performance, which includes a method for preparing a slow-rebound foam. However, the introduction of the amine catalyst used causes the obtained slow-rebound polyurethane composite material to have irritating odor and VOC source risks. At the same time, its technical solution is to use a slow-rebound polyether polyol 2000D with a molecular weight of 700, and the product also has poor mechanical properties such as stretching and tearing.

[0005] Chinese patent document CN109021193A discloses a highly breathable viscoelastic polyurethane foam of an MDI system and a preparation method thereof, which uses a polyether monool with a functionality of 1 and a low molecular weight polyether polyol. The polyurethane foam also has the problems of having a strong odor, high VOC, 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. The research on odor and VOC indicators is not involved.

[0007] Therefore, a technical solution for viscoelastic polyurethane foam 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 purpose of the present invention is to provide a polyether polyol and a preparation method thereof, a polyurethane foam and a preparation method thereof, in view of some technical problems existing in the existing traditional viscoelastic polyurethane foam, which can reduce the amount of catalyst used or not use a catalyst, and at the same time, by regulating the influence of the ethylene oxide content in the polyether polyol on the damping performance of the product, break the modification method of the traditional low molecular weight slow rebound polyether polyol, fundamentally reduce the VOC and odor of the viscoelastic polyurethane foam, and obtain a viscoelastic foam with an adjustable loss factor, and have both excellent mechanical properties and can meet the 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 at least comprises one or more polyamines having a tertiary amine group or a 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 having a tertiary amine group or a secondary amine group at one end and a primary amine group at the other end has a specific structure as shown below:

[0014]

[0015] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 Each is independently one or more of -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3.

[0016] 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 (ie, shown in formula (I) and formula (IV)).

[0017] In the structure of the polyamine initiator containing a tertiary amine group or a secondary amine group at one end and a primary amine group at the other end, one end of the molecule contains a secondary amine group / primary amine group, and the N atom in the amine group, after being polymerized with a polymerization monomer as an initiator, forms a polyether polyol with a tertiary amine group at one end, and the steric hindrance of the terminal N atom is small, so that the high activity of its lone pair of electrons is maintained; this enables the polyamine initiator to play the role of a catalyst and eliminates the addition of an amine catalyst, thereby avoiding the generation of VOC and odor by the amine catalyst, and further reducing the VOC content of the final product polyurethane foam.

[0018] 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 amine group or a 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 amine group or a 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).

[0019] 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.

[0020] In some embodiments, the content of ethylene oxide in the highly active polyether polyol A1 is ≥40wt% (e.g., 42wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%), preferably 40wt% to 90wt%.

[0021] The high content of ethylene oxide in the highly active polyether polyol A1 makes the system rich in -CH2-CH2-O- segments, which have high regularity. Compared with the oxygen in the structural ether bond 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, and 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 high-content ethylene oxide components during the polymerization process can effectively reduce the side reactions generated by the isomerization of propylene oxide in the system, and can 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 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.

[0022] 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.

[0023] 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%.

[0024] 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, 2400 mPa·s, 2600 mPa·s, 2700 mPa·s, 2800 mPa·s, 2900 mPa·s, 3000 mPa·s, 3100 mPa·s, 3200 mPa·s, 3300 mPa·s, 3400 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, 610 The pressure may be within the range of 900-1200 mPa·s, within the range of 1000-1500 mPa·s, within the range of 1200-2000 mPa·s, within the range of 2000-2300 mPa·s, within the range of 1000-2400 mPa·s, within the range of 1500-2400 mPa·s, and within the range of 1800-2400 mPa·s.

[0025] 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).

[0026] In a second aspect, a method for preparing the highly active polyether polyol A1 as described above is provided, comprising the following steps:

[0027] S1: adding the initiator and the catalyst into the reaction kettle, heating the system, and introducing the alkylene oxide compound to react;

[0028] S2: adjusting the system temperature, and then introducing the alkylene oxide compound to continue the reaction;

[0029] S3: The reaction material obtained in step S3 is transferred to a refining kettle, and then an acid solution is added thereto for neutralization, followed by dehydration and filtration to obtain a highly active polyether polyol.

[0030] 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 metallic sodium, sodium hydroxide, potassium hydroxide, potassium tert-butoxide, nitrile phosphine, nitrile acid and phosphate ester; the added amount of the catalyst is 0.02-0.8wt% (for example, 0.03wt%, 0.04wt%, 0.08wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.5wt%, 0.6wt%) of the total amount of the initiator and the alkylene oxide compound, preferably 0.05-0.4wt%.

[0031] 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 0.5MPaG (e.g., 0.4MPaG and below, 0.3MPaG and below);

[0032] 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 h (e.g., 6 h, 8 h, 9 h); the reaction time is 0.5-2 h (e.g., 1 h, 1.5 h).

[0033] 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);

[0034] In some embodiments, in step S2, the added alkylene oxide compound is ethylene oxide, and the addition period of the alkylene oxide compound is 1-3 h (e.g., 1.5 h, 2 h, 2.5 h); the reaction time is 0.5-2 h (e.g., 1 h, 1.5 h).

[0035] In the present invention, there is no special restriction 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 guaranteed to be ≥40wt%.

[0036] According to the method for preparing polyether polyols 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;

[0037] 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.

[0038] 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.

[0039] In a third aspect, a viscoelastic polyurethane foam is provided, wherein the raw material components include: component A and component B; component A is an isocyanate reactive component, and component B is an isocyanate; wherein:

[0040] 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%;

[0041] The isocyanate reactive component comprises a polyether polyol composition and a foaming agent, wherein the polyether polyol composition comprises 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.

[0042] According to the viscoelastic polyurethane foam provided by the present invention, in some embodiments, the isocyanate is selected from one or more of polyphenylmethane polyisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate and polyol-modified isocyanate prepolymer; preferably, it is a mixture of polyphenylmethane polyisocyanate, 4,4-diphenylmethane diisocyanate and polyol-modified isocyanate prepolymer. The polyphenylmethane polyisocyanate may refer to a mixture of polyphenylmethane polyisocyanates having a functionality greater than or equal to 3.

[0043] 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 use ordinary glycerol or other polyamines other than the one end containing a tertiary amine group or a secondary amine group and the other end containing a primary amine group as an initiator);

[0044] In some embodiments, the average functionality of the polyether polyol A2 is 3 to 5 (e.g., 4), the hydroxyl value is 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); the molecular weight is 3200-6000;

[0045] 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).

[0046] According to the viscoelastic polyurethane foam provided by the present invention, in some embodiments, the blowing agent is selected from one or more of water, CO2, dichlorofluoroethane, butane, n-pentane, cyclopentane and isopentane, preferably water.

[0047] 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:

[0048] 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;

[0049] 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;

[0050] The amount of 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 high-activity polyether polyol A1 and the polyether polyol A2.

[0051] In some embodiments, the isocyanate reactive component may further include an auxiliary agent; the auxiliary agent may be a known additive and auxiliary agent; for example, commonly used additives in polyurethane soft foam include foam stabilizers, surfactants, crosslinking agents, etc.; in order to assist molding and other functional effects, auxiliary agents such as catalysts, chain extenders, cell openers, flame retardants, color pastes and other fillers may also be added. The amount of the additive and auxiliary agent may be a conventional choice in the art and will not be described in detail here.

[0052] 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 using Evonik B8734LF2 as an example; the cross-linking agent is a trihydric or polyhydric alcohol or amine commonly used in polyurethane foam products, preferably using triethanolamine and diethanolamine as examples.

[0053] The mass fraction of the surfactant can be 0-1 part (for example, 0.1 part, 0.2 part, 0.4 part, 0.5 part, 0.8 part); the mass fraction of the cross-linking agent can be 0-1 part (for example, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.8 part). The amount of the surfactant and the cross-linking agent is based on 100 parts of the total amount of the highly active polyether polyol A1 and the polyether polyol A2.

[0054] 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).

[0055] In a fourth aspect, there is provided a method for preparing the viscoelastic polyurethane foam as described above, comprising the following steps:

[0056] (1) uniformly mixing the raw materials of the isocyanate-reactive component to obtain the A component;

[0057] (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 s (e.g., 65 s, 70 s, 75 s, 80 s, 85 s, 90 s, 95 s), 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.).

[0058] In the preparation steps of the viscoelastic polyurethane foam, specific preparation parameters and processes and other conditions not described in detail may be prepared by those skilled in the art.

[0059] The polyurethane foam obtained by the preparation method has a molding density of 50 to 80 kg / m 3 , suitable for foaming in molds at 50-80°C, with high production efficiency.

[0060] 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.).

[0061] In the present invention, the use of the viscoelastic polyurethane foam in the high-resilience polyurethane soft foam, its specific operation and process conditions can be conventionally selected in the art, and will not be described in detail here.

[0062] 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.

[0063] The beneficial effects of the technical solution of the present invention are at least:

[0064] The present invention selects highly active polyether polyols, and by improving the raw material composition thereof, highly active polyethers 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 characteristics, and is suitable for the production process requirements of parts such as automobiles and homes, and 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, and has excellent mechanical properties, while meeting normal production process efficiency. DETAILED DESCRIPTION

[0065] 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 embodiments, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments described herein. For those who do not specify specific conditions in the embodiments, they are carried out according to normal conditions or the conditions recommended by the manufacturer.

[0066] In the following examples and comparative examples, the sources of some reagents or raw materials used, if the manufacturer of the reagents or raw materials is not indicated, are conventional products that can be purchased from the market.

[0067] Among them, some of the raw materials used in each embodiment and comparative example are described as follows:

[0068] 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 is end-capped, wherein the ethylene oxide content is 60wt%; the primary hydroxyl content is 87%, the hydroxyl value is 28mgKOH / g, and the viscosity (25°C) is 2050-2350mPa·s;

[0069] Structure 1, i.e., 3-dimethylaminopropylamine, was purchased from Aladdin;

[0070] The preparation method of highly active polyether polyol A1-1 comprises the following steps:

[0071] 1) Add 102.18 g (1 mol) of 3-dimethylaminopropylamine and potassium hydroxide (the amount 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, replace it with nitrogen three times, and evacuate the reactor for 1 hour when the temperature rises to 65° C., 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, and perform aging reaction until the pressure no longer decreases;

[0072] 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 h, and continue the aging reaction until the pressure no longer decreases;

[0073] 3) The reaction material obtained in step S3 is transferred to a refining kettle, the material is cooled to 75-80°C to remove the monomer for 1 hour, and then a hydrochloric acid aqueous solution is added to the obtained product for neutralization, and the pH value of the system is adjusted to about 7, and then the water (the water content is reduced to <500ppm) and unreacted hydrochloric acid are removed, and the material is filtered and discharged to obtain a highly active polyether polyol A1-1. The primary hydroxyl content, hydroxyl value, viscosity and other indicators of the obtained product are measured.

[0074] Highly active polyether polyol A1-2 is obtained by using a mixture of a polyamine compound and diethylenetriamine as a mixed initiator, propylene oxide and ethylene oxide as polymerization monomers, and ethylene oxide is end-capped by ring-opening polymerization, wherein the ethylene oxide content is 90wt%; the primary hydroxyl content is 91%, the hydroxyl value is 34mgKOH / g, and the viscosity (25°C) is 1850-2150mPa·s;

[0075] Diethylenetriamine, purchased from Aladdin;

[0076] The preparation method of highly active polyether polyol A1-2 comprises the following steps:

[0077] 1) Add 61.3g (0.6mol) of 3-dimethylaminopropylamine, 41.24 (0.4mol) of diethylenetriamine and a phosphazene composite catalyst (the amount is equivalent to 0.05wt% of the total mass of 3-dimethylaminopropylamine, diethylenetriamine, propylene oxide and ethylene oxide, and the composition of the phosphazene composite catalyst is a mass ratio of phosphazene to potassium hydroxide of 1:1) in a self-priming reactor; close the reactor, replace it with nitrogen three times, wait for the reactor to be heated to 70°C and evacuate for 1h, heat the reactor to 110°C and control the pressure below 0.4MPa, add 1100g of ethylene oxide, and complete the addition within 1h, add 500g of propylene oxide and 2100g of ethylene oxide, and complete the addition within 4h, and perform aging reaction until the pressure no longer decreases;

[0078] 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, and continue the aging reaction until the pressure no longer decreases;

[0079] 3) The reaction material obtained in step S3 is transferred to a refining kettle, the material is cooled to 75-80°C to remove the monomer for 1 hour, and then a hydrochloric acid aqueous solution is added to the obtained product for neutralization, and the pH value of the system is adjusted to about 7, and then the water (the water content is reduced to <500ppm) and unreacted hydrochloric acid are removed, and the material is filtered and discharged to obtain a highly active polyether polyol A1-2. The primary hydroxyl content, hydroxyl value, viscosity and other indicators of the obtained product are measured.

[0080] 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 is end-capped, 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 900-1100mPa·s;

[0081] Structure 2, i.e., N,N-dimethyldipropylenetriamine, was purchased from Aladdin;

[0082] The preparation method of highly active polyether polyol A1-3 comprises the following steps:

[0083] 1) Add 159.3 g (1 mol) of N,N-dimethyldipropylenetriamine and a phosphazene composite catalyst into 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 it with nitrogen three times, and when the reactor is heated to 90°C, evacuate it for 1 hour, heat the reactor to 110°C and 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, and perform aging reaction until the pressure no longer decreases;

[0084] 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 h, and continue the aging reaction until the pressure no longer decreases;

[0085] 3) The reaction material obtained in step S3 is transferred to a refining kettle, the material is cooled to 75-80°C to remove the monomer for 1 hour, and then a hydrochloric acid aqueous solution is added to the obtained product for neutralization, and the pH value of the system is adjusted to about 7, and then the water (the water content is reduced to <500ppm) and unreacted hydrochloric acid are removed, and the material is filtered and discharged to obtain a highly active polyether polyol A1-3. The primary hydroxyl content, hydroxyl value, viscosity and other indicators of the obtained product are measured.

[0086] Highly active polyether polyol A1-4 is obtained by ring-opening polymerization using the polyamine compound shown in the structure 2 as an initiator, propylene oxide and ethylene oxide as polymerization monomers, and ethylene oxide is end-capped, wherein the ethylene oxide content is 60wt%; the primary hydroxyl content is 88%, the hydroxyl value is 35mgKOH / g, and the viscosity (25°C) is 1250-1450mPa·s;

[0087] The preparation method of highly active polyether polyol A1-4 comprises the following steps:

[0088] 1) Add 159.3g (1mol) of N,N-dimethyldipropylenetriamine and a phosphazene composite catalyst into a self-priming reactor (the amount is equivalent to 0.05wt% 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); seal the reactor, replace it with nitrogen three times, and when the reactor is heated to 90°C, evacuate it for 1h, heat the reactor to 110°C and control the pressure below 0.4MPa, add 950g of ethylene oxide, and complete the addition within 1h, continue to add 1900g of propylene oxide and 950g of ethylene oxide, and complete the addition within 4h, and perform aging reaction until the pressure no longer decreases;

[0089] 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 h, and continue the aging reaction until the pressure no longer decreases;

[0090] 3) The reaction material obtained in step S3 is transferred to a refining kettle, the material is cooled to 75-80°C to remove the monomer for 1 hour, and then a hydrochloric acid aqueous solution is added to the obtained product for neutralization, and the pH value of the system is adjusted to about 7, and then the water (the water content is reduced to <500ppm) and unreacted hydrochloric acid are removed, and the material is filtered and discharged to obtain a highly active polyether polyol A1-4. The primary hydroxyl content, hydroxyl value, viscosity and other indicators of the obtained product are measured.

[0091] 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 is end-capped, wherein the ethylene oxide content is 80wt%; the primary hydroxyl content is 90%, the hydroxyl value is 36mgKOH / g, and the viscosity (25°C) is 1950-2250mPa·s;

[0092] The preparation method of high-activity polyether polyol A1-5 is similar to that of high-activity polyether polyol A1-4, except that: according to the content of ethylene oxide, the feeding amount of ethylene oxide and propylene oxide is adjusted in the feeding process of step 2) and step 3); wherein, the feeding amount of ethylene oxide in step S2 is 2000g and the feeding amount of propylene oxide is 900g, and the feeding amount of ethylene oxide in step S3 is 1650g; the remaining steps are the same as the preparation process of high-activity polyether polyol A1-4; high-activity polyether polyol A1-5 is obtained. The primary hydroxyl content, hydroxyl value, viscosity and other indicators of the obtained product are measured.

[0093] 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%, the hydroxyl value is 28mgKOH / g; the molecular weight is 6000;

[0094] Polyether polyol A2-2, trimethylolpropane as the initiator, propylene oxide and ethylene oxide as the polymerization monomers and ethylene oxide end-capping, wherein the ethylene oxide content is 35wt%, the primary hydroxyl content is 88%, the hydroxyl value is 34mgKOH / g; the molecular weight is 4950;

[0095] Polyether polyol A2-3, glycerol as initiator, propylene oxide as polymerization monomer, hydroxyl value is 240mgKOH / g;

[0096] 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;

[0097] 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;

[0098] Surfactant: Evonik B8734LF2;

[0099] Cross-linking agent 1: triethanolamine;

[0100] Cross-linking agent 2: diethanolamine;

[0101] Isocyanate B1, a mixture of polyphenylmethane polyisocyanate, 4,4-diphenylmethane diisocyanate and polyol-modified isocyanate prepolymer, with an NCO content of 30%;

[0102] Isocyanate B2, a mixture of polyphenylmethane polyisocyanate, 4,4-diphenylmethane diisocyanate and a polyol-modified isocyanate prepolymer, having an NCO content of 22%;

[0103] Isocyanate B3, a mixture of polyphenylmethane polyisocyanate, 4,4-diphenylmethane diisocyanate and polyol-modified isocyanate prepolymer, with an NCO content of 32%;

[0104] Catalyst 1: Huntsman, dimethylaminopropylamine;

[0105] Catalyst 2: Huntsman, N,N-dimethyl-N,N-bis(2-hydroxypropyl)-1,3-propylenediamine.

[0106] Performance tests of the polyurethane foams prepared in various embodiments and comparative examples:

[0107] (1) Hydroxyl value: Tested in accordance with GB / T12008.3-1989 "Determination of hydroxyl value in polyether polyols";

[0108] (2) Viscosity: Tested in accordance with GB / T12008.7-2010 "Plastic polyether polyols Part 7: Determination of viscosity";

[0109] (3) Foam density: tested according to standard ISO845;

[0110] (4) Odor and VOC evaluation standards: BMW cubic warehouse test method, GS97014-3:2022 (VOC) GS97014-4:2021 (Odour);

[0111] (5) Loss factor test: The results are obtained by using a dynamic Young's modulus and loss factor tester.

[0112] Please see Table 1 and Table 2 for the test results.

[0113] [Examples 1-12]

[0114] The preparation steps of viscoelastic polyurethane foam are:

[0115] The raw material components include: component A and component B; the formula thereof is as shown in Table 1;

[0116] According to the measurement shown in Table 1, the raw materials of the isocyanate reactive component are uniformly mixed at 25°C to obtain component A; then, at 25°C, the obtained component A is fully stirred and mixed with component B according to the measurement shown in Table 1, and then quickly injected into a mold with a mold temperature of 65°C for reaction foaming. After 120 seconds, the mold is opened and the foam is taken out (the gel time needs to be less than 70 seconds) to obtain a polyurethane foam.

[0117] [Comparative Examples 1-5]

[0118] The preparation steps of viscoelastic polyurethane foam are:

[0119] The raw material components include: component A and component B; the formula thereof is as shown in Table 2;

[0120] According to the measurement shown in Table 2, the raw materials of the isocyanate reactive component are uniformly mixed at 25°C to obtain component A; then, at 25°C, the obtained component A is fully stirred and mixed with component B according to the measurement shown in Table 1, and then quickly injected into a mold with a mold temperature of 65°C for reaction foaming. After 120 seconds, the mold is opened to take out the foam (the gel time needs to be less than 70 seconds) to prepare a polyurethane foam.

[0121] 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, Comparative Examples 1 and Comparative Examples 4-5 could not be tested for product performance.

[0122] In Table 1 and Table 2, each raw material component is calculated in parts by mass.

[0123]

[0124]

[0125]

[0126]

[0127]

[0128] It can be seen from the data of the examples that by adopting the technical solution of the present invention, the polyurethane foam formula can achieve rapid maturation without using a catalyst, and at the same time, the damping performance of the product can be regulated by controlling the EO segment content in the system, ultimately achieving the preparation of damping foam with low odor and low VOC content.

[0129] Comparison of Comparative Examples 1-2 with the Example shows that when the highly active polyether selected by the present technical solution is not used in Comparative Example 1 and the catalyst is not added to the formula, the foam cannot be formed normally; in Comparative Example 2, the highly active polyether selected by the present technical solution is not used and the catalyst is added to the formula, although the foam can be formed normally, the odor and VOC content are both high;

[0130] Compared with the embodiment, comparative example 3 is a traditional technical solution for slow rebound foam, which requires adding a catalyst to the formula and using a low molecular weight polyol, but the odor and VOC content of the obtained foam are both high;

[0131] Comparative Example 4 shows that when the amount ratio of the active polyether polyol used in the non-present technical solution is within the 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 an amine initiator other than the present technical solution is used to prepare a polyether polyol, the reaction activity of the obtained polyether polyol is adversely affected, and foam molding cannot be guaranteed when there is no catalyst in the formula.

[0132] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes 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 amine group or a secondary amine group at one end and a primary amine group at the other end, and optionally comprises other small molecule amine compounds and / or small molecule polyols; The functionality of the highly active polyether polyol A1 is 2-5.

2. The polyether polyol A1 according to claim 1, characterized in that The polyamine having a tertiary amine group or a 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, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 and R 13 Each is independently one or more of -CH3, -CH2CH3, -CH2CH2CH3, -CH2CH2CH2CH3.

3. The polyether polyol A1 according to claim 1, characterized in that 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 ≥40wt%.

4. The polyether polyol A1 according to claim 1, characterized in that The highly active polyether polyol A1 has a hydroxyl value of 22-112 mgKOH / g and a primary hydroxyl content of ≥65%; The viscosity of the highly active polyether polyol A1 is in the range of 800-2500 mPa·s.

5. The method for preparing the highly active polyether polyol A1 according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1: adding the initiator and the catalyst into the reaction kettle, heating the system, and introducing the alkylene oxide compound to react; S2: adjusting the system temperature, and then introducing the alkylene oxide compound to continue the reaction; S3: The reaction material obtained in step S3 is transferred to a refining kettle, and then an acid solution is added thereto for neutralization, followed by dehydration and filtration to obtain a highly active polyether polyol.

6. The preparation method according to claim 5, 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 0.5MPaG; In step S1, the introduced alkylene oxide compound 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.

7. 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 isocyanate; wherein the NCO content of the isocyanate is 18-35wt%; The isocyanate-reactive components include a polyether polyol composition and a blowing agent, wherein the polyether polyol composition includes at least one highly active polyether polyol A1 as described in any one of claims 1 to 4 or a highly active polyether polyol A1 prepared by the preparation method as described in any one of claims 5 to 6.

8. The viscoelastic polyurethane foam according to claim 7, 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.

9. The viscoelastic polyurethane foam according to claim 7, characterized in that The polyether polyol composition further comprises polyether polyol A2; The average functionality of the polyether polyol A2 is 3 to 5, and the hydroxyl value is 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; wherein 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%.

10. The viscoelastic polyurethane foam according to claim 9, 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 each component 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.

11. The viscoelastic polyurethane foam according to claim 7, characterized in that The mass ratio of the A component to the B component is 100:(30-70).

12. The method for preparing a viscoelastic polyurethane foam according to any one of claims 7 to 11, 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.

13. Use of the viscoelastic polyurethane foam according to any one of claims 7 to 11 or the viscoelastic polyurethane foam prepared by the preparation method according to claim 12 in the preparation of high-resilience polyurethane soft foam.

Images