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

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 therefor, and a polyurethane foam and a preparation method therefor. The raw material components of the viscoelastic polyurethane foam comprise a component A, which is an isocyanate-reactive component, and a component B, which is an isocyanate, wherein the isocyanate has an NCO content of 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 highly active polyether polyol A1. The present invention can reduce the VOC content and odor of viscoelastic polyurethane foam, while providing viscoelastic foam having an adjustable loss factor and excellent mechanical properties and satisfying the normal production process efficiency.

Description

Polyether polyols and their preparation methods, polyurethane foams and their preparation methods Technical Field

[0001] This invention belongs to the field of viscoelastic polyurethane foam technology, and particularly relates to a polyether polyol and its preparation method, and polyurethane foam and its preparation method. Background Technology

[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 airplanes. The damping properties of viscoelastic polyurethane foam further endow it with excellent tactile feel and sound insulation and noise reduction effects, and it is commonly used in the manufacture of automotive acoustic components and furniture mattresses.

[0003] In recent years, manufacturers in both the automotive and home furnishing industries have placed increasingly stringent demands on their foam suppliers, particularly regarding the volatile organic compound (VOC) content and odor standards for polyurethane foam. According to the national standard GB18586-2001, a stricter definition of VOC is adopted: the general term for volatile organic compounds with melting points below room temperature and boiling points between 50 and 260°C. VOCs are irritating and somewhat toxic, mainly including aldehydes, amines, benzene compounds, and low-molecular-weight alcohols. VOCs and odors primarily originate from catalysts, polyethers, silicone oils, and other small- to medium-molecular-weight alcohols in the system, with catalysts and polyethers being the dominant components. In addition, the traditional viscoelastic polyurethane foam technology often uses a combination 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 of 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, high VOC content, and slightly poor mechanical properties such as tensile and tear resistance.

[0004] Chinese patent document CN104149455A discloses a slow rebound polyurethane composite material for automobiles with high damping loss factor and sound insulation performance. It includes a method for preparing slow rebound foam. However, the introduction of amine catalysts used results in the slow rebound polyurethane composite material having an irritating odor and potential VOC sources. In addition, the technical solution uses slow rebound polyether polyol 2000D with a molecular weight of 700, and the tensile, tear and other mechanical properties of the product are also poor.

[0005] Chinese patent document CN109021193A discloses a high-permeability viscoelastic polyurethane foam based on MDI system and its preparation method. It uses polyether monool with a functionality of 1 and low molecular weight polyether polyol. However, it also has the problems of polyurethane foam having a strong odor, high VOC content, and slightly poor mechanical properties such as tensile and tear resistance.

[0006] Chinese patent document CN104031235A discloses a method for preparing viscoelastic polyurethane sound-absorbing foam, which uses a polyether polyol component with 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. Furthermore, the study on odor and VOC index is not covered.

[0007] Therefore, there is a need for a viscoelastic polyurethane foam technology using a highly active polyether polyol system. The research aims to find a viscoelastic foam with an adjustable loss factor that can reduce the VOC and odor of the viscoelastic polyurethane foam, while also possessing superior mechanical properties and meeting the efficiency requirements of normal production processes. Summary of the Invention

[0008] The purpose of this invention is to address some technical problems existing in conventional viscoelastic polyurethane foams by providing a polyether polyol and its preparation method, as well as a polyurethane foam and its preparation method. This method can reduce the amount of catalyst used or eliminate the need for a catalyst, while simultaneously controlling the influence of the ethylene oxide content in the polyether polyol on the damping performance of the product. This breaks away from the modification methods using traditional low molecular weight slow-rebound polyether polyols, fundamentally reducing the VOC and odor of viscoelastic polyurethane foams, while obtaining viscoelastic foams with adjustable loss factors, superior mechanical properties, and the ability to meet normal production process efficiency requirements.

[0009] To achieve the above objectives, the present invention provides the following technical solution:

[0010] In a first aspect, a highly reactive polyether polyol A1 is provided, said highly reactive polyether polyol A1 being a product obtained by ring-opening polymerization of an initiator and an epoxide compound as 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 includes other small molecule amine compounds (such as triethanolamine, diethylenetriamine, and other small amine molecules), and / or small molecule polyols (such as ethylene glycol, glycerol, trimethylolpropane, pentaquatetrapentol, and sucrose).

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

[0013] In some embodiments of the polyether polyol A1 provided by the present invention, the polyamine having a tertiary or secondary amine group at one end and a primary amine group at the other end has the following specific structure:

[0014] Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 and R 13 Each can be independently one or more of -CH3, -CH2CH3, -CH2CH2CH3, and -CH2CH2CH2CH3.

[0015] 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., as shown in formula (I) and formula (IV)).

[0016] 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, the molecule contains a secondary / primary amine group at one end. After the N atom in this amine group polymerizes with the monomer as an initiator, it forms a polyether polyol with a tertiary amine group at one end. The steric hindrance of the N atom at the end group is small, maintaining the high activity of its lone pair electrons. This allows the polyamine initiator to act as a catalyst, eliminating the need for the addition of amine catalysts, avoiding the generation of VOCs and odors by amine catalysts, and thus reducing the VOC content of the final product, polyurethane foam.

[0017] In some embodiments of the polyether polyol A1 provided by the present invention, 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.), the molar ratio of the two in the mixture may 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 small molecule polyols (such as ethylene glycol, glycerol, trimethylolpropane, pentaerythritol, and sucrose), the molar ratio of the two in the mixture may be (2-8):(8-2).

[0018] In some embodiments of the polyether polyol A1 provided by the present invention, the alkyl oxide compound is ethylene oxide, or a mixture of ethylene oxide with at least one of propylene oxide and butane oxide, preferably a mixture of ethylene oxide and propylene oxide.

[0019] 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%.

[0020] The high ethylene oxide content in the highly active polyether polyol A1 enriches the system with -CH2-CH2-O- segments. These segments exhibit high regularity, and compared to the oxygen in the ether bonds obtained from propylene oxide, they are more polar and have better crystallinity due to the absence of interference from side methyl groups. This results in a polyurethane product with excellent damping performance, and the damping ratio of the viscoelastic polyurethane foam can be controlled by adjusting the ethylene oxide content in polyether polyol A1. The addition of a high ethylene oxide content during polymerization effectively reduces the side reactions caused by propylene oxide isomerization in the system, thereby reducing the unsaturation of the obtained polyether polyol, improving its stability and quality, and further reducing the odor and VOCs of the obtained polyurethane foam. The high ethylene oxide content results in a higher primary hydroxyl content in the obtained polyether polyol, ensuring its high activity. In addition, the high hydrophilicity of ethylene oxide is beneficial to the stability of the aqueous foaming system.

[0021] 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 alkyl oxide compound is 1:k, where k can be selected from an integer from 1 to 400 (e.g., 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, where m and n can each be independently selected from an integer from 0 to 200 (e.g., 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.

[0022] In some embodiments of the polyether polyol A1 provided by the present invention, the hydroxyl value of the highly active polyether polyol A1 is 22-112 mgKOH / g (e.g., 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% (e.g., 68%, 70%, 72%, 75%, 80%, 82%, 84%, 85%, 88%, 90%), preferably ≥80%.

[0023] In some embodiments, the viscosity range of the highly reactive polyether polyol A1 is 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). Pa·s, 2400 mPa·s), can be in the range of 900-1200 mPa·s, can be in the range of 1000-1500 mPa·s, can be in the range of 1200-2000 mPa·s, can be in the range of 2000-2300 mPa·s, can be in the range of 1000-2400 mPa·s, can be in the range of 1500-2400 mPa·s, can be in the range of 1800-2400 mPa·s.

[0024] 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).

[0025] In a second aspect, a method for preparing the highly active polyether polyol A1 as described above is provided, comprising the following steps:

[0026] S1: The initiator and catalyst are added to the reactor, the system is heated, and the epoxide compound is introduced to carry out the reaction;

[0027] S2: Adjust the system temperature, then introduce the epoxide compound again to continue the reaction;

[0028] S3: Transfer the reaction material obtained in step S3 to a refining kettle, then add acid to neutralize it, and then dehydrate and filter it to obtain a highly active polyether polyol.

[0029] According to the method for preparing polyether polyols provided by the present invention, in some embodiments, in step S1, the catalyst is one or more selected from alkali metal catalysts, inorganic bases, organic bases, and phosphazene catalysts, preferably selected from one or more selected from sodium metal, sodium hydroxide, potassium hydroxide, potassium tert-butoxide, nitrile phosphonate, cyanic acid, and phosphate esters; the amount of catalyst added is 0.02-0.8 wt% (e.g., 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 initiator and alkyl oxide compound, preferably 0.05-0.4 wt%.

[0030] In some implementations, 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 below 0.5 MPaG (e.g., 0.4 MPaG and below, 0.3 MPaG and below);

[0031] In some embodiments, in step S1, the introduced alkyl oxide compound is a mixture of propylene oxide and ethylene oxide, and the addition cycle of the alkyl oxide compound is 5-10h (e.g., 6h, 8h, 9h); the reaction time is 0.5-2h (e.g., 1h, 1.5h).

[0032] According to the method for preparing polyether polyols 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 below 0.5 MPaG (e.g., 0.4 MPaG and below, 0.3 MPaG and below);

[0033] In some embodiments, in step S2, the added alkyl epoxide compound is ethylene oxide, and the addition cycle of the alkyl epoxide compound is 1-3h (e.g., 1.5h, 2h, 2.5h); the reaction continues for 0.5-2h (e.g., 1h, 1.5h).

[0034] In this invention, there are no special restrictions on the amount of epoxide compound added in step S1 and step S2, as long as the content of ethylene oxide in the final high-activity polyether polyol is ≥40wt%.

[0035] 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 phosphoric acid aqueous solution, sulfuric acid aqueous solution, acetic acid aqueous solution and hydrochloric acid aqueous solution, preferably phosphoric acid aqueous solution and / or hydrochloric acid aqueous solution;

[0036] In some implementations, during the neutralization process, the pH of the system is adjusted to 4-7 by adding acid.

[0037] In some embodiments, in step S3, the water content in the reactants is reduced to <500 ppm by the dehydration process, 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, or below 5 ppm.

[0038] In a third aspect, a viscoelastic polyurethane foam is provided, the raw material components of which include: component A and component B; component A is an isocyanate reactive component, and component B isocyanate; wherein...

[0039] The isocyanate has an NCO content of 18–35 wt% (e.g., 20 wt%, 24 wt%, 25 wt%, 28 wt%, 30 wt%, 34 wt%), preferably 22–32 wt%.

[0040] 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 as described above or a highly active polyether polyol A1 prepared by the preparation method described above.

[0041] In some embodiments of the viscoelastic polyurethane foam provided by the present invention, the isocyanate is selected from one or more of polyphenylmethane polyisocyanates, 2,4-diphenylmethane diisocyanates, 4,4-diphenylmethane diisocyanates, and polyol-modified isocyanate prepolymers; preferably, a mixture of polyphenylmethane polyisocyanates, 4,4-diphenylmethane diisocyanates, and polyol-modified isocyanate prepolymers. The polyphenylmethane polyisocyanates can all refer to mixtures of polyphenylmethane polyisocyanates with a functionality greater than or equal to 3.

[0042] In some embodiments of the viscoelastic polyurethane foam provided by the present invention, the polyether polyol composition further includes polyether polyol A2 (which may be polyether polyol A2 that uses ordinary glycerol or other polyamines that do not contain a tertiary or secondary amine group at one end and a primary amine group at the other end as an initiator).

[0043] 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 to 6000.

[0044] In some embodiments, the polyether polyol A2 is a product obtained by ring-opening polymerization using a small molecule alcohol or small molecule amine with a functionality of 3-5 as an initiator and an alkyl oxide compound as a polymerization monomer; wherein the alkyl oxide compound is a mixture of ethylene oxide and propylene oxide, and the content of ethylene oxide is 20-40 wt% (e.g., 22 wt%, 24 wt%, 25 wt%, 28 wt%, 30 wt%, 32 wt%, 34 wt%, 35 wt%, 38 wt%); based on the weight of the polyether polyol A2, the primary hydroxyl content is ≥80%, for example, 82 wt%, 84 wt%, 85 wt%, 90 wt% (calculated based on the amount of primary and secondary hydroxyl groups).

[0045] In some embodiments of the viscoelastic polyurethane foam provided by the present invention, the foaming agent is selected from one or more of water, CO2, dichlorofluoroethane, butane, n-pentane, cyclopentane and isopentane, preferably water.

[0046] In some embodiments of the viscoelastic polyurethane foam provided by the present invention, the amounts of each component in the isocyanate reactive component are as follows:

[0047] Highly active polyether polyol A1, 60-100 parts by weight, for example, 62 parts by weight, 65 parts by weight, 68 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, and 95 parts by weight.

[0048] Polyether polyol A2, 0-40 parts by weight, for example, 1 part by weight, 2 parts by weight, 4 parts by weight, 5 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 38 parts by weight.

[0049] The foaming agent is used in 3 to 6 parts by weight, for example, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, and 5.5 parts by weight; wherein the amount of the foaming agent is based on a total of 100 parts of high-activity polyether polyol A1 and polyether polyol A2.

[0050] In some embodiments, the isocyanate reactive component may further include additives; these additives may be known additives and auxiliaries; for example, commonly used additives in polyurethane flexible foam include foam stabilizers, surfactants, crosslinking agents, etc.; to assist in molding and other functional effects, auxiliaries such as catalysts, chain extenders, cell openers, flame retardants, color pastes, and other fillers may also be added. The amounts of the additives and auxiliaries used are conventional choices in the art and will not be elaborated here.

[0051] In the technical solution of the present invention, the isocyanate reactive component can be used in combination with a surfactant and a crosslinking agent; wherein, the surfactant can be a foam stabilizer, such as a polysiloxane-polyepoxy block copolymer, to stabilize or adjust the cell structure of the foam plastic, preferably Evonik B8734LF2 as an example; the crosslinking agent is a ternary or polyol or amine commonly used in polyurethane foam products, preferably triethanolamine or diethanolamine as examples.

[0052] The surfactant can be present in 0-1 parts by weight (e.g., 0.1, 0.2, 0.4, 0.5, or 0.8 parts); the crosslinking agent can be present in 0-1 parts by weight (e.g., 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, or 0.8 parts). The amounts of the surfactant and crosslinking agent are based on a total of 100 parts of highly active polyether polyol A1 and polyether polyol A2.

[0053] In some embodiments of the viscoelastic polyurethane foam provided by the present invention, the mass ratio of component A to 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).

[0054] In a fourth aspect, a method for preparing the viscoelastic polyurethane foam as described above is provided, comprising the following steps:

[0055] (1) The raw materials of the isocyanate reactive component are mixed evenly to obtain component A;

[0056] (2) At 20-40℃ (e.g., 25℃, 30℃, 35℃), the obtained component A and component B are thoroughly mixed and stirred, and then quickly injected into a mold to foam. After 60-100s (e.g., 65s, 70s, 75s, 80s, 85s, 90s, 95s), the mold is opened to obtain the polyurethane foam; wherein the temperature of the mold is 50-80℃ (e.g., 55℃, 60℃, 65℃, 70℃, 75℃).

[0057] In the preparation steps of the viscoelastic polyurethane foam, the specific preparation parameters and process conditions not described in detail can all be prepared using the preparation parameters and processes commonly used by those skilled in the art.

[0058] The polyurethane foam prepared by the method has a molding density of 50–80 kg / m³. 3 It is suitable for foaming and molding in molds at 50-80℃, and has high production efficiency.

[0059] In a fifth aspect, the viscoelastic polyurethane foam described above or the viscoelastic polyurethane foam prepared by the method described above is provided for use in the preparation of high-resilience polyurethane flexible foams (such as automotive parts, furniture mattresses, etc.).

[0060] In this invention, the application of the viscoelastic polyurethane foam in high-resilience polyurethane flexible foam, and the specific operation and process conditions can be conventional choices in the field, which will not be elaborated here.

[0061] The viscoelastic polyurethane foam of the present invention has applications, for example, in the manufacture of interior products such as automotive carpets and front fascias.

[0062] The beneficial effects of the technical solution of this invention are at least as follows:

[0063] This invention selects highly active polyether polyols. By improving the composition of its raw materials, highly active polyethers can be obtained. The viscoelastic polyurethane foam prepared using this polyether polyol as a raw material has controllable damping, excellent low VOC and odor characteristics, and low density and rapid production characteristics. It is suitable for the production process requirements of automotive, home furnishing and other parts, and further improves the health and comfort of end users. In other words, this invention can reduce the VOC and odor of viscoelastic polyurethane foam while obtaining viscoelastic foam with adjustable loss factor, and also has superior mechanical properties, while meeting the efficiency requirements of normal production processes. Detailed Implementation

[0064] To provide a detailed understanding of the technical features and content of this invention, preferred embodiments will be described in more detail below. While preferred embodiments are described in the examples, it should be understood that the invention can be implemented in various forms and should not be limited to the embodiments set forth herein. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer shall apply.

[0065] In the following examples and comparative examples, the sources of some reagents or raw materials used, unless otherwise specified, are all conventional products that can be purchased commercially.

[0066] The raw materials used in each embodiment and comparative example are described below:

[0067] 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 monomers, and ethylene oxide as end-capping agent. The ethylene oxide content is 60 wt%; the primary hydroxyl content is 87%; the hydroxyl value is 28 mg KOH / g; and the viscosity (25℃) is 2050~2350 mPa·s.

[0068] Structure 1, namely 3-dimethylaminopropylamine, was purchased from Aladdin;

[0069] The preparation method of highly active polyether polyol A1-1 includes the following steps:

[0070] 1) Add 102.18 g (1 mol) of 3-dimethylaminopropylamine and potassium hydroxide (the amount of which 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 purge it with nitrogen three times. When the reactor temperature reaches 65°C, evacuate it for 1 hour. Then, raise the reactor temperature 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 feeding in 5 hours. Then, carry out the aging reaction until the pressure no longer decreases.

[0071] 2) Adjust the system temperature to 120℃, control the system pressure below 0.4MPa, add 780g of ethylene oxide, and complete the addition in 2 hours. Continue the aging reaction until the pressure no longer decreases.

[0072] 3) Transfer the reaction material obtained in step S3 to a refining kettle. Cool the material to 75-80℃ for 1 hour to remove monomers. Then, add hydrochloric acid aqueous solution to the obtained product for neutralization, adjust the pH of the system to about 7, and then remove water (reduce water content to <500ppm) and unreacted hydrochloric acid. Filter and discharge to obtain highly active polyether polyol A1-1. Measure the primary hydroxyl content, hydroxyl value, viscosity, and other indicators of the obtained product.

[0073] Highly active polyether polyol A1-2 is obtained by ring-opening polymerization of a mixture of a polyamine compound as shown in structure 1 above and diethylenetriamine as a mixing initiator, propylene oxide and ethylene oxide as polymerization monomers, and ethylene oxide end-capping. The ethylene oxide content is 90 wt%; the primary hydroxyl content is 91%; the hydroxyl value is 34 mg KOH / g; and the viscosity (25℃) is 1850~2150 mPa·s.

[0074] Diethylenetriamine, purchased from Aladdin;

[0075] The preparation method of highly active polyether polyol A1-2 includes the following steps:

[0076] 1) Add 61.3g (0.6mol) of 3-dimethylaminopropylamine, 41.24g (0.4mol) of diethylenetriamine, and a phosphazene composite catalyst (the amount of which is equivalent to 0.05wt% of the total mass of 3-dimethylaminopropylamine, diethylenetriamine, propylene oxide, and ethylene oxide; the composition of the phosphazene composite catalyst is phosphazene to potassium hydroxide in a mass ratio of 1:1) to a self-priming reactor; seal the reactor and purge it with nitrogen three times; after the reactor is heated to 70℃, evacuate it for 1 hour; then heat the reactor to 110℃ and control the pressure below 0.4MPa; add 1100g of ethylene oxide and complete the addition in 1 hour; then add 500g of propylene oxide and 2100g of ethylene oxide and complete the addition in 4 hours; and carry out the aging reaction until the pressure no longer decreases.

[0077] 2) Adjust the system temperature to 125℃, control the system pressure below 0.3MPa, add 1500g of ethylene oxide, and complete the addition in 2 hours. Continue the aging reaction until the pressure no longer decreases.

[0078] 3) Transfer the reaction material obtained in step S3 to a refining kettle. Cool the material to 75-80℃ for 1 hour to remove monomers. Then, add hydrochloric acid aqueous solution to the obtained product for neutralization, adjust the pH of the system to about 7, and then remove water (reducing the water content to <500ppm) and unreacted hydrochloric acid. Filter and discharge to obtain highly active polyether polyol A1-2. Measure the primary hydroxyl content, hydroxyl value, viscosity, and other indicators of the obtained product.

[0079] Highly active polyether polyol A1-3 is obtained by ring-opening polymerization of propylene oxide and ethylene oxide as monomers, with the polyamine compound shown in structure 2 as the initiator and ethylene oxide as the monomers, and the end capping of ethylene oxide. The ethylene oxide content is 40 wt%, the primary hydroxyl content is 84%, the hydroxyl value is 35 mg KOH / g, and the viscosity (25℃) is 900~1100 mPa·s.

[0080] Structure 2, namely N,N-dimethyldipropylenetriamine, was purchased from Aladdin;

[0081] The preparation method of highly active polyether polyol A1-3 includes the following steps:

[0082] 1) Add 159.3g (1mol) of N,N-dimethyldipropylenetriamine and phosphazene composite catalyst (the amount of which 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 phosphazene to potassium hydroxide in a mass ratio of 2:1) to a self-priming reactor; seal the reactor and purge it with nitrogen three times. When the reactor temperature reaches 90℃, evacuate it for 1 hour. Then, raise the reactor temperature to 110℃ and control the pressure below 0.4MPa. Add 2890g of propylene oxide and 950g of ethylene oxide, and complete the feeding in 5 hours. Then, carry out the aging reaction until the pressure no longer decreases.

[0083] 2) Adjust the system temperature to 130℃, control the system pressure below 0.3MPa, add 980g of ethylene oxide, and complete the addition in 2 hours. Continue the aging reaction until the pressure no longer decreases.

[0084] 3) Transfer the reaction material obtained in step S3 to a refining reactor. Cool the material to 75-80℃ for 1 hour to remove monomers. Then, add hydrochloric acid aqueous solution to the obtained product for neutralization, adjust the pH of the system to about 7, and then remove water (reduce water content to <500ppm) and unreacted hydrochloric acid. Filter and discharge to obtain highly active polyether polyol A1-3. Measure the primary hydroxyl content, hydroxyl value, viscosity, and other indicators of the obtained product.

[0085] Highly active polyether polyol A1-4 is obtained by ring-opening polymerization of a polyamine compound as shown in structure 2 above as an initiator, propylene oxide and ethylene oxide as monomers, and ethylene oxide end-capping. The ethylene oxide content is 60 wt%; the primary hydroxyl content is 88%; the hydroxyl value is 35 mg KOH / g; and the viscosity (25℃) is 1250~1450 mPa·s.

[0086] The preparation method of highly active polyether polyol A1-4 includes the following steps:

[0087] 1) Add 159.3g (1mol) of N,N-dimethyldipropylenetriamine and phosphazene composite catalyst (the amount of which 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 phosphazene to potassium hydroxide in a mass ratio of 2:1) to a self-priming reactor; seal the reactor and purge it with nitrogen three times. When the reactor temperature reaches 90℃, evacuate it for 1 hour. Then, raise the reactor temperature to 110℃ and control the pressure below 0.4MPa. Add 950g of ethylene oxide and complete the addition in 1 hour. Continue to add 1900g of propylene oxide and 950g of ethylene oxide and complete the addition in 4 hours. Perform an aging reaction until the pressure no longer decreases.

[0088] 2) Adjust the system temperature to 130℃, control the system pressure below 0.3MPa, add 980g of ethylene oxide, and complete the addition in 2 hours. Continue the aging reaction until the pressure no longer decreases.

[0089] 3) Transfer the reaction material obtained in step S3 to a refining kettle. Cool the material to 75-80℃ for 1 hour to remove monomers. Then, add hydrochloric acid aqueous solution to the obtained product for neutralization, adjust the pH of the system to about 7, and then remove water (reduce water content to <500ppm) and unreacted hydrochloric acid. Filter and discharge to obtain highly active polyether polyol A1-4. Measure the primary hydroxyl content, hydroxyl value, viscosity, and other indicators of the obtained product.

[0090] 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 polymerizing monomers, and ethylene oxide as the end-capping agent. The ethylene oxide content is 80 wt%; the primary hydroxyl content is 90%; the hydroxyl value is 36 mg KOH / g; and the viscosity (25℃) is 1950~2250 mPa·s.

[0091] The preparation method of highly reactive polyether polyol A1-5 is the same as that of highly reactive polyether polyol A1-4 above, except that the amounts of ethylene oxide and propylene oxide added in steps 2) and 3) are adjusted according to the content of ethylene oxide. Specifically, in step S2, the amount of ethylene oxide added is 2000g and the amount of propylene oxide added is 900g, and in step S3, the amount of ethylene oxide added is 1650g. The remaining steps are the same as those for highly reactive polyether polyol A1-4, thus obtaining highly reactive polyether polyol A1-5. The primary hydroxyl content, hydroxyl value, viscosity, and other indicators of the obtained product are measured.

[0092] Polyether polyol A2-1 uses glycerol as an initiator, propylene oxide and ethylene oxide as polymerization monomers with ethylene oxide end capping. The ethylene oxide content is 23wt%, the primary hydroxyl content is 85%, the hydroxyl value is 28mgKOH / g, and the molecular weight is 6000.

[0093] Polyether polyol A2-2 uses trimethylolpropane as an initiator, propylene oxide and ethylene oxide as monomers with ethylene oxide end capping, wherein the ethylene oxide content is 35wt%, the primary hydroxyl content is 88%, the hydroxyl value is 34mgKOH / g, and the molecular weight is 4950.

[0094] Polyether polyol A2-3, with glycerol as the initiator and propylene oxide as the polymerization monomer, has a hydroxyl value of 240 mgKOH / g;

[0095] Polyether polyol A2-4, with triethanolamine as the initiator, propylene oxide and ethylene oxide as the 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;

[0096] Polyether polyol A2-5, with triethylenediamine as the initiator, propylene oxide and ethylene oxide as the 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;

[0097] Surfactant: Evonik B8734LF2;

[0098] Crosslinking agent 1: Triethanolamine;

[0099] Crosslinking agent 2: diethanolamine;

[0100] A mixture of isocyanate B1, polyphenylmethane polyisocyanate, 4,4-diphenylmethane diisocyanate and polyol-modified isocyanate prepolymer, with an NCO content of 30%.

[0101] A mixture of isocyanate B2, polyphenylmethane polyisocyanate, 4,4-diphenylmethane diisocyanate and polyol-modified isocyanate prepolymer, with an NCO content of 22%.

[0102] A mixture of isocyanate B3, polyphenylmethane polyisocyanate, 4,4-diphenylmethane diisocyanate and polyol-modified isocyanate prepolymer, with an NCO content of 32%.

[0103] Catalyst 1: Huntsman, dimethylaminopropylamine;

[0104] Catalyst 2: Huntsman, N,N-dimethyl-N,N-bis(2-hydroxypropyl)-1,3-propanediamine.

[0105] Performance tests of polyurethane foams prepared in each embodiment and comparative example:

[0106] (1) Hydroxyl value: Tested according to GB / T12008.3-1989 "Determination of hydroxyl value in polyether polyols";

[0107] (2) Viscosity: Tested in accordance with GB / T12008.7-2010 "Plastic Polyether Polyols Part 7: Determination of Viscosity";

[0108] (3) Foam density: The test was conducted in accordance with standard ISO 845;

[0109] (4) Odor and VOC evaluation standards: BMW cubic test method, GS97014-3:2022 (VOC) GS97014-4:2021 (Odour);

[0110] (5) Loss factor test: The results were obtained by using a dynamic method Young's modulus and loss factor measuring instrument.

[0111] The test results are shown in Tables 1 and 2.

[0112] 【Examples 1-12】

[0113] The preparation steps of viscoelastic polyurethane foam are as follows:

[0114] The raw material components include: component A and component B; their formulation is as shown in Table 1;

[0115] According to the measurements 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 thoroughly mixed with component B according to the measurements shown in Table 1, and then quickly injected into a mold with a mold temperature of 65°C for reaction and foaming. After 120 seconds, the mold is opened and the foam is removed (the gelation time needs to be less than 70 seconds) to obtain polyurethane foam.

[0116] Comparative Examples 1-5

[0117] The preparation steps of viscoelastic polyurethane foam are as follows:

[0118] The raw material components include: component A and component B; the formula is as shown in Table 2;

[0119] According to the measurements 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 thoroughly mixed with component B according to the measurements shown in Table 1, and then quickly injected into a mold with a mold temperature of 65°C for reaction and foaming. After 120 seconds, the mold is opened and the foam is removed (the gelation time needs to be less than 70 seconds) to prepare polyurethane foam.

[0120] In Comparative Examples 1 and 4-5, no catalyst was added to the formulation system, so the polyurethane foam could not be formed, i.e., it could not form foam normally; therefore, Comparative Examples 1 and 4-5 could not be used for product performance testing.

[0121] In Tables 1 and 2, each raw material component is calculated in parts by mass.

[0122] As can be seen from the data in the examples, by adopting the technical solution of the present invention, rapid curing can be achieved in the polyurethane foam formulation without the use of a catalyst. At the same time, the damping performance of the product can be regulated by controlling the content of EO segments in the system, and finally, damping foam with low odor and low VOC content can be prepared.

[0123] Compared with the examples, Comparative Examples 1-2 show that in Comparative Example 1, when the highly active polyether selected by this technical solution was not used and no catalyst was added to the formulation, the foam could not be formed normally; in Comparative Example 2, when the highly active polyether selected by this technical solution was not used and a catalyst was added to the formulation, although the foam could be formed normally, the odor and VOC content were both high.

[0124] Compared with the examples, Comparative Example 3 is a traditional technology for slow rebound foam, which requires the addition of a catalyst and the use of low molecular weight polyols in the formulation, but the resulting foam has a higher odor and VOC content.

[0125] Comparative Example 4 shows that when the proportion of active polyether polyol used in a method other than the one described in this technical solution is not within the range of the proportion of active polyether polyol used in this technical solution, the reactivity of the polyether polyol will be adversely affected, and foam formation cannot be guaranteed when no catalyst is added to the formulation; Comparative Example 5 shows that when polyether polyol is prepared using an amine initiator other than the one described in this technical solution, the reactivity of the polyether polyol is adversely affected, and foam formation cannot be guaranteed when no catalyst is added to the formulation.

[0126] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they 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 invention.

Claims

1. A highly active polyether polyol A1, characterized in that, The highly reactive polyether polyol A1 is a product obtained by ring-opening polymerization of an initiator and an epoxide compound as a 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 includes 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 containing a tertiary or secondary amine group at one end and a primary amine group at the other end has the following specific structure: Among them, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 and R 13 Each can be independently one or more of -CH3, -CH2CH3, -CH2CH2CH3, and -CH2CH2CH2CH3.

3. The polyether polyol A1 according to claim 1, characterized in that, The alkyl oxide compound is ethylene oxide, or a mixture of ethylene oxide with at least one of propylene oxide and butane oxide; The content of ethylene oxide in the highly active polyether polyol A1 is ≥40wt%.

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

5. The method for preparing the highly active polyether polyol A1 according to any one of claims 1-4, characterized in that, Includes the following steps: S1: The initiator and catalyst are added to the reactor, the system is heated, and the epoxide compound is introduced to carry out the reaction; S2: Adjust the system temperature, then introduce the epoxide compound again to continue the reaction; S3: Transfer the reaction material obtained in step S3 to a refining kettle, then add acid to neutralize it, and then dehydrate and filter it 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 alkali metal catalysts, inorganic bases, organic bases, and phosphazene catalysts; In step S1, the system temperature is 85-110℃ and the system pressure is below 0.5MPaG; In step S1, the introduced alkyl oxide compound is a mixture of propylene oxide and ethylene oxide, and the addition cycle of the alkyl oxide compound is 5-10 hours. In step S2, the system temperature is adjusted to 110-130℃ and the system pressure is lower than 0.5MPaG; In step S2, the added alkyl oxide compound is ethylene oxide, and the addition cycle of the alkyl oxide compound is 1-3 hours; In step S3, the acid solution is selected from one or more of the following: phosphoric acid aqueous solution, sulfuric acid aqueous solution, acetic acid aqueous solution, and hydrochloric acid aqueous solution.

7. A viscoelastic polyurethane foam, characterized in that, Its raw material components include: component A and component B; component A is the isocyanate reactive component, and component B isocyanate; wherein, The isocyanate has an NCO content of 18–35 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 as described in any one of claims 1-4 or a highly active polyether polyol A1 prepared by the preparation method as described in any one of claims 5-6.

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 prepolymers.

9. The viscoelastic polyurethane foam according to claim 7, characterized in that, The polyether polyol composition further includes polyether polyol A2; The polyether polyol A2 has an average functionality of 3-5 and a hydroxyl value of 24-42 mgKOH / g; The polyether polyol A2 is a product obtained by ring-opening polymerization using a small molecule alcohol or small molecule amine with a functionality of 3-5 as an initiator and an epoxide compound as a polymerization monomer; wherein the epoxide compound is a mixture of ethylene oxide and propylene oxide, and the content of ethylene oxide is 20-40 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 weight; Polyether polyol A2, 0-40 parts by weight; Foaming agent, 3-6 parts by weight.

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

12. The method for preparing viscoelastic polyurethane foam according to any one of claims 7-11, characterized in that, Includes the following steps: (1) The raw materials of the isocyanate reactive component are mixed evenly to obtain component A; (2) At 20-40°C, the obtained component A and component B are thoroughly mixed and stirred, and then quickly injected into the mold to foam. 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 7-11 or the viscoelastic polyurethane foam prepared by the preparation method according to claim 12 in the preparation of high-resilience polyurethane flexible foam.

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