A method for preparing a polyether polyol, the resulting polyether polyol, and its application in flexible polyurethane foam.

Abstract

This invention discloses a method for preparing polyether polyol, the obtained polyether polyol, and its application in flexible polyurethane foam. The method for preparing the polyether polyol includes: (1) reacting raw material I, including an initiator, a multi-metal composite catalyst, and an epoxy compound, to obtain a prepolymer; and (2) end-capping the prepolymer to obtain the polyether polyol. The method for preparing the polyether polyol uses a multi-metal composite catalyst and a novel process to obtain the polyether polyol of this invention. The flexible polyurethane foam prepared using the polyether polyol exhibits excellent constant load repeated indentation fatigue performance, effectively solving the problem that flexible polyurethane foam in packaging rolls cannot recover its original shape.

Description

Technical Field

[0001] This invention belongs to the field of polyether polyols, and particularly relates to a method for preparing polyether polyols, the obtained polyether polyols and their application in flexible polyurethane foams. Background Technology

[0002] Flexible polyurethane foam (also known as polyurethane flexible foam) refers to a type of flexible polyurethane foam with a certain degree of elasticity. It is the most widely used polyurethane product. Main products include high-resilience foam (HRF), block sponge, slow-resilience foam, self-skinning foam (SF), and semi-rigid energy-absorbing foam.

[0003] Flexible polyurethane foam, due to its low density, breathability, sound absorption, heat insulation, and good resilience, is mainly used as a material for vehicle seats, furniture cushioning, various laminated composite materials, as well as for sound insulation, filtration, decoration, shock absorption, and packaging. Because of its low density, it occupies a large volume during export transportation. Therefore, it is usually vacuum-packed to significantly compress its volume before export. The vacuum packaging is then removed before sale to restore its original shape.

[0004] Polyether polyols are important intermediate raw materials for the synthesis of polyurethane. Since the 1950s, with the development of the polyurethane industry and the increase in consumption, the production of polyether polyols has increased year by year. Polyether polyols also have the greatest impact on the properties of flexible polyurethane foams.

[0005] However, conventional flexible polyurethane foams are mostly prepared using polyether polyols prepared with alkaline catalysts. These polyether polyols contain a large amount of unsaturated byproduct monools and other low-molecular-weight polyethers, which degrades the physical and mechanical properties of the polyurethane foam products. After prolonged vacuum compression, most foams cannot return to their original shape, severely affecting the quality of the foam products. Specifically, under strongly alkaline conditions, isopropyl alcohol with propylene oxide as the terminal group easily isomerizes to allyl alcohol, which further isomerizes to allyl ether, thus generating unsaturated polyethers with allyl terminal groups in the long polyether chain. Because the allyl terminal groups in the polyether cannot react with isocyanates during foam production, the degree of crosslinking of the foam decreases, affecting its performance. Furthermore, the wet heat aging performance and dry heat aging performance of polyurethane foam directly affect the product's service life and are important performance indicators for polyurethane foam. Summary of the Invention

[0006] To overcome the problems existing in the prior art, this invention discloses a method for preparing polyether polyol, the obtained polyether polyol, and its application in flexible polyurethane foam. This solves the problem that flexible polyurethane foam in packaging rolls cannot return to its original shape. The flexible polyurethane foam prepared by the polyether polyol described in this invention can still return to its original shape after prolonged vacuum compression. Furthermore, because this foam has excellent constant load repeated indentation fatigue performance, wet heat aging performance, and dry heat aging performance, it can be used in environments with high requirements for indentation fatigue, allowing the product to maintain its comfort even after long-term use.

[0007] One of the objectives of this invention is to provide a method for preparing polyether polyol, comprising: (1) reacting raw material I, including an initiator, a multi-metal composite catalyst and an epoxy compound, to obtain a prepolymer; and (2) end-capping the prepolymer to obtain the polyether polyol.

[0008] In a preferred embodiment, the initiator is an oligomeric polyol containing multiple active hydrogen groups.

[0009] In a further preferred embodiment, the oligomeric polyol has a molecular weight of 200 to 2000 and contains 2 to 6 active hydrogen groups (e.g., hydroxyl groups).

[0010] In a further preferred embodiment, the oligomeric polyol has a molecular weight of 300 to 2000 and contains 2 to 4 active hydrogen groups (e.g., hydroxyl groups).

[0011] For example, the oligomeric polyol has a molecular weight of 300, 400, 500, 600, 700, 800, 900, 1000, 1200 or 1500, and contains 2, 3 or 4 active hydrogen groups.

[0012] In a preferred embodiment, in step (1), the ratio of the initiator, the epoxy compound and the multi-metal composite catalyst is (50-500):(1000-2000):(0.1-10), preferably (100-350):(1100-1400):(0.2-8).

[0013] In a preferred embodiment, in step (1), the amount of the initiator is 50 to 500 parts by weight, preferably 100 to 350 parts by weight.

[0014] For example, the amount of the initiator is 50 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 150 parts by weight, 180 parts by weight, 200 parts by weight, 220 parts by weight, 250 parts by weight, 280 parts by weight, 300 parts by weight, or 350 parts by weight.

[0015] In a preferred embodiment, the multimetallic composite catalyst comprises a multimetallic cyanide complex and a dispersant.

[0016] In a further preferred embodiment, based on a total weight of 100 wt% of the multimetallic composite catalyst, the weight content of the multimetallic cyanide complex is 1 to 10 wt%, preferably 3 to 7 wt%.

[0017] For example, in the multi-metal composite catalyst, the weight content of the multi-metal cyanide complex is 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%.

[0018] The multimetallic cyanide complex is dispersed in the dispersant to obtain the multimetallic composite catalyst.

[0019] In a preferred embodiment, the structure of the polymetallic cyanide complex is shown in formula (I):

[0020] M 1 a [M 2 d (CN) f ].M 1 b [M 3 e (CN) g ].M 1 c X h .Y i .Z j .kH2O Formula (I)

[0021] In formula (I):

[0022] M 1 M 3 Each is independently selected from Zn, Fe, Ni, Mn, Co, Sn, Ph, Mo, Al, V, Sr, W, Cu, or Cr; among which, M 1 Preferably Zn, Ni, or Co; M 3 Preferably Zn or Fe;

[0023] M 2 It is selected from Fe, Co, Cr, Mn, Ir, Ni, Rh, Ru or V, preferably Fe or Co;

[0024] X is selected from halogen elements, OH - NO3 - CO3 2- SO4 2- or ClO32- ;

[0025] Y is selected from C4-C6 cells with a tertiary alcohol structure. 10 Organic alcohols, preferably tert-butanol or tert-amyl alcohol;

[0026] Z is selected from aliphatic esters, aromatic monoesters or aromatic diesters, preferably aromatic diesters, and more preferably phthalates;

[0027] a, b, and c represent M 1 The number of ions; d and e represent M respectively. 2 M 3 Number of ions; f and g represent the number of CN ions; h, i, j, and k represent the number of X, Y, Z, and H2O ions, respectively.

[0028] Each of a, b, c, d, e, f, g, h, i, j, and k is independently 0.01 to 10, preferably 0.02 to 5, for example 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.08, 0.1, 0.2, 0.5, 0.8, 1, 1.5, 2, 2.5, 3, 3.5, 4, 5, 6, 7, 8, 9, 9, or 10.

[0029] In a preferred embodiment, the dispersant is a polymer that is liquid at -10°C to 40°C, and contains polar groups other than hydroxyl groups.

[0030] In a further preferred embodiment, the dispersant is selected from at least one of capped polyether, polyester, and organosilicon polymer.

[0031] In a further preferred embodiment, the dispersant is a capped polyether having the molecular structure shown in formula (II):

[0032]

[0033] In formula (II), R1 is selected from C1 to C8 alkyl groups, R2 is selected from hydrogen, C1 to C8 alkyl groups or phenyl groups, R3 is selected from C1 to C8 alkyl groups, and n = 5 to 12.

[0034] For example: R1 is selected from C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl or C8 alkyl; R2 is selected from hydrogen, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl or phenyl; R3 is selected from C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl or C8 alkyl; n = 5, 6, 7, 8, 9, 10, 11, 12.

[0035] In a preferred embodiment, in step (1), the amount of the multi-metal composite catalyst is 0.1 to 10 parts by weight, preferably 0.2 to 8 parts by weight.

[0036] For example, the amount of the multi-metal composite catalyst is 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 1 part by weight, 1.2 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2 parts by weight, 3 parts by weight, 5 parts by weight, 8 parts by weight, or 10 parts by weight.

[0037] In this invention, the multi-metal composite catalyst is prepared as follows:

[0038] (a) Water-soluble cyanide metal salts (including those containing metal M) 2 Water-soluble cyanide metal salts and metal-containing M 3 Aqueous solutions of water-soluble metal cyanide salts, containing M 1 An aqueous solution of a water-soluble salt (e.g., a water-soluble zinc salt) and an organic ligand Y are mixed and reacted to generate a cyanide complex catalyst suspension.

[0039] (b) Add organic ligand Z or its aqueous solution to the above cyanide complex suspension, disperse evenly, and filter;

[0040] (c) Disperse the filter cake obtained in (b) with organic ligand Y or its aqueous solution, then add organic ligand 2 or its aqueous solution, disperse evenly, and filter.

[0041] (d) Disperse the filter cake obtained in (c) in organic ligand Y, then add organic ligand Z, disperse evenly, and filter.

[0042] (e) Disperse the filter cake obtained in (d) in a dispersant to obtain the multi-metal composite catalyst;

[0043] The water-soluble cyanide metal salt is selected from at least one or a mixture of two or more of potassium hexacyanocobaltate, potassium hexacyanoferrate, potassium hexacyanoferrate, calcium hexacyanocobaltate, and potassium tetracyanobenzene; the water-soluble zinc salt is selected from at least one of zinc chloride, zinc bromide, zinc acetate, or zinc sulfate. Preferably, the water-soluble cyanide metal salt is a mixture of potassium hexacyanocobaltate and potassium hexacyanoferrate.

[0044] In a preferred embodiment, the epoxy compound is selected from at least one of ethylene oxide, propylene oxide, and butane oxide.

[0045] In a further preferred embodiment, in step (1), the amount of the epoxy compound used is 1000 to 2000 parts by weight, preferably 1100 to 1400 parts by weight.

[0046] For example, the amount of the epoxy compound used is 1000 parts by weight, 1100 parts by weight, 1200 parts by weight, 1300 parts by weight, 1400 parts by weight, 1500 parts by weight, 1600 parts by weight, 1700 parts by weight, 1800 parts by weight, 1900 parts by weight, or 2000 parts by weight.

[0047] In a preferred embodiment, in step (1), the raw material I further comprises a small molecule polyol.

[0048] In step (1), adding small molecule polyols can reduce the generation of ultra-high molecular weight substances and avoid the phenomenon of foam collapse or foam shrinkage caused by ultra-high molecular weight substances during the foaming process.

[0049] In a further preferred embodiment, the small molecule polyol is selected from at least one of ethylene glycol, propylene glycol, glycerol, diethylene glycol, trimethylolpropane, and butanediol.

[0050] The small molecule polyols can be selected from any one, any two, or any more of the above-mentioned types.

[0051] In a further preferred embodiment, the amount of the small molecule polyol is 0 to 20 parts by weight, preferably excluding 0, and more preferably 1 to 12 parts by weight.

[0052] The amount of the small molecule polyol used is 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, 9.5 parts by weight, 10 parts by weight, 11 parts by weight, or 12 parts by weight.

[0053] The ratio of the initiator, epoxy compound and multi-metal composite catalyst is (50-500):(1000-2000):(0.1-10):(0-20, preferably excluding 0); preferably, the ratio of the initiator, epoxy compound and multi-metal composite catalyst is (100-350):(1100-1400):(0.2-8):(1-12).

[0054] In this invention, the small molecule polyol and the oligomer polyol form a composite initiator.

[0055] In a preferred embodiment, step (1) includes the following sub-steps:

[0056] (1.1) Mix the oligomeric polyol and the multi-metal composite catalyst;

[0057] (1.2) After heating, an epoxy compound and a small molecule polyol are added to the system of step (1.1), and the prepolymer is obtained by reaction.

[0058] The inventors discovered through numerous experiments that adding the small molecule polyol in step (1.2) yields better results than adding it in step (1.1). The reason for this is that adding the small molecule polyol in step (1.1) may affect the activity of the multi-metal composite catalyst to some extent.

[0059] In addition, in the preparation method described in this invention, the multi-metal composite catalyst does not need to be subjected to initiation treatment in step (1), which is completely different from the prior art.

[0060] In a preferred embodiment, in step (1.2), the temperature is raised to 90–150°C, preferably to 110–130°C.

[0061] In a preferred embodiment, in step (1.2), the control pressure is not higher than 0.4 MPa, preferably not higher than 0.25 MPa.

[0062] In this invention, pressure refers to gauge pressure.

[0063] In a preferred embodiment, a removal treatment is performed after the reaction described in step (1) and before the end-capping treatment described in step (2) to remove small molecule volatiles from the system.

[0064] In a further preferred embodiment, the removal process is carried out under reduced pressure and / or at a high temperature of 80–110°C.

[0065] In a preferred embodiment, in step (2), the prepolymer is end-capped using ethylene oxide in the presence of an alkali metal catalyst.

[0066] In a further preferred embodiment, the end-sealing process in step (2) is performed at 90-150°C, preferably at 100-130°C.

[0067] For example, the end-sealing process described in step (2) is performed at 90°C, 100°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C or 150°C.

[0068] In a preferred embodiment, the alkali metal catalyst is selected from at least one of alkali metals, alkali metal hydroxides, alkali metal alkoxides, and alkali metal oxides.

[0069] In a further preferred embodiment, the alkali metal catalyst is selected from at least one of potassium hydroxide, sodium hydroxide, cesium hydroxide, potassium methoxide, potassium acetate, potassium tert-butoxide, metallic potassium, metallic sodium, etc.

[0070] In a further preferred embodiment, the alkali metal catalyst is selected from potassium hydroxide and / or potassium methoxide.

[0071] In a preferred embodiment, based on a theoretical weight of 100 wt% for the polyether polyol, the amount of the alkali metal catalyst is 1000–5000 ppm, preferably 2000–3000 ppm.

[0072] In a preferred embodiment, based on a prepolymer weight of 100 wt%, the amount of ethylene oxide is 5 to 40 wt%, preferably 10 to 30 wt%.

[0073] For example, based on the theoretical weight of the polyether polyol being 100 wt%, the amount of ethylene oxide used is 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, or 40 wt%.

[0074] In a preferred embodiment, the reaction in step (1) and the end-capping treatment in step (2) are both carried out under a protective atmosphere, preferably nitrogen and / or argon.

[0075] In a preferred embodiment, refining is optionally performed after the end-capping process described in step (2).

[0076] In a further preferred embodiment, the refining process includes: adding 2-10% water based on the total mass of the crude ether to the crude ether after the end-capping treatment in step (2), emulsifying at 50-100°C for 0.2-2 hours, then adding an acid solution for neutralization, maintaining the neutralization at 50-100°C for 0.2-2 hours, adding 0.2-5‰ adsorbent based on the total mass of the crude ether, adsorbing at 60-120°C for 0.2-5 hours, removing water (e.g., vacuum dehydration), and filtering.

[0077] For example, the refining process is as follows: 5% pure water based on the total mass of the crude ether is added to the crude ether after the end-capping treatment described in step (2), and emulsification is carried out at 80°C for 1 hour. Then, an aqueous solution of phosphoric acid that can neutralize the alkali metal in step (2) is added, and neutralization is carried out at 80°C for 1 hour. Then, an adsorbent based on 1.5‰ of the total mass of the crude ether is added, and adsorption is carried out at 90°C for 2 hours. Then, vacuum dehydration is carried out at 90-110°C, and filtration is performed to obtain a low-unsaturation, high-molecular-weight, high-activity polyether polyol.

[0078] A second objective of this invention is to provide a polyether polyol obtained by the preparation method described in one objective of this invention.

[0079] In a preferred embodiment, the polyether polyol has a functionality of 2 to 6 (preferably 2 to 4) and a relative molecular mass of 6,000 to 12,000.

[0080] In a preferred embodiment, the degree of unsaturation of the polyether polyol is no more than 0.02 mmol / kg, preferably no more than 0.01 mmol / kg.

[0081] A third objective of this invention is to provide the application of the polyether polyol obtained by the preparation method described in one objective of this invention in the preparation of flexible polyurethane foam.

[0082] The low-unsaturation polyether polyols disclosed in the prior art are prone to collapse or shrinkage when applied to flexible polyurethane foam. This is related to the catalysts and preparation processes of the polyether polyols described in the prior art.

[0083] However, after extensive experimental research, the inventors discovered that the soft polyurethane foam prepared using the polyether polyol described in this invention exhibits a 40% reduction in indentation hardness loss rate after repeated indentation fatigue under constant load, which is more than 30% lower than that of polyether polyols disclosed in the prior art. The foam's permanent compression deformation also shows a significant decrease.

[0084] Therefore, using this foam in flexible polyurethane foams such as export roll packaging, or in environments where repeated compression of the foam is required, can maintain the shape of the foam, extend its service life, and ensure excellent product quality.

[0085] The fourth objective of this invention is to provide a method for preparing flexible polyurethane foam, comprising: using a component including a polyol component, a catalyst, a foaming agent, a crosslinking agent, a foam stabilizer, and a polyisocyanate as raw material II, and reacting to obtain the flexible polyurethane foam; wherein the polyol component includes a polymeric polyol and a polyether polyol prepared by the method described in one objective of this invention.

[0086] In a preferred embodiment, the total amount of the polyol component is 100 parts by weight, and the amount of the polyether polyol is 1-100 parts by weight, preferably 10-90 parts by weight.

[0087] In a preferred embodiment, the polymeric polyol is selected from polymeric polyols containing a solid content of 0 to 50 wt%.

[0088] The polymer polyol can be prepared in-house using methods disclosed in the prior art, or it can be purchased.

[0089] In a further preferred embodiment, the total amount of the polyol component is 100 parts by weight, and the amount of the polymer polyol is 0 to 99 parts by weight, preferably 10 to 90 parts by weight.

[0090] In a preferred embodiment, the catalyst is selected from amine catalysts, preferably from tertiary amine catalysts, and more preferably from at least one of triethylenediamine, bis(dimethylaminoethyl) ether, dimethylethanolamine, and trimethylaminoethylethanolamine.

[0091] In a further preferred embodiment, based on a total amount of 100 parts by weight of the polyol components, the amount of the catalyst is 0.05 to 2 parts by weight, preferably 0.1 to 1 parts by weight.

[0092] In a preferred embodiment, the foaming agent is selected from at least one of water, air, nitrogen, liquefied carbon dioxide, and inert gas.

[0093] In a further preferred embodiment, the total amount of the polyol components is 100 parts by weight, and the amount of the foaming agent is 0 to 10 parts by weight, preferably 1 to 5 parts by weight.

[0094] In a preferred embodiment, the crosslinking agent is selected from at least one of triethanolamine, diethanolamine, triisopropanolamine, and methyldiethanolamine.

[0095] In a further preferred embodiment, based on the total amount of the polyol components being 100 parts by weight, the amount of the crosslinking agent being 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight.

[0096] In a preferred embodiment, the foam stabilizer is selected from siloxane foam stabilizers.

[0097] In a further preferred embodiment, based on the total amount of the polyol components being 100 parts by weight, the amount of the foam stabilizer is 0.1 to 20 parts by weight, preferably 0.1 to 10 parts by weight.

[0098] In a preferred embodiment, the polyisocyanate is selected from at least one of aromatic diisocyanates, preferably from at least one of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and 4,4'-diphenylmethane diisocyanate.

[0099] In a further preferred embodiment, the isocyanate index is 0.8 to 1.2, preferably 0.9 to 1.1.

[0100] In a preferred embodiment, the method for preparing the flexible polyurethane foam includes:

[0101] (A) Mixing components including polyol components, catalysts, foaming agents, crosslinking agents and foam stabilizers to form a premix;

[0102] (B) The polyisocyanate is rapidly mixed with the premixed material and cured, followed by aging treatment to obtain the flexible polyurethane foam.

[0103] In a further preferred embodiment, prior to the rapid mixing in step (B), the temperature of the premix and the polyisocyanate is controlled at 20-30°C, preferably 25±2°C.

[0104] Among them, aging is the foam performance tested after aging for 72 hours according to national standards.

[0105] The fifth objective of this invention is to provide a flexible polyurethane foam obtained by the preparation method described in the fourth objective of this invention.

[0106] Compared with the prior art, the present invention has the following beneficial effects:

[0107] (1) When the polyether polyol described in this invention is applied to polyurethane, the problem that soft polyurethane foam in packaging rolls cannot restore its original shape is solved. Specifically, the soft polyurethane foam prepared by the polyether polyol described in this invention can still restore its original shape after being vacuum compressed for a long time.

[0108] (2) Because the foam has excellent constant load repeated indentation fatigue performance, wet heat aging performance and dry heat aging performance, it can be used in environments with high requirements for indentation fatigue, so that the product can still maintain its comfort after long-term use. Detailed Implementation

[0109] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0110] The trifunctional polyether with a molecular weight of 700 used in the examples and comparative examples, and the polyoxyethylene glycol with a molecular weight of 500 used in Comparative Example 2, were prepared by a known alkaline catalytic method or are commercially available.

[0111] The polymer polyol CHP-H45 (with a solid content of 45% wt) used in the examples and comparative examples was purchased from Jiangsu Changhua Polyurethane Technology Co., Ltd.

[0112] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0113]

Example 1

[0114] 5.6 g of K3[Co(CN)6] and 2.52 g of K2[CoFe(CN)6] were dissolved in 150 mL of deionized water. Then, 65 g of a 38.5% (by weight) ZnCl2 aqueous solution was added at 8000 rpm. Next, a mixture of 100 mL of tert-butanol and 100 mL of deionized water was added and stirred for 25 min. Then, a mixture of 14.5 g of dimethyl phthalate and 200 mL of deionized water was added and stirred for another 10 min. The mixture was then filtered under vacuum using a sintered glass funnel. Finally, the resulting solid was added to a mixture of 150 mL of tert-butanol and 50 mL of deionized water and stirred at 8000 rpm for 10 min. Then, 10.6 g of dimethyl phthalate was added and stirred for another 10 min. The mixture was then centrifuged. The obtained solid was then added to 220 mL of tert-butanol and stirred at 8000 r / min for 10 min. Next, 6.8 g of dimethyl phthalate was added, and the mixture was stirred for another 10 min. After centrifugation, a solid sample of a polymetallic cyanide complex was obtained. Elemental analysis, thermogravimetric analysis, mass spectrometry, and atomic spectroscopy revealed the following composition of the solid sample: dimethyl phthalate 13 wt%, tert-butanol 10.1 wt%, Zn 20.2 wt%, Co 7.3 wt%, Fe 2.1 wt%, and H₂O 0.2 wt%.

[0115] The corresponding structural formula is:

[0116] Zn 0.186 [Co 0.124 (CN) 0.744 ].Zn 0.05 [Fe 0.038 (CN) 0.228 ].Zn 0.067 Cl 0.134 .Y 0.136 .Z 0.067 0.011H2O.

[0117] Finally, 14g of the obtained solid was dispersed in 150g of end-capped polyether with a molecular weight of 500, wherein R1 is ethyl, R2 is H, R3 is methyl, and n=10, to obtain 164g of multi-metal composite catalyst.

[0118]

Example 2

[0119] In a reactor equipped with a temperature gauge, a stirring device, and a 2.5L feed inlet, 154.2g of a trifunctional polyether with a molecular weight of 700 and 0.878g of the multi-metal composite catalyst prepared in Example 1 were added. The mixture was purged with nitrogen several times and evacuated for 1 hour. When the temperature reached 125°C, a mixture of 1178.4g of propylene oxide, 294.6g of ethylene oxide, and 6.76g of propylene glycol was introduced, maintaining a pressure not exceeding 1.0MPa. After aging, small molecule volatiles were removed under reduced pressure to obtain a prepolymer. 5.3g of KOH catalyst was added to the prepolymer, purged with nitrogen several times, and evacuated to remove moisture and small molecule impurities. Then, 264.7g of ethylene oxide was added dropwise for end-capping. After the addition was complete, the mixture was aged at the reaction temperature to form a crude ether.

[0120] The crude ether was added to a refining reactor, and 5% of the total mass of the crude ether was added to pure water. The mixture was emulsified at 80°C for 1 hour. 16.6 g of 50% phosphoric acid aqueous solution was added, and the mixture was neutralized at 80°C for 1 hour. Magnesium silicate adsorbent at 1.5‰ of the total mass of the crude ether was added, and the mixture was adsorbed at 90°C for 2 hours. Vacuum was slowly opened and the pressure was maintained at -0.10 to -0.07 MPa. The mixture was dehydrated for 3 hours and filtered to obtain a low-unsaturation, high-molecular-weight, highly active polyether polyol.

[0121] The premixed materials prepared in this example were mixed in the following ways: 60 parts by weight of polyether polyol, 40 parts by weight of polymer polyol, 0.05 parts by weight of amine catalyst A-1, 0.20 parts by weight of amine catalyst A-33, 0.17 parts by weight of tin catalyst D-19, 2.4 parts by weight of foaming agent water, 2 parts by weight of crosslinking agent diethanolamine, and 0.85 parts by weight of silicone oil L-5333. Toluene diisocyanate was used, with an isocyanate index of 1.07. The temperature of the premixed material and the polyisocyanate was controlled at 25±2℃. The mixture was quickly stirred and poured into a box for curing. After curing, the mixture was removed from the box and aged for 72 hours before foam performance testing was performed.

[0122] The foam properties in this embodiment are shown in Table 1.

[0123]

Example 3

[0124] In a reactor equipped with a temperature gauge, a stirring device, and a 2.5L feed inlet, 129.4g of an initiator with a molecular weight of 700 and 0.878g of the multi-metal composite catalyst prepared in Example 1 were added. The mixture was purged with nitrogen several times and evacuated for 1 hour. When the temperature reached 125°C, a mixture of 1108.0g of propylene oxide, 369.3g of ethylene oxide, and 5.67g of propylene glycol was introduced, maintaining a pressure not exceeding 1.0MPa. After aging, small molecule volatiles were removed under reduced pressure to obtain a prepolymer. 5.3g of KOH catalyst was added to the prepolymer, purged with nitrogen several times, and evacuated to remove moisture and small molecule impurities. Then, 264.7g of ethylene oxide was added dropwise for end-capping. After the addition was complete, the mixture was aged at the reaction temperature to form a crude ether.

[0125] The crude ether was added to a refining reactor, and 5% of the total mass of the crude ether was added to pure water. The mixture was emulsified at 80°C for 1 hour. 16.3 g of 50% phosphoric acid aqueous solution was added, and the mixture was neutralized at 80°C for 1 hour. Magnesium silicate adsorbent at 1.5‰ of the total mass of the crude ether was added, and the mixture was adsorbed at 90°C for 2 hours. Vacuum was slowly opened and the pressure was maintained at -0.10 to -0.07 MPa. The mixture was dehydrated for 3 hours and filtered to obtain a low-unsaturation, high-molecular-weight, highly active polyether polyol.

[0126] The premixed materials prepared in this example were mixed in the following ways: 60 parts by weight of polyether polyol, 40 parts by weight of polymer polyol, 0.05 parts by weight of amine catalyst A-1, 0.20 parts by weight of amine catalyst A-33, 0.17 parts by weight of tin catalyst D-19, 2.4 parts by weight of foaming agent water, 2 parts by weight of crosslinking agent diethanolamine, and 0.85 parts by weight of silicone oil L-5333. Toluene diisocyanate was used, with an isocyanate index of 1.07. The temperature of the premixed material and the polyisocyanate was controlled at 25±2℃. The mixture was quickly stirred and poured into a box for curing. After curing, the mixture was removed from the box and aged for 72 hours before foam performance testing was performed.

[0127] The foam properties in this embodiment are shown in Table 1.

[0128]

Example 4

[0129] In a reactor equipped with a temperature gauge, a stirring device, and a 2.5L feed inlet, 112.0g of an initiator with a molecular weight of 700 and 0.878g of the multi-metal composite catalyst prepared in Example 1 were added. The reactor was purged with nitrogen several times and evacuated for 1 hour. When the temperature reached 125°C, a mixture of 1151.4g of propylene oxide, 329.0g of ethylene oxide, and 4.91g of propylene glycol was introduced, maintaining a pressure not exceeding 1.0MPa. After aging, small molecule volatiles were removed under reduced pressure to obtain a prepolymer. 5.3g of KOH catalyst was added to the prepolymer, purged with nitrogen several times, and evacuated to remove moisture and small molecule impurities. Then, 264.7g of ethylene oxide was added dropwise for end-capping. After the addition was complete, the reactor was aged at the reaction temperature to form a crude ether.

[0130] The crude ether was added to a refining reactor, and 5% of the total mass of the crude ether was added to pure water. The mixture was emulsified at 80°C for 1 hour. 16.3 g of 50% phosphoric acid aqueous solution was added, and the mixture was neutralized at 80°C for 1 hour. Magnesium silicate adsorbent at 1.5‰ of the total mass of the crude ether was added, and the mixture was adsorbed at 90°C for 2 hours. Vacuum was slowly opened and the pressure was maintained at -0.10 to -0.07 MPa. The mixture was dehydrated for 3 hours and filtered to obtain a low-unsaturation, high-molecular-weight, highly active polyether polyol.

[0131] The premixed materials prepared in this example were mixed in the following ways: 60 parts by weight of polyether polyol, 40 parts by weight of polymer polyol, 0.05 parts by weight of amine catalyst A-1, 0.20 parts by weight of amine catalyst A-33, 0.17 parts by weight of tin catalyst D-19, 2.4 parts by weight of foaming agent water, 2 parts by weight of crosslinking agent diethanolamine, and 0.85 parts by weight of silicone oil L-5333. Toluene diisocyanate was used, with an isocyanate index of 1.07. The temperature of the premixed material and the polyisocyanate was controlled at 25±2℃. The mixture was quickly stirred and poured into a box for curing. After curing, the mixture was removed from the box and aged for 72 hours before foam performance testing was performed.

[0132] The foam properties in this embodiment are shown in Table 1.

[0133]

Example 5

[0134] 5.5 g of K3[Co(CN)6] and 2.51 g of K2[CoFe(CN)6] were dissolved in 150 mL of deionized water. Then, 65 g of a 38.5% (by weight) ZnCl2 aqueous solution was added at 8000 rpm. Next, a mixture of 100 mL of tert-butanol and 100 mL of deionized water was added and stirred for 25 min. Then, a mixture of 14.5 g of dimethyl phthalate and 200 mL of deionized water was added and stirred for another 10 min. The mixture was then filtered under vacuum using a sintered glass funnel. Finally, the resulting solid was added to a mixture of 150 mL of tert-butanol and 50 mL of deionized water and stirred at 8000 rpm for 10 min. Then, 10.6 g of dimethyl phthalate was added and stirred for another 10 min. The mixture was then centrifuged to obtain a solid sample of a polymetallic cyanide complex. After elemental analysis, thermogravimetric analysis, mass spectrometry, and atomic spectroscopy, the composition of the solid sample was obtained as follows: dimethyl phthalate 15%, tert-butanol 9.8%, Zn 21.2%, Co 7.1%, Fe 2.2%, and H₂O 0.18wt%. The corresponding structural formula is:

[0135] Zn 0.18 [Co 0.12 (CN) 0.72 ].Zn 0.06 [Fe 0.04 (CN) 0.24 ].Zn 0.08 Cl 0.16 .Y 0.132 .Z 0.077 0.01H2O.

[0136] The obtained solid was then added to 220 mL of tert-butanol and stirred at 8000 r / min for 10 min. 6.8 g of dimethyl phthalate was then added, and the mixture was stirred for another 10 min before centrifugation. Finally, 14 g of the obtained solid was dispersed in 300 g of polysiloxane with a molecular weight of 500 to obtain 314 g of a multi-metal composite catalyst.

[0137]

Example 6

[0138] In a reactor equipped with a temperature gauge, a stirring device, and a 2.5L feed inlet, 83.9g of a trifunctional polyether with a molecular weight of 500 and 0.673g of the multi-metal composite catalyst prepared in Example 5 were added. The mixture was purged with nitrogen several times and evacuated for 1 hour. When the temperature reached 125°C, a mixture of 1181.6g of propylene oxide, 295.4g of ethylene oxide, and 7.61g of propylene glycol was introduced, maintaining a pressure not exceeding 1.0MPa. After aging, small molecule volatiles were removed under reduced pressure to obtain a prepolymer. 5.1g of KOH catalyst was added to the prepolymer, purged with nitrogen several times, and evacuated to remove moisture and small molecule impurities. Then, 204.5g of ethylene oxide was added dropwise for end-capping. After the addition was complete, the mixture was aged at the reaction temperature to form a crude ether.

[0139] The crude ether was added to a refining reactor, and 5% of the total mass of the crude ether was added to pure water. The mixture was emulsified at 80°C for 1 hour. 16.1 g of 50% phosphoric acid aqueous solution was added, and the mixture was neutralized at 80°C for 1 hour. Magnesium silicate adsorbent at 1.5‰ of the total mass of the crude ether was added, and the mixture was adsorbed at 90°C for 2 hours. Vacuum was slowly opened and the pressure was maintained at -0.10 to -0.07 MPa. The mixture was dehydrated for 3 hours and filtered to obtain a low-unsaturation, high-molecular-weight, highly active polyether polyol.

[0140] The premix was prepared by mixing 80 parts by weight of polyether polyol, 20 parts by weight of polymer polyol, 0.07 parts by weight of amine catalyst A-1, 0.25 parts by weight of amine catalyst A-33, 2.4 parts by weight of foaming agent water, 1 part by weight of crosslinking agent diethanolamine, and 0.9 parts by weight of silicone oil Y-10366. The isocyanate index was 1.05. The temperature of the premix and polyisocyanate was controlled at 25±2℃. The mixture was quickly stirred and poured into a box for curing. After curing, the mixture was removed from the box and aged for 72 hours before foam performance testing was performed.

[0141] The foam properties in this embodiment are shown in Table 1.

[0142]

Example 7

[0143] 5.6 g of K3[Co(CN)6] and 2.52 g of K2[CoFe(CN)6] were dissolved in 150 mL of deionized water. Then, 65 g of a 38.5% (by weight) ZnCl2 aqueous solution was added at 8000 rpm. Next, a mixture of 100 mL of tert-butanol and 100 mL of deionized water was added, and the mixture was stirred for 25 min. Then, a mixture of 14.5 g of dimethyl phthalate and 200 mL of deionized water was added, and the mixture was stirred for another 10 min. The mixture was then filtered under vacuum using a sintered glass funnel. Finally, the resulting solid was added to a mixture of 150 mL of tert-butanol and 50 mL of deionized water, and stirred at 8000 rpm for 10 min. Then, 10.6 g of dimethyl phthalate was added, and the mixture was stirred for another 10 min. The mixture was then centrifuged to obtain a polymetallic cyanide complex. After elemental analysis, thermogravimetric analysis, mass spectrometry, and atomic spectroscopy, the composition of the solid sample was obtained as follows: phthalate 14.7%, tert-butanol 10.2%, Zn 21.1%, Co 6.9%, Fe 2.2%, and H₂O 0.23wt%. The corresponding structural formula is: Zn 0.176 [Co 0.117 (CN) 0.702 ].Zn 0.056 [Fe 0.039 (CN) 0.234 ].Zn 0.091 Cl 0.182 .Y 0.138 .Z 0.076 0.013H2O.

[0144] The obtained solid was then added to 220 mL of tert-butanol and stirred at 8000 r / min for 10 min. 6.8 g of dimethyl phthalate was then added, and the mixture was stirred for another 10 min before centrifugation. Finally, 15 g of the obtained solid was dispersed in 300 g of end-capped polyether with a molecular weight of 500 to obtain 315 g of a multi-metal composite catalyst.

[0145]

Example 8

[0146] In a reactor equipped with a temperature gauge, a stirring device, and a 2.5L feed inlet, 186.1g of a trifunctional polyether with a molecular weight of 1000 and 0.945g of the multimetallic composite catalyst prepared in Example 7 were added. The mixture was purged with nitrogen several times and evacuated for 1 hour. When the temperature reached 125°C, a mixture of 1184.8g of propylene oxide, 296.2g of ethylene oxide, and 1.2g of propylene glycol was introduced, maintaining a pressure not exceeding 1.0MPa. After aging, small molecule volatiles were removed under reduced pressure to obtain a prepolymer. 5.1g of KOH catalyst was added to the prepolymer, purged with nitrogen several times, and evacuated to remove moisture and small molecule impurities. Then, 204.5g of ethylene oxide was added dropwise for end-capping. After the addition was complete, the mixture was aged at the reaction temperature to form a crude ether.

[0147] The crude ether was added to a refining reactor, and 5% of the total mass of the crude ether was added to pure water. The mixture was emulsified at 80°C for 1 hour. 16.1 g of 50% phosphoric acid aqueous solution was added, and the mixture was neutralized at 80°C for 1 hour. Magnesium silicate adsorbent at 1.5‰ of the total mass of the crude ether was added, and the mixture was adsorbed at 90°C for 2 hours. Vacuum was slowly opened and the pressure was maintained at -0.10 to -0.07 MPa. The mixture was dehydrated for 3 hours and filtered to obtain a low-unsaturation, high-molecular-weight, highly active polyether polyol.

[0148] The premix was prepared by mixing 50 parts by weight of polyether polyol, 50 parts by weight of polymer polyol, 0.1 parts by weight of amine catalyst EF-1000, 0.35 parts by weight of amine catalyst EF-6000, 2.4 parts by weight of foaming agent water, 2 parts by weight of crosslinking agent diethanolamine, and 0.9 parts by weight of silicone oil Y-10366J. The isocyanate index was 1.05. The temperature of the premix and polyisocyanate was controlled at 25±2℃. The mixture was quickly stirred and poured into a box for curing. After curing, the mixture was removed from the box and aged for 72 hours before foam performance testing was performed.

[0149] The foam properties in this embodiment are shown in Table 1.

[0150] Comparative Example 1

[0151] 5.6 g of K3[Co(CN)6] and 2.52 g of K2[CoFe(CN)6] were dissolved in 150 mL of deionized water. Then, 65 g of a 38.5% (by weight) ZnCl2 aqueous solution was added at 8000 rpm. Next, a mixture of 100 mL of tert-butanol and 100 mL of deionized water was added and stirred for 25 min. Then, a mixture of 14.5 g of dimethyl phthalate and 200 mL of deionized water was added and stirred for another 10 min. The mixture was then filtered under vacuum using a sintered glass funnel. Finally, the resulting solid was added to a mixture of 150 mL of tert-butanol and 50 mL of deionized water and stirred at 8000 rpm for 10 min. Then, 10.6 g of dimethyl phthalate was added and stirred for another 10 min. The mixture was then centrifuged. The obtained solid was then added to 220 mL of tert-butanol and stirred at 8000 r / min for 10 min. Next, 6.8 g of dimethyl phthalate was added, and the mixture was stirred for another 10 min before centrifugation. Finally, the obtained solid was vacuum dried at 60 °C to constant weight to obtain 13.40 g of the polymetallic cyanide complex catalyst.

[0152] Comparative Example 2

[0153] In a reactor equipped with a temperature gauge, a stirring device, and a 2.5L feed inlet, 154.2g of a trifunctional polyether with a molecular weight of 700 and 0.045g of the polymetallic cyanide complex catalyst prepared in Comparative Example 1 were added. The mixture was purged with nitrogen several times and evacuated for 1 hour. When the temperature reached 125℃, a mixture of 1178.4g of propylene oxide, 294.6g of ethylene oxide, and 6.76g of propylene glycol was introduced, maintaining a pressure not exceeding 1.0MPa. After aging, small molecule volatiles were removed under reduced pressure to obtain a prepolymer. 5.3g of KOH catalyst was added to the prepolymer, purged with nitrogen several times, and evacuated to remove moisture and small molecule impurities. Then, 264.7g of ethylene oxide was added dropwise for end-capping. After the addition was complete, the mixture was aged at the reaction temperature to form a crude ether.

[0154] The crude ether was added to a refining reactor, 88g of pure water was added, and emulsification was carried out at 80℃ for 1 hour. 16.7g of 50% phosphoric acid aqueous solution was added, and neutralization was carried out at 80℃ for 1 hour. 2.6g of magnesium silicate adsorbent was added and adsorbed at 90℃ for 2 hours. Vacuum was slowly opened and the pressure was maintained at -0.10 to -0.07MPa. Dehydration was carried out for 3 hours, and filtration was performed to obtain a low-unsaturation, high-molecular-weight, highly active polyether polyol.

[0155] The premixed product was prepared by mixing 60 parts by weight of polyether polyol, 40 parts by weight of polymer polyol, 0.05 parts by weight of amine catalyst A-1, 0.20 parts by weight of amine catalyst A-33, 0.17 parts by weight of tin catalyst D-19, 2.4 parts by weight of foaming agent water, 2 parts by weight of crosslinking agent diethanolamine, and 0.85 parts by weight of silicone oil L-5333. Toluene diisocyanate was used, with an isocyanate index of 1.07. The temperature of the premixed product and the polyisocyanate was controlled at 25±2℃. The mixture was quickly stirred and poured into a box for curing. After the foam bubble-jumping was completed, the foam sank very severely. After curing, the product was removed from the box and aged for 72 hours before foam performance testing was performed.

[0156] Due to severe foam settling, the resulting foam body could not be used for sample preparation or performance measurement.

[0157] Comparative Example 3

[0158] 13.40 g of the polymetallic cyanide complex obtained in Comparative Example 1 was dispersed in 143.6 g of polyoxyethylene glycol with a molecular weight of 500 to obtain a catalyst slurry.

[0159] Comparative Example 4

[0160] In a reactor equipped with a temperature gauge, a stirring device, and a 2.5L feed inlet, 154.2g of a trifunctional polyether with a molecular weight of 700 and 0.878g of the multi-metal composite catalyst prepared in Comparative Example 3 were added. The mixture was purged with nitrogen several times and evacuated for 1 hour. When the temperature reached 125℃, a mixture of 1178.4g of propylene oxide, 294.6g of ethylene oxide, and 6.76g of propylene glycol was introduced, maintaining a pressure not exceeding 1.0MPa. After aging, small molecule volatiles were removed under reduced pressure to obtain a prepolymer. 5.3g of KOH catalyst was added to the prepolymer, purged with nitrogen several times, and evacuated to remove moisture and small molecule impurities. Then, 264.7g of ethylene oxide was added dropwise for end-capping. After the addition was complete, the mixture was aged at the reaction temperature to form a crude ether.

[0161] The crude ether was added to a refining reactor, 88g of pure water was added, and emulsification was carried out at 80℃ for 1 hour. 16.7g of 50% phosphoric acid aqueous solution was added, and neutralization was carried out at 80℃ for 1 hour. 2.6g of magnesium silicate adsorbent was added and adsorbed at 90℃ for 2 hours. Vacuum was slowly opened and the pressure was maintained at -0.10 to -0.07MPa. Dehydration was carried out for 3 hours, and filtration was performed to obtain a low-unsaturation, high-molecular-weight, highly active polyether polyol.

[0162] A premix was prepared by mixing 60 parts by weight of polyether polyol, 40 parts by weight of polymer polyol, 0.25 parts by weight of amine catalyst A-1, 0.2 parts by weight of tin catalyst D-19, 2.4 parts by weight of foaming agent water, 2 parts by weight of crosslinking agent diethanolamine, and 0.85 parts by weight of silicone oil L-5333. Toluene diisocyanate was used with an isocyanate index of 1.07. The temperature of the premix and polyisocyanate was controlled at 25±2℃, and the mixture was quickly stirred and poured into a box for curing. During the curing process, it was found that the foam settled very seriously, with a settling rate of up to 30%. After curing, the foam was removed from the box and aged for 72 hours before foam performance testing was conducted.

[0163] The foam properties in this comparative example are shown in Table 1.

[0164] Comparative Example 5

[0165] In a reactor equipped with a thermometer, a stirring device, and a 2.5L feed inlet, 231.6g of a trifunctional polyether with a molecular weight of 700 and 5.3g of KOH catalyst were added. The mixture was purged with nitrogen several times and evacuated for 1 hour. When the temperature reached 95℃, 1268.4g of propylene oxide was added, maintaining a pressure not exceeding 1.0MPa. After aging and degassing, 265.0g of ethylene oxide was added dropwise for end-capping. After the addition was complete, aging was carried out at the reaction temperature to form crude ether. The purified end-capped product was finally filtered to obtain a highly active polyether polyol.

[0166] A premix was prepared by mixing 60 parts by weight of polyether polyol, 40 parts by weight of polymer polyol, 0.05 parts by weight of amine catalyst A-1, 0.20 parts by weight of amine catalyst A-33, 0.17 parts by weight of tin catalyst D-19, 2.4 parts by weight of foaming agent water, 2 parts by weight of crosslinking agent diethanolamine, and 0.85 parts by weight of silicone oil L-5333. Toluene diisocyanate was used, with an isocyanate index of 1.07. The temperature of the premix and polyisocyanate was controlled at 25±2℃, and the mixture was quickly stirred and poured into a box for curing. After curing, the mixture was removed from the box and aged for 72 hours before foam performance testing was conducted.

[0167] The foam properties in this comparative example are shown in Table 1.

[0168] Comparative Example 6

[0169] The process of Example 2 was repeated, except that propylene glycol was added together with a trifunctional polyether initiator with a molecular weight of 700.

[0170] It was found that when propylene glycol and 700 catalyst were added to the reactor as a raw mixture, the catalyst would be deactivated.

[0171] Comparative Example 7

[0172] In a reactor equipped with a temperature gauge, a stirring device, and a 2.5L feed inlet, 195.6g of a trifunctional polyether initiator with a molecular weight of 700 and 0.527g of the multi-metal composite catalyst prepared in Example 1 were added. The mixture was purged with nitrogen several times and evacuated for 1 hour. When the temperature reached 125°C, a mixture of 1179.4g of propylene oxide and 294.8g of ethylene oxide was introduced, maintaining a pressure not exceeding 1.0MPa. After aging, small molecule volatiles were removed under reduced pressure to obtain a prepolymer. 5.3g of KOH catalyst was added to the prepolymer, purged with nitrogen several times, and evacuated to remove moisture and small molecule impurities. Then, 264.7g of ethylene oxide was added dropwise for end-capping. After the addition was complete, the mixture was aged at the reaction temperature to form a crude ether.

[0173] The crude ether was added to a refining reactor, 88g of pure water was added, and emulsification was carried out at 80℃ for 1 hour. 16.7g of 50% phosphoric acid aqueous solution was added, and neutralization was carried out at 80℃ for 1 hour. 2.6g of magnesium silicate adsorbent was added and adsorbed at 90℃ for 2 hours. Vacuum was slowly opened and the pressure was maintained at -0.10 to -0.07MPa. Dehydration was carried out for 3 hours, and filtration was performed to obtain a low-unsaturation, high-molecular-weight, highly active polyether polyol.

[0174] A premix was prepared by mixing 60 parts by weight of polyether polyol, 40 parts by weight of polymer polyol, 0.05 parts by weight of amine catalyst A-1, 0.20 parts by weight of amine catalyst A-33, 0.17 parts by weight of tin catalyst D-19, 2.4 parts by weight of foaming agent water, 2 parts by weight of crosslinking agent diethanolamine, and 0.85 parts by weight of silicone oil L-5333. Toluene diisocyanate was used, with an isocyanate index of 1.07. The temperature of the premix and polyisocyanate was controlled at 25±2℃, and the mixture was rapidly stirred and poured into a box. During the foam rise, the system exhibited a boiling-like change, followed by foam collapse, failing to form normal foam. Therefore, foam performance testing was not possible.

[0175] Table 1. Results of foam performance tests

[0176]

[0177] In Table 1, compression set refers to the compression ratio of 75%, the test temperature of 70℃, and the test time of 22h; the indentation hardness loss rate refers to the 40% indentation hardness loss rate after repeated indentation fatigue under constant load.

Claims

1. A method for preparing a polyether polyol, comprising: (1) React raw material I, including initiator, multi-metal composite catalyst and epoxy compound, to obtain prepolymer, wherein the initiator is an oligomeric polyol containing multiple active hydrogen groups; (2) End-capping treatment of the prepolymer to obtain polyether polyol; Step (1) includes the following sub-steps: (1.1) Mix the oligomeric polyol and multi-metal composite catalyst; (1.2) After heating, an epoxy compound and a small molecule polyol are added to the system of step (1.1), and the prepolymer is obtained by reaction. The small molecule polyol is selected from at least one of ethylene glycol, propylene glycol, glycerol, diethylene glycol, trimethylolpropane, and butanediol. The amount of the initiator is 50-500 parts by weight, and the amount of the small molecule polyol is 0.5-10 parts by weight. The multi-metal composite catalyst comprises a multi-metal cyanide complex and a dispersant, wherein the structure of the multi-metal cyanide complex is shown in formula (I): M 1 a [M 2 d (CN) f . M 1 b [M 3 e (CN) g . M 1 c X h . Y i . Z j . kH2O Formula (I) In formula (I): M 1 M 3 Each is independently selected from Zn, Fe, Ni, Mn, Co, Sn, Ph, Mo, Al, V, Sr, W, Cu, or Cr; M 2 Selected from Fe, Co, Cr, Mn, Ir, Ni, Rh, Ru, or V; X is selected from halogen elements, OH... - NO3 - CO3 2- SO4 2- or ClO3 2- Y is selected from C4~C with a tertiary alcohol structure. 10 Organic alcohols; Z is selected from aliphatic esters, aromatic monoesters, or aromatic diesters; a, b, and c represent M. 1 The number of ions; d and e represent M respectively. 2 M 3 Number of ions; f and g represent the number of CN ions; h, i, j, and k represent the number of X, Y, Z, and H2O ions, respectively; a, b, c, d, e, f, g, h, i, j, and k are each independently 0.01 to 10; the dispersant is a polymer that is liquid at -10℃ to 40℃, containing polar groups other than hydroxyl groups.

2. The method for preparing polyether polyol according to claim 1, characterized in that, The epoxy compound is selected from at least one of ethylene oxide, propylene oxide, and butane oxide.

3. The method for preparing polyether polyol according to claim 2, characterized in that, The oligomeric polyol has a molecular weight of 200-2000 and contains 2-6 active hydrogen groups.

4. The method for preparing polyether polyol according to claim 1, characterized in that, In step (1), the ratio of the initiator, the epoxy compound and the multi-metal composite catalyst is (50~500):(1000~2000):(0.1~10).

5. The method for preparing polyether polyol according to claim 1, characterized in that, In step (1), the amount of the initiator is 100-350 parts by weight; and / or, In step (1), the amount of the epoxy compound used is 1000-2000 parts by weight; and / or, In step (1), the amount of the multi-metal composite catalyst is 0.1 to 10 parts by weight; and / or, Based on a total weight of 100 wt% for the multi-metal composite catalyst, the weight content of the multi-metal cyanide complex is 1-10 wt%.

6. The method for preparing polyether polyol according to claim 1, characterized in that, In step (1), the amount of the initiator is 100-350 parts by weight; and / or, In step (1), the amount of the epoxy compound used is 1100-1400 parts by weight; and / or, In step (1), the amount of the multi-metal composite catalyst is 0.2 to 8 parts by weight; and / or, Based on a total weight of 100 wt% for the multi-metal composite catalyst, the weight content of the multi-metal cyanide complex is 3-7 wt%.

7. The method for preparing polyether polyol according to claim 1, characterized in that, In step (2), the prepolymer is end-capped using ethylene oxide in the presence of an alkali metal catalyst.

8. A polyether polyol obtained by the preparation method according to any one of claims 1 to 7, wherein the polyether polyol has a functionality of 2 to 6 and a relative molecular mass of 6000 to 12000.

9. The application of the polyether polyol obtained by the preparation method according to any one of claims 1 to 7 in the preparation of flexible polyurethane foam.

10. A method for preparing flexible polyurethane foam, comprising: The flexible polyurethane foam is obtained by reacting a component including a polyol component, a catalyst, a foaming agent, a crosslinking agent, a foam stabilizer, and a polyisocyanate as raw material II; wherein the polyol component includes a polymeric polyol and a polyether polyol obtained by the preparation method according to any one of claims 1 to 7.

11. The method for preparing flexible polyurethane foam according to claim 10, characterized in that, The polymer polyol is selected from polymer polydisperse polyols containing 0-50 wt% polymer microparticles; and / or, The catalyst is selected from amine catalysts; and / or, The foaming agent is selected from at least one of water, air, nitrogen, liquefied carbon dioxide, and inert gas; and / or, The crosslinking agent is selected from at least one of triethanolamine, diethanolamine, triisopropanolamine, and methyldiethanolamine; and / or, The foam stabilizer is selected from siloxane foam stabilizers; and / or, The polyisocyanate is selected from at least one of aromatic diisocyanates.

12. The method for preparing flexible polyurethane foam according to claim 10, characterized in that, The catalyst is selected from tertiary amine catalysts; and / or, The polyisocyanate is selected from at least one of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and 4,4'-diphenylmethane diisocyanate.

13. The method for preparing flexible polyurethane foam according to claim 10, characterized in that, The catalyst is selected from at least one of triethylenediamine, bis(dimethylaminoethyl) ether, dimethylethanolamine, and trimethylaminoethylethanolamine.

14. The method for preparing flexible polyurethane foam according to claim 10, characterized in that, Based on the total amount of the polyol components being 100 parts by weight: The amount of the polyether polyol used is 1-100 parts by weight; and / or, The amount of the polymer polyol used is 0-99 parts by weight; and / or, The amount of the foaming agent used is 0-10 parts by weight; and / or, The amount of the crosslinking agent is 0.1 to 20 parts by weight; and / or, The amount of the foam stabilizer used is 0.1 to 20 parts by weight; and / or, The amount of catalyst used is 0.05 to 2 parts by weight.

15. The method for preparing flexible polyurethane foam according to claim 10, characterized in that, Based on the total amount of the polyol components being 100 parts by weight: The amount of the polyether polyol used is 10-90 parts by weight; and / or, The amount of the polymer polyol used is 10-90 parts by weight; and / or, The amount of the foaming agent used is 1 to 5 parts by weight; and / or, The amount of the crosslinking agent is 0.3 to 10 parts by weight; and / or, The amount of the foam stabilizer is 0.1 to 10 parts by weight; and / or, The amount of the catalyst used is 0.1 to 1 part by weight.

16. The method for preparing flexible polyurethane foam according to any one of claims 10 to 15, characterized in that, The method for preparing the flexible polyurethane foam includes: (A) Mixing components including polyol components, catalysts, foaming agents, crosslinking agents and foam stabilizers to form a premix; (B) The polyisocyanate is rapidly mixed with the premix and cured, and then aged to obtain the flexible polyurethane foam.

17. A flexible polyurethane foam obtained by the method for preparing flexible polyurethane foam according to any one of claims 10 to 16.

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