Amide modified polyether polyol, preparation method thereof and soft foam

Abstract

The invention discloses amide modified polyether polyol, a preparation method thereof and flexible foam. The structural formula of the amide modified polyether polyol is shown in the specification, wherein R1 is hydrogen or methyl; the number-average molecular weight is 1000-10000, and the functionality is 2-4. The polyurethane foam prepared by the method overcomes the problem that ester bonds are easy to hydrolyze, has excellent mechanical properties and water and oil resistance, is low in product viscosity, and can directly replace an existing polyester type flexible foam system.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of polyols and polyurethanes, in particular to a modified polyether polyol for polyurethane flexible foam. BACKGROUND

[0002] Polyurethane is one of the plastics widely used in many fields of modern society. The addition of a blowing agent to polyurethane can make the polymer expand, producing polyurethane foams of various purposes and properties. Among them, the more commonly used polyurethane flexible foam (hereinafter referred to as soft foam) is polyether type polyurethane foam. Some special fields use partially added polyester to improve the mechanical properties, wear resistance and oil resistance of the foam, but numerous studies have shown that the addition of polyester polyol to the foam will cause the foam to lose weather resistance, especially water resistance, which is due to the nature of the ester bond. The industry usually tries to reduce the erosion of water to the foam structure as much as possible by reducing the hydrophilicity of the alcohol segment, but this is only a temporary solution. For example, in outdoor foam application scenarios that require high strength, the problems of polyester type foam are magnified, but the performance of soft foam needs to be improved, so poly carbonate or polyether ester types have been developed.

[0003] CN1900136A provides a method for preparing a polyether ester polyol. Using this polyol, a mixture that can be mixed and pumped at room temperature and processing temperature, and has a significantly lower viscosity than pure polyester polyol, can be prepared to produce a PUR soft foam material suitable for flame-laminated cotton and meeting the performance requirements in the field. The main problem solved is that while introducing an ester bond to improve performance, the viscosity of the pure polyester polyol is reduced by introducing a polyether, but the problem of ester bond hydrolysis resistance is not solved.

[0004] CN110964167A provides a method for preparing a polycarbonate type polyurethane foam. The prepared polyurethane foam has excellent mechanical properties. The main method is to modify isocyanate with polycarbonate polyol (hereinafter referred to as PCDL) to obtain pure PCDL type soft foam by foaming. However, the pre-polymer method has the characteristics of low production efficiency, and the viscosity of the pre-polymer modified with PCDL isocyanate is large, so the commonly used foaming stirring equipment cannot realize large-scale production, and the operability of this method is low.

[0005] Existing polyols improve the mechanical properties of the foam by using polyester and polycarbonate diols, but the viscosity of the product prepared by using PCDL is large, and the product prepared by using polyester polyol is prone to hydrolysis. The problems are very prominent. The present application solves the problems of mechanical properties, viscosity and water resistance by changing the structure of the functional group. SUMMARY

[0006] The purpose of this invention is to provide an amide-modified polyether polyol, its preparation method, and a flexible foam. The non-polyester polyurethane foam prepared in this way overcomes the problem of easy hydrolysis of ester bonds. At the same time, the prepared polyurethane flexible foam has excellent mechanical properties and water and oil resistance, and the product has low viscosity, which can directly replace the existing polyester flexible foam system.

[0007] To achieve the above technical effects, the present invention adopts the following technical solution:

[0008] This invention provides an amide-modified polyether polyol, the structural formula of which is as follows:

[0009]

[0010] R1 is hydrogen or methyl, with a number average molecular weight of 1000-10000 and a functionality of 2-4.

[0011] This invention provides a method for preparing amide-modified polyether polyols, comprising the following steps:

[0012] 1) Halogenation: Halogenated polyethers are prepared by reacting polyethers with halogenating agents;

[0013] 2) Cyanidation: The reaction of halogenated polyethers with cyaniding agents prepares cyano-terminated polyethers;

[0014] 3) Hydrolysis: Hydrolysis of cyano-terminated polyethers to prepare carboxyl-terminated polyethers;

[0015] 4) Amide synthesis: Carboxyl-terminated amide-modified polyethers are prepared by amidation reaction of carboxyl-terminated polyethers and polyetheramines;

[0016] 5) Esterification, hydrogenation, and desolventization: The carboxyl-terminated amide-modified polyether is first esterified with methanol to prepare esterified end-capped polyether, and then hydrogenated and reduced.

[0017] As a preferred embodiment, the reaction temperature in step 1) is 20–120°C, the N2 pressure is 0.1 MPaA–1.0 MPaA, and the reaction time is 0.5–5 h.

[0018] As a preferred embodiment, the halogenated agent in step 1) is selected from thionyl chloride and / or phosgene, preferably thionyl chloride.

[0019] As a preferred embodiment, the polyether in step 1) has a number average molecular weight of 400-2000 and a functionality of 2-4, wherein the EO in the polymer monomer accounts for 0-100% of the total mass of EO and PO, and the initiator is selected from one or more of ethylene glycol, diethylene glycol, 1,3-propanediol, glycerol, trimethylolpropane, and pentaerythritol.

[0020] As a preferred embodiment, the amount of halogenated agent in step 1) is 1.0 to 2.0 times the molar amount of hydroxyl groups in the polyether.

[0021] As a preferred embodiment, after the reaction in step 1) is completed, the halogenated byproducts are removed under negative pressure and then the temperature is lowered.

[0022] As a preferred embodiment, the removal temperature in step 1) is 50–150°C, the removal pressure is 0.1 kPaA–90 kPaA, and the removal time is 0.5–5 h.

[0023] As a preferred embodiment, the reaction temperature in step 2) is 10–100°C, and the reaction time is 0.5–5 h.

[0024] As a preferred embodiment, the cyaniding agent in step 2) is selected from sodium cyanide and / or potassium cyanide.

[0025] As a preferred embodiment, the amount of cyaniding agent used in step 2) is 1.0 to 1.2 times the molar amount of halogen in the halogenated polyether.

[0026] As a preferred embodiment, step 2) is carried out in the presence of a solvent, preferably N,N-dimethylformamide.

[0027] As a preferred embodiment, the amount of solvent used in step 2) is 1 to 4 times the mass of the halogenated polyether.

[0028] As a preferred embodiment, after the reaction in step 2) is completed, the solvent is removed under negative pressure and then filtered.

[0029] As a preferred embodiment, the solvent removal temperature in step 2) is 100–180°C, the removal pressure is 0.1 kPaA–90 kPaA, and the removal time is 1–8 h.

[0030] As a preferred embodiment, the reaction temperature in step 3) is 80–150°C, and the reaction time is 0.5–5 h.

[0031] As a preferred embodiment, in step 3), hydrolysis is carried out in the presence of water and an alkaline catalyst, and the remaining water and alkaline catalyst are removed under negative pressure after hydrolysis.

[0032] As a preferred embodiment, the alkaline catalyst in step 3) is liquid ammonia.

[0033] As a preferred embodiment, the amount of alkaline catalyst used in step 3) is 0.1-10% of the mass of the cyano-terminated polyether.

[0034] As a preferred embodiment, the amount of water used in step 3) is 2.0 to 3.0 times the molar amount of cyano groups in the cyano-terminated polyether.

[0035] As a preferred embodiment, the removal temperature in step 3) is 50–150°C, the removal pressure is 0.1 kPaA–90 kPaA, and the removal time is 0.5–5 h.

[0036] As a preferred embodiment, in step 4), the polyetheramine is selected from WANAMINE 8100.

[0037] As a preferred embodiment, in step 4), the molar ratio of polyetheramine to carboxyl-terminated polyether is 0.4-0.9, preferably 0.428-0.894, depending on the designed molecular weight.

[0038] As a preferred embodiment, the reaction temperature in step 4) is 50–150°C, and the reaction time is 1–8 h.

[0039] As a preferred embodiment, the carboxyl-terminated amide-modified polyether in step 4) has a number-average molecular weight of 1000-10000 and a functionality of 2-4.

[0040] As a preferred embodiment, the esterification reaction temperature in step 5) is 100–180°C, the reaction time is 0.5–5 h, and the pressure is 2 kPaA–80 kPaA.

[0041] As a preferred embodiment, the catalyst for the esterification reaction in step 5) is selected from tetrabutyl titanate and / or isopropyl titanate, and the amount used is 0.05wt% to 0.5wt% of the carboxyl-terminated amide-modified polyether.

[0042] As a preferred embodiment, the catalyst for the hydrogenation reduction is a Raney nickel catalyst, used in an amount of 0.1 wt% to 5 wt% of the esterified end-capped polyether.

[0043] As a preferred embodiment, in step 5), the amount of methanol used is 0.5 to 5.0 times the mass of the carboxyl-terminated amide-modified polyether.

[0044] As a preferred embodiment, in step 5), during the hydrogenation reduction, the hydrogen gas is pressurized to 1.1 MPaA to 50.1 MPaA, the hydrogenation reduction temperature is 90 to 180°C, and the reaction time is 1 to 5 hours.

[0045] As a preferred embodiment, in step 5), after hydrogenation reduction, methanol removal is further included under the following conditions: temperature of 50-150°C, removal pressure of 0.1 kPaA-90 kPaA, and removal time of 0.5-5 h.

[0046] A flexible foam comprising the following components:

[0047] The amide-modified polyether polyol of this invention: 100

[0048] Water: 5-8

[0049] Dichloromethane: 8-30

[0050] Foam stabilizer: 1-3

[0051] Catalyst A33: 0.05~0.80

[0052] Catalyst T9: 0.05~0.2

[0053] Isocyanate: TDI80

[0054] In the flexible foam formulation of this invention, the NCO index is 110.

[0055] The foam stabilizer described in this invention comprises L580 and / or DC6070, preferably L580.

[0056] The density of the flexible foam described in this invention is 8-15 kg / m³. 3 .

[0057] The amide-modified polyether polyol of the present invention can directly replace polyethers of the same molecular weight in the prior art for the preparation of flexible foam.

[0058] The beneficial effects of this invention are: it can improve the mechanical properties of flexible foam without reducing its water and oil resistance, and the viscosity of the polyol raw material is much lower than that of the same type of polyester, which can facilitate large-scale production and rapid switching. Detailed Implementation

[0059] The present invention will be described in detail below with reference to embodiments. These embodiments will help those skilled in the art to further understand the present invention, but do not limit the invention in any way. It should be noted that those skilled in the art can make several adjustments and improvements without departing from the concept of the present invention. These all fall within the protection scope of the present invention.

[0060] In this embodiment, the method for determining the acid value is GB / T12008.5 Determination of acid value of polyether polyols, and the method for determining the hydroxyl value is GB / T12008.3 Determination of hydroxyl value of polyether polyols.

[0061] Example 1

[0062] The polyether raw material used in this embodiment has a functionality of 2. The initiator is a mixture of ethylene glycol and 1,3-propanediol in a mass ratio of 50:50 with a molecular weight of 1000. The mass ratio of EO to PO in the polymer monomer is 0:100, which is pure PO polymerized polyether.

[0063] 1) Halogenation: 2000g of polyether was added to a 5L reactor, purged with N2 and pressurized to 0.1MPaA, heated to 20℃, and then 476g of thionyl chloride (molecular weight 119, 4mol, molar ratio of hydroxyl value to polyether 1:1) was added. After reacting for 0.5h, the halogenation agent was removed under vacuum at 50℃ and 0.1KPaA for 0.5h, followed by cooling. NMR analysis showed a conversion rate greater than 99.7% (H-NMR, δ=3.9cm). -1 (CDCl3 as a solvent);

[0064]

[0065] 2) Cyanidation: 1037g of the halogenated polyether from step 1) (molecular weight 1037, halogenation rate 99.7%, halogen molar amount 1.994mol) was added to a 5L reactor along with 97.71g of cyaniding agent NaCN (molecular weight 49, 1.994mol, halogen molar ratio 1.0:1) and solvent N,N-dimethylformamide. After cooling to 10℃ and reacting for 0.5hr, the temperature was raised to 100℃ and the solvent was removed under vacuum at 0.1KPaA for 1hr. The mixture was filtered to obtain cyano-terminated polyether. The conversion rate was greater than 99.9% according to NMR (H-NMR, δ=2.9cm). -1 (CDCl3 as a solvent);

[0066]

[0067] 3) Hydrolysis: 1018 g of cyano-terminated polyether (molecular weight 1018, cyanidation rate 99.9%, cyano molar amount 1.998 mol) from step 2) was added to a 5 L reactor, along with 71.93 g of water (molecular weight 18, 3.996 mol, cyano molar ratio to the polyether cyano molar amount 2.0:1). 1.01 g of liquid ammonia was added as an alkaline catalyst, and the temperature was raised to 150 °C for hydrolysis for 0.5 h. After hydrolysis, the remaining water and alkali were removed at 50 °C and 0.1 kPa A negative pressure for 1 h to obtain carboxyl-terminated polyether. The conversion rate was greater than 99.9% according to NMR (C-NMR, δ = 181 cm⁻¹). -1 (CDCl3 as a solvent);

[0068]

[0069] 4) Amide synthesis: 1056g of carboxyl-terminated polyether (molecular weight 1056, cyanidation rate 99.9%, carboxyl molar amount 1.998mol) from step 3) and 199.5g of polyetheramine WANAMINE 8100 (molecular weight 228, 0.875mol) were added to a 5L reactor and amidated at 50℃ for 1h to prepare carboxyl-terminated amide-modified polyether. The acid value of the product was measured to be 11.20mgKOH / g, the molecular weight was 10000, and the functionality was 2.

[0070]

[0071] 5) Esterification, hydrogenation, and desolventization: 2000g of the carboxyl-terminated amide-modified polyether from step 4) was added to a 5L reactor, along with 1000g of methanol. Tetrabutyl titanate was used as the esterification catalyst at a dosage of 1g. The mixture was heated to 100℃ and subjected to negative pressure dehydration and reflux methanol esterification for 0.5h. After esterification, 2g of Raney nickel hydrogenation catalyst was added, the temperature was raised to 90℃, and hydrogen was introduced and pressurized to 1.1MPaA for reduction for 1hr. The hydrogenation catalyst was then filtered off, and hydrogen and the hydrogenation byproduct methanol were removed at 50℃ and negative pressure at 0.1KPaA for 0.5h to obtain the final product. Its hydroxyl value was measured to be 11.20mgKOH / g, and the product indicators were qualified.

[0072]

[0073] Example 2

[0074] The polyether raw material used in this embodiment has a functionality of 4, the initiator is pentaerythritol with a molecular weight of 2000, and the mass ratio of EO to PO in the polymer monomer is 100:0, i.e., pure EO polymerized polyether.

[0075] 1) Halogenation: 2000g of polyether was added to a 5L reactor, purged with N2 and pressurized to 1.0MPaA, heated to 120℃, and then 792g of phosgene (molecular weight 99.8 mol, molar ratio of phosgene to hydroxyl group in polyether 2.0:1) was added. After reacting for 5 hours, the halogenation agent was removed under vacuum at 150℃ and 90kPaA for 5 hours, followed by cooling. NMR analysis showed a conversion rate greater than 99.8% (H-NMR, δ=3.9cm). -1 (CDCl3 as a solvent);

[0076] 2) Cyanidation: 1037g of the halogenated polyether from step 1) (molecular weight 2074, halogenation rate 99.8%, halogen molar amount 1.996mol) was added to a 5L reactor along with 155.69g of cyaniding agent KCN (molecular weight 65, 2.39mol, halogen molar ratio 1.2:1) and solvent N,N-dimethylformamide 2074g. After heating to 100℃ and reacting for 5 hours, the temperature was raised to 180℃ and the solvent was removed under vacuum at 50KPaA for 8 hours. The mixture was filtered to obtain cyano-terminated polyether. NMR spectroscopy showed a conversion rate greater than 99.9% (H-NMR, δ=2.9cm). -1 (CDCl3 as a solvent);

[0077] 3) Hydrolysis: 1018g of cyano-terminated polyether (molecular weight 2036, cyanidation rate 99.9%, cyano molar amount 1.998mol) from step 2) was added to a 5L reactor, along with 107.89g of water (molecular weight 18, 5.994mol, cyano molar ratio to polyether 3.0:1), and 101.8g of liquid ammonia (10% wt of polyether mass) was added as an alkaline catalyst. The temperature was raised to 120℃ for hydrolysis for 5h. After hydrolysis, the remaining water and alkali were removed at 150℃ and 90KPaA negative pressure for 3h to obtain carboxyl-terminated polyether. The conversion rate was greater than 99.9% (C-NMR, δ=181cm). -1 (CDCl3 as a solvent);

[0078] 4) Amide synthesis: 2112 g of carboxyl-terminated polyether (molecular weight 2112, cyanidation rate 99.9%, carboxyl molar amount 3.996 mol) from step 3) and 789.96 g of polyetheramine WANAMINE 8100 (molecular weight 228, 3.465 mol) were added to a 5L reactor and amidated at 150℃ for 8 h to prepare carboxyl-terminated amide-modified polyether. The acid value of the product was measured to be 28.07 mg KOH / g; the molecular weight was 8000; and the functionality was 4.

[0079] 5) In a 5L reactor for esterification, hydrogenation, and desolventization, 500g of the carboxyl-terminated amide-modified polyether from step 4) was added, along with 2500g of methanol. Isopropyl titanate was used as the esterification catalyst at a dosage of 2.5g. The mixture was heated to 180℃ and subjected to negative pressure dehydration and reflux methanol esterification for 5h. After esterification, 25g of Raney nickel hydrogenation catalyst was added, the temperature was raised to 180℃, and hydrogen gas was introduced and pressurized to 50.1MPaA for reduction for 1h. The hydrogenation catalyst was then filtered off, and hydrogen gas and the hydrogenation byproduct methanol were removed under negative pressure at 150℃ and 90KPaA for 5h to obtain the final product. Its hydroxyl value was measured to be 28.20mgKOH / g, and the product indicators were qualified.

[0080] Example 3

[0081] The polyether raw material used in this embodiment has a functionality of 2, the initiator is diethylene glycol with a molecular weight of 400, and the mass ratio of EO to PO in the polymer monomers is 50:50.

[0082] 1) Halogenation: 2000g of polyether was added to a 5L reactor, purged with N2 and pressurized to 0.5MPaA, heated to 70℃, and then 1485g of phosgene (molecular weight 99.15mol, molar ratio of phosgene to hydroxyl group in polyether 1.5:1) was added. After reacting for 3 hours, the halogenation agent was removed under vacuum at 100℃ and 50kPaA for 3 hours, followed by cooling. NMR analysis showed a conversion rate greater than 99.7% (H-NMR, δ=3.9cm). -1 (CDCl3 as a solvent);

[0083] 2) Cyanidation: 437g of the halogenated polyether from step 1) (molecular weight 437, halogenation rate 99.7%, halogen molar amount 1.994mol) was added to a 5L reactor along with 107.48g of cyaniding agent NaCN (molecular weight 49, 1.994mol, halogen molar ratio 1.1:1) and solvent N,N-dimethylformamide. After reacting at 50℃ for 3 hours, the temperature was raised to 140℃ and vacuum desolvation was carried out at 90KPaA for 4 hours. The mixture was filtered to obtain cyano-terminated polyether. NMR spectroscopy showed a conversion rate greater than 99.9% (H-NMR, δ=2.9cm). -1 (CDCl3 as a solvent);

[0084] 3) Hydrolysis: 1254g of cyano-terminated polyether (molecular weight 418, cyanidation rate 99.9%, cyano molar amount 2.997mol) from step 2) was added to a 5L reactor, along with 134.87g of water (molecular weight 18, 7.493mol, cyano molar ratio to the polyether cyano group 2.5:1). 62.7g of liquid ammonia was added as an alkaline catalyst, and the temperature was raised to 80℃ for hydrolysis for 5h. After hydrolysis, the remaining water and alkali were removed at 100℃ and 50KPaA negative pressure for 3h to obtain carboxyl-terminated polyether. The conversion rate was greater than 99.9% according to NMR (C-NMR, δ=181cm). -1 (CDCl3 as a solvent);

[0085] 4) Amide synthesis: 912 g of carboxyl-terminated polyether (molecular weight 456, cyanidation rate 99.9%, carboxyl molar amount 3.996 mol) from step 3) and 539.11 g of polyetheramine WANAMINE 8100 (molecular weight 228, 2.364 mol) were added to a 5 L reactor and amidated at 100 °C for 5 h to prepare carboxyl-terminated amide-modified polyether. The acid value of the product was measured to be 113.0 mg KOH / g; the molecular weight was 1000; and the functionality was 2.

[0086] 5) Esterification, hydrogenation, and desolventization: 1000g of the carboxyl-terminated amide-modified polyether from step 4) was added to a 5L reactor, along with 2500g of methanol. Tetrabutyl titanate was used as the esterification catalyst at a dosage of 3g. The temperature was raised to 140℃, and the methanol was refluxed under negative pressure at 40KPaA for 3 hours for dehydration and esterification. After esterification, 30g of Raney nickel hydrogenation catalyst was added, and the temperature was raised to 140℃. Hydrogen gas was introduced and pressurized to 25.1MPaA for reduction for 3 hours. The hydrogenation catalyst was then filtered off, and hydrogen gas and the hydrogenation byproduct methanol were removed under negative pressure at 100℃ and 50KPaA for 3 hours to obtain the final product. Its hydroxyl value was measured to be 112.50mgKOH / g, and the product indicators were qualified.

[0087] Example 4

[0088] The polyether raw material used in this embodiment has a functionality of 3, and the initiator is a mixture of trimethylolpropane and glycerol in a mass ratio of 50:50 with a molecular weight of 1500. The mass ratio of EO to PO in the polymer monomer is 25:75.

[0089] 1) Halogenation: 1500g of polyether was added to a 5L reactor, purged with N2 and pressurized to 0.8MPaA, and heated to 90℃. Then, 357g of thionyl chloride (molecular weight 119, 3mol, molar ratio of hydroxyl value in the polyether to 357g) was added. After reacting for 3h, the halogenation agent was removed under vacuum at 100℃ and 0.1KPaA for 3h, followed by cooling. The conversion rate was greater than 99.7% according to NMR (H-NMR, δ=3.9cm). -1 (CDCl3 as a solvent);

[0090] 2) Cyanidation: 778g of the halogenated polyether from step 1) (molecular weight 1556, halogenation rate 99.7%, halogen molar amount 1.496mol) was added to a 5L reactor along with 80.61g of cyaniding agent NaCN (molecular weight 49, 1.645mol, halogen molar ratio 1.1:1) and solvent N,N-dimethylformamide 2334g. After heating to 80℃ and reacting for 5 hours, the temperature was raised to 16℃ and vacuum desolvation was carried out at 8KPaA for 3 hours. The mixture was then filtered to obtain cyano-terminated polyether. NMR spectroscopy showed a conversion rate greater than 99.9% (H-NMR, δ=2.9cm). -1 (CDCl3 as a solvent);

[0091] 3) Hydrolysis: 1527g of cyano-terminated polyether (molecular weight 1527, cyanidation rate 99.9%, cyano molar amount 2.997mol) from step 2) was added to a 5L reactor, along with 107.89g of water (molecular weight 18, 5.994mol, cyano molar ratio to the polyether 2.0:1), and 15.37g of liquid ammonia was added as an alkaline catalyst. The temperature was raised to 150℃ for hydrolysis for 1h. After hydrolysis, the remaining water and alkali were removed at 80℃ and 10KPaA negative pressure for 0.5h to obtain carboxyl-terminated polyether. The conversion rate was greater than 99.9% according to NMR (C-NMR, δ=181cm). -1 (CDCl3 as a solvent);

[0092] 4) Amide synthesis: 1584 g of carboxyl-terminated polyether from step 3) (molecular weight 1584, cyanidation rate 99.9%, carboxyl molar amount 2.997 mol) and 610.84 g of polyetheramine WANAMINE 8100 (molecular weight 228, 2.679 mol) were added to a 5 L reactor and amidated at 120 °C for 4 h to prepare carboxyl-terminated amide-modified polyether. The acid value of the product was measured to be 28.10 mg KOH / g; the molecular weight was 6000; and the functionality was 3.

[0093] 5) Esterification, hydrogenation, and desolventization: 1000g of the carboxyl-terminated amide-modified polyether from step 4) was added to a 5L reactor, along with 2000g of methanol. Tetrabutyl titanate was used as the esterification catalyst at a dosage of 5g. The temperature was raised to 150℃, and the methanol was refluxed under negative pressure at 40KPaA for 0.5h for dehydration. After esterification, 30g of Raney nickel hydrogenation catalyst was added, and the temperature was raised to 130℃. Hydrogen was introduced and pressurized to 10.1MPaA for reduction for 3hr. The hydrogenation catalyst was then filtered off, and hydrogen and the hydrogenation byproduct methanol were removed under negative pressure at 90℃ and 3KPaA for 4h to obtain the final product. Its hydroxyl value was measured to be 28.30mgKOH / g, and the product indicators were qualified.

[0094] Example 5

[0095] The polyether raw material used in this embodiment has a functionality of 2.5, and the initiators are a mixture of 1,3-propanediol and glycerol in a mass ratio of 50:50 with a molecular weight of 1000. The mass ratio of EO to PO in the polymer monomers is 10:90.

[0096] 1) Halogenation: 1000g of polyether was added to a 5L reactor, purged with N2 and pressurized to 1.0MPaA, heated to 120℃, and then 495g of phosgene (molecular weight 99.5mol, molar ratio of phosgene to hydroxyl group in polyether 2:1) was added. After reacting for 5h, the halogenation agent was removed under vacuum at 80℃ and 5KPaA for 4h, followed by cooling. NMR analysis showed a conversion rate greater than 99.7% (H-NMR, δ=3.9cm). -1 (CDCl3 as a solvent);

[0097] 2) Cyanidation: 1056g of the halogenated polyether from step 1) (molecular weight 1056, halogenation rate 99.7%, halogen molar amount 2.493mol) was added to a 5L reactor along with 146.56g of cyaniding agent NaCN (molecular weight 49, 2.991mol, halogen molar ratio 1.2:1) and solvent N,N-dimethylformamide. After heating to 30℃ and reacting for 3 hours, the temperature was raised to 130℃ and vacuum desolventized under a negative pressure of 20KPaA for 1 hour. The mixture was filtered to obtain cyano-terminated polyether. NMR spectroscopy showed a conversion rate greater than 99.9% (H-NMR, δ=2.9cm). -1 (CDCl3 as a solvent);

[0098] 3) Hydrolysis: 1023g of cyano-terminated polyether (molecular weight 1023, cyanidation rate 99.9%, cyano molar amount 1.998mol) from step 2) was added to a 5L reactor, along with 71.93g of water (molecular weight 18, 3.996mol, cyano molar ratio to the polyether cyano group 2.0:1). 20.46g of liquid ammonia was added as an alkaline catalyst, and the temperature was raised to 120℃ for hydrolysis for 5 hours. After hydrolysis, the remaining water and alkali were removed at 120℃ and 30KPaA negative pressure for 5 hours to obtain carboxyl-terminated polyether. The conversion rate was greater than 99.9% according to NMR (C-NMR, δ=181cm). -1 (CDCl3 as a solvent);

[0099] 4) Amide synthesis: 1070 g of carboxyl-terminated polyether from step 3) (molecular weight 1070, cyanidation rate 99.9%, carboxyl molar amount 2.498 mol) and 423.56 g of polyetheramine WANAMINE 8100 (molecular weight 228, 1.858 mol) were added to a 5 L reactor and amidated at 150 °C for 8 h to prepare carboxyl-terminated amide-modified polyether. The acid value of the product was measured to be 28.08 mg KOH / g; the molecular weight was 5000; and the functionality was 2.5.

[0100] 5) Esterification, hydrogenation, and desolventization: 500g of the carboxyl-terminated amide-modified polyether from step 4) was added to a 5L reactor, along with 1500g of methanol. Tetrabutyl titanate was used as the esterification catalyst at a dosage of 0.25g. The temperature was raised to 180℃, and the methanol was refluxed under negative pressure at 70KPaA for 0.5h for dehydration. After esterification, 5g of Raney nickel hydrogenation catalyst was added, and the temperature was raised to 90℃. Hydrogen was introduced and pressurized to 1.1MPaA for 1hr for reduction. The hydrogenation catalyst was then filtered off, and hydrogen and the hydrogenation byproduct methanol were removed under negative pressure at 50℃ and 0.1KPaA for 0.5h to obtain the final product. Its hydroxyl value was measured to be 28.10mgKOH / g, and the product indicators were qualified.

[0101] Comparative Example

[0102] Comparative Example 1 is a mixture of ethylene glycol and 1,3-propanediol in a mass ratio of 50:50 with a hydroxyl value of 11.20 mg KOH / g and a functionality of 2. The polymer monomers are EO and PO in a mass ratio of 0:100, i.e., pure PO polymerized polyether with a calculated number average molecular weight of 10,000.

[0103] Comparative Example 2 has a hydroxyl value of 28.42 mgKOH / g, a functionality of 4, and pentaerythritol as the initiator. The mass ratio of EO to PO in the monomer is 100:0, which is pure EO polymerized polyether with a calculated number-average molecular weight of 8000.

[0104] Comparative Example 3 has a hydroxyl value of 112.60 mg KOH / g, a functionality of 2, diethylene glycol as the initiator, a EO to PO mass ratio of 50:50 in the monomers, and a calculated number-average molecular weight of 1000.

[0105] Comparative Example 4 is a mixture of trimethylolpropane and glycerol in a mass ratio of 50:50 with a hydroxyl value of 28.50 mg KOH / g and a functionality of 3. The monomers are EO and PO in a mass ratio of 25:75 and have a calculated number average molecular weight of 6000.

[0106] Comparative Example 5 was a mixture of 1,3-propanediol and glycerol in a mass ratio of 50:50, with a hydroxyl value of 28.10 mg KOH / g, a functionality of 2.5, and the monomers being EO to PO in a mass ratio of 10:90, with a calculated number-average molecular weight of 5000 and a functionality of 2.5.

[0107] Comparative Example 6 is a hydroxyl value of 11.40 mg KOH / g, an acid value of 0.23 mg KOH / g, a functionality of 2, and an initiator of a mixture of ethylene glycol and 1,3-propanediol in a mass ratio of 50:50. The mass ratio of EG to PG in the monomers is 0:100, i.e., pure PG polyester. The dicarboxylic acid used is 1,6-adipic acid, and the equivalent number-average molecular weight is 10,000.

[0108] Comparative Example 7 has a hydroxyl value of 28.00 mgKOH / g, an acid value of 0.22 mgKOH / g, a functionality of 4, and pentaerythritol as the initiator. The mass ratio of EG to PG in the monomers is 100:0, i.e., pure EG polyester. The dicarboxylic acid used is 1,6-adipic acid, and the equivalent number-average molecular weight is 8000.

[0109] Comparative Example 8 has a hydroxyl value of 112.10 mgKOH / g, an acid value of 0.25 mgKOH / g, a functionality of 2, and diethylene glycol as the initiator. The mass ratio of EG to PG in the monomers is 50:50, the dicarboxylic acid is 1,6-adipic acid, and the equivalent number-average molecular weight is 1000.

[0110] Comparative Example 9 was a mixture of 1,3-propanediol and glycerol in a mass ratio of 50:50, with a hydroxyl value of 112.10 mg KOH / g, an acid value of 0.24 mg KOH / g, a functionality of 3, and EG and PG in a mass ratio of 25:75 in the monomers. The dicarboxylic acid used was 1,6-adipic acid, and the equivalent number-average molecular weight was 6000.

[0111] Comparative Example 10 was a mixture of trimethylolpropane and glycerol in a mass ratio of 50:50, with a hydroxyl value of 28.30 mg KOH / g, an acid value of 0.22 mg KOH / g, a functionality of 2.5, and EG to PG in a mass ratio of 10:90. The dicarboxylic acid used was 1,6-adipic acid, and the equivalent number-average molecular weight was 5000.

[0112] Preparation of flexible foam

[0113] Prepare flexible foam according to the following raw materials and mass proportions.

[0114] Amide-modified polyether polyol of Example 1: 100;

[0115] Water: 5;

[0116] Dichloromethane: 8;

[0117] Foam stabilizer: 3;

[0118] Catalyst A33: 0.18;

[0119] Catalyst T9: 0.2;

[0120] TDI80;

[0121] NCO index: 110.

[0122] Flexible foams were prepared using the polyols from Examples 2-5 and Comparative Examples 1-10, respectively, and their performance was tested. The results are shown in Table 1.

[0123] Table 1. Performance of Flexible Foam

[0124]

[0125]

Claims

1. An amide-modified polyether polyol, whose structural formula is as follows: ###0001### wherein R1 is hydrogen or methyl; the number average molecular weight is 1000-10000, and the functionality is 2-4. wherein 2. A method for preparing the amide-modified polyether polyol according to claim 1, comprising the following steps: 1) halogenation: reacting a polyether with a halogenating agent to prepare a halogenated polyether; 2) cyanation: reacting the halogenated polyether with a cyanating agent to prepare a cyano-terminated polyether; 3) hydrolysis: hydrolyzing the cyano-terminated polyether to prepare a carboxyl-terminated polyether; 4) amide synthesis: carrying out an amide reaction between the carboxyl-terminated polyether and a polyether amine to prepare a carboxyl-terminated amide-modified polyether; and 5) esterification and hydrogenation: first carrying out an esterification reaction between the carboxyl-terminated amide-modified polyether and methanol to prepare an ester-terminated polyether, and then carrying out hydrogenation reduction. The halogenating agent of step 1) is selected from thionyl chloride and / or phosgene, preferably thionyl chloride. The polyether of step 1) has a number average molecular weight of 400-2000 and a functionality of 2-4, wherein the EO in the polymerized monomers accounts for 0-100% of the total mass of EO and PO, and the starter agent is selected from one or more of ethylene glycol, diethylene glycol, 1,3-propanediol, glycerol, trimethylolpropane, and pentaerythritol. The cyanating agent of step 2) is selected from sodium cyanide and / or potassium cyanide. In step 3), the hydrolysis is carried out in the presence of water and an alkaline catalyst, and the alkaline catalyst is preferably liquid ammonia. In step 4), the polyether amine is selected from WANAMINE 8100. In step 4), the molar ratio of the polyether amine to the carboxyl-terminated polyether is 0.4-0.9, preferably 0.428-0.

894.

3. The method of claim 2, wherein, The catalyst for the esterification reaction of step 5) is selected from tetrabutyl titanate and / or isopropyl titanate; and the catalyst for the hydrogenation reduction is a Raney nickel catalyst.

4. The method of claim 2, wherein, 10. A soft foam, comprising the following components by mass fraction: the amide-modified polyether polyol according to claim 1: 100; water: 5-8; dichloromethane: 8-30; a foam stabilizer: 1-3; catalyst A33: 0.05-0.80; catalyst T9: 0.05-0.2; isocyanate: TDI80; and NCO index:

110.

5. The method of claim 2, wherein, 10. A soft foam, comprising the following components by mass fraction: the amide-modified polyether polyol according to claim 1: 100; water: 5-8; dichloromethane: 8-30; a foam stabilizer: 1-3; catalyst A33: 0.05-0.80; catalyst T9: 0.05-0.2; isocyanate: TDI80; and NCO index:

110.

6. The method of claim 2, wherein, ​ 7. The method of claim 2, wherein, ​ 8. The method of claim 2, wherein, ​ 9. The method of claim 2, wherein, ​ ​ ​ ​ ​ ​ ​ ​ ​ ​

Images