P-aminophenol polyether polyol as well as preparation method and application thereof

Abstract

The invention discloses p-aminophenol polyether polyol, a preparation method of the p-aminophenol polyether polyol, and application of the p-aminophenol polyether polyol in an all-water foaming polyurethane open-cell system. The structure of the p-aminophenol polyether polyol is shown as follows: # imgabs0 # n is 5-10, and m is 1-5. The p-aminophenol polyether polyol contains benzene rings, has good compatibility with high-molecular polyether and a flame retardant TCPP, contains ether bonds, and has good compatibility with water. Meanwhile, the benzene ring structure has certain rigidity, and certain strength can be provided for all-water low-density polyurethane open-cell foam. The p-aminophenol polyether polyol can be used as main polyether of an all-water foaming polyurethane open-cell system, and compared with a traditional all-water foaming polyurethane open-cell system, the p-aminophenol polyether polyol has the advantages of being good in compatibility, high in latitude, high in compression strength, low in cost and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and specifically relates to a p-aminophenol polyether polyol and a preparation method thereof, and also relates to the field of polyurethane, and specifically relates to polyurethane rigid foam. Background Art

[0002] In the manufacturing process of rigid polyurethane foam, the foaming agent, as a filler in the polyurethane skeleton and the driving force of foam growth, has a huge impact on the thermal conductivity, fluidity and physical properties of the foam. HCFC-141B (hereinafter referred to as 141B) is widely used as a second-generation foaming agent in various fields of energy conservation and insulation due to its excellent thermal conductivity and safety. However, as a hydrochlorofluorocarbon foaming agent, 141B has a high ODP value and has a certain degree of damage to the ozone layer. In October 2018, my country banned the use of 141B in refrigerators, freezers, refrigerated containers and electric water heaters, and plans to completely eliminate 141B in the entire polyurethane industry by the end of 2025. Overseas, the use of 141B has been banned in Europe, America, India and other regions. At present, pentane has been used to replace 141B in domestic industries such as panels and refrigerators, but pentane is flammable and explosive, and there are certain risks in production, transportation and storage, which limits its application in certain areas and fields. The all-water system uses water as the foaming agent. Due to its advantages such as environmental protection and safety, it has been widely studied and has flourished in the fields of pipelines and spraying. However, the all-water system also has the following disadvantages that limit its development:

[0003] 1) Since the all-water system does not contain a physical foaming agent, the viscosity of the polyether composite material is high and the fluidity is poor, which is not suitable for making large polyurethane sandwich panels. Low-viscosity polyether is needed to adjust the viscosity of the composite material and improve its fluidity to obtain products with uniform density;

[0004] 2) Water and isocyanate react to generate CO2 and amines, and amines and isocyanates further react to generate a large number of urea structures. The presence of polyurea will make the polyurethane foam powdery and brittle, and the adhesion between the foam and the substrate will be insufficient. It is necessary to adjust the appropriate hydroxyl value and index to reduce the generation of polyurea.

[0005] 3) The gas in the pores of all-water foam is CO2. CO2 not only has a high thermal conductivity, but also has a much greater diffusion coefficient than air. It is easy to diffuse from the inside of the pores to the outside of the pores, causing the pressure inside the pores to drop. If the pore wall strength is not enough to balance the pressure difference between the inside and outside, the foam is prone to shrinkage and has poor high and low temperature dimensional stability. Generally, to maintain good stability, the density of all-water foams must be above 43kg / m.

[0006] Therefore, it is necessary to develop suitable polyether polyols for application in all-water foamed polyurethane open-cell systems, which can overcome the shortcomings of poor strength, poor adhesion and easy shrinkage of all-water systems. Summary of the invention

[0007] In view of the above problems existing in the prior art, the first object of the present invention is to provide a p-aminophenol polyether polyol. The p-aminophenol polyether polyol contains both a benzene ring and an ether bond, and has good compatibility with polymer polyether, flame retardant TCPP and water; at the same time, the benzene ring structure has a certain rigidity, which can provide a certain strength for the all-water low-density polyurethane open-cell foam.

[0008] The second object of the present invention is to provide a method for preparing the p-aminophenol polyether polyol.

[0009] The third object of the present invention is to provide a polyurethane full water open-cell foam prepared by the p-aminophenol polyether polyol and a preparation method thereof. The p-aminophenol polyether polyol can be used as the main polyether of the full water foaming polyurethane open-cell system, and compared with the traditional full water foaming polyurethane open-cell system, it has the advantages of good compatibility, high tolerance, high compression strength, low cost, etc.

[0010] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0011] In a first aspect, the present invention provides a p-aminophenol polyether polyol having a structure as shown in formula (1):

[0012]

[0013] Wherein, n is each independently 5 to 10, preferably any integer from 6 to 8;

[0014] m is each independently 1 to 5, and preferably any integer of 1 to 3.

[0015] Specifically, n can be 5, 6, 7, 8, 9, 10 or a range consisting of any two thereof, and m can be 1, 2, 3, 4, 5 or a range consisting of any two thereof.

[0016] In a preferred embodiment, the hydroxyl value of the p-aminophenol polyether polyol is 100-180 mgKOH / g, including but not limited to 100 mgKOH / g, 110 mgKOH / g, 120 mgKOH / g, 130 mgKOH / g, 140 mgKOH / g, 150 mgKOH / g, 160 mgKOH / g, 170 mgKOH / g, 180 mgKOH / g or a range consisting of any two thereof, preferably 120-160 mgKOH / g;

[0017] The functionality of the p-aminophenol polyether polyol is 3-4.

[0018] In a second aspect, the present invention provides a method for preparing the above-mentioned p-aminophenol polyether polyol. In an embodiment of the present invention, it can be prepared by conventional processes in the art, for example, p-aminophenol (ODTA) is used as a starting material, and reacts with an oxidized olefin in the presence of a catalyst to obtain a p-aminophenol polyether polyol as shown in formula (1).

[0019] The relevant operations and process conditions in the preparation method of the present invention, and the devices used therein, can all be carried out by using the corresponding conventional selections in the art, and there is no particular limitation thereto. The technicians can optimize the processes known in the prior art according to actual needs. Specifically, for example, the conditions listed in the following embodiments of the present invention can be used:

[0020] The oxidized olefins are ethylene oxide (EO) and / or propylene oxide (PO);

[0021] The molar ratio of p-aminophenol to olefin oxide is 1:18-45, including but not limited to 1:18, 1:21, 1:24, 1:27, 1:30, 1:33, 1:36, 1:39, 1:42, 1:45 or a range consisting of any two thereof.

[0022] In a specific embodiment, the preparation method of p-aminophenol polyether polyol comprises the following steps:

[0023] S1: mixing p-aminophenol and a catalyst, heating to a reaction temperature, and introducing ethylene oxide to react until the pressure stops decreasing;

[0024] S2: Propylene oxide is introduced to react until the pressure stops decreasing;

[0025] S3: removing unreacted ethylene oxide and propylene oxide in vacuo, adding acid for neutralization, and obtaining the p-aminophenol polyether polyol.

[0026] In some specific examples, the p-aminophenol and the catalyst are mixed in step S1 and then a dehydration operation process is included, for example, a dehydration treatment under vacuum can be used. Preferably, during the dehydration process, the pressure is not limited, and the vacuum state is sufficient. The temperature is 100-120°C and the time is 0.5-1h. Specifically, the temperature can be 100°C, 102°C, 105°C, 107°C, 110°C, 112°C, 115°C, 117°C, 120°C, or a range between any two of them. The time can be 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, or a range between any two of them. In specific implementation, p-aminophenol and the catalyst are added to a reactor, and the air in the reactor is replaced with nitrogen. Under vacuum, the temperature is raised to 100°C for dehydration for 0.5-1h.

[0027] In some specific examples, the catalyst in step S1 is selected from alkaline hydroxides, preferably one or more of sodium hydroxide and potassium hydroxide, more preferably potassium hydroxide;

[0028] Preferably, the amount of the catalyst is 1-3wt% of the mass of p-aminophenol, including but not limited to 1wt%, 1.2wt%, 1.5wt%, 1.8wt%, 2wt%, 2.2wt%, 2.5wt%, 2.8wt%, 3wt% or a range consisting of any two thereof.

[0029] In some specific examples, the molar ratio of p-aminophenol to ethylene oxide in step S1 is 1:15-30, including but not limited to 1:15, 1:18, 1:21, 1:24, 1:27, 1:30 or a range consisting of any two thereof, and the preferred molar ratio is 1:18-24.

[0030] In some specific examples, the reaction in step S1 has a temperature of 130 to 160° C., preferably 140 to 150° C., and a reaction pressure of 0.2 to 0.3 MPa; specifically, the temperature may be 130° C., 135° C., 140° C., 145° C., 150° C., 155° C., 160° C., or a range consisting of any two thereof, and the reaction pressure may be 0.2 MPa, 0.22 MPa, 0.24 MPa, 0.26 MPa, 0.28 MPa, 0.3 MPa, or a range consisting of any two thereof;

[0031] Specifically, in the above reaction process, the amount of ethylene oxide added satisfies the above reaction pressure (i.e., ethylene oxide is charged into the reactor and pressurized to a preset reaction pressure, and ethylene oxide can be fed continuously or intermittently). In specific implementation, the dehydrated p-aminophenol and the catalyst are heated to the reaction temperature, and a small amount of ethylene oxide is introduced. When the reaction is stable, the ethylene oxide feed valve is often opened, and the temperature is maintained at 130 to 160° C. at the reaction temperature, and the pressure in the reactor is 0.2 to 0.3 MPa. When the feed amount of ethylene oxide reaches the theoretical value, the feed valve is closed, and the temperature is maintained at the reaction temperature for a certain period of time (e.g., 1 to 2 hours) until the pressure in the reactor no longer decreases (e.g., the pressure drops to negative pressure and no longer changes).

[0032] In some specific examples, the molar ratio of p-aminophenol to propylene oxide in step S2 is 1:3-15, including but not limited to 1:3, 1:6, 1:9, 1:12, 1:15 or a range consisting of any two thereof, and the preferred molar ratio is 1:3-9.

[0033] In some specific examples, the reaction in step S2 has a temperature of 130 to 160° C., preferably 140 to 150° C., and a reaction pressure of 0.2 to 0.3 MPa; specifically, the temperature may be 130° C., 135° C., 140° C., 145° C., 150° C., 155° C., 160° C., or a range consisting of any two thereof, and the reaction pressure may be 0.2 MPa, 0.22 MPa, 0.24 MPa, 0.26 MPa, 0.28 MPa, 0.3 MPa, or a range consisting of any two thereof;

[0034] Specifically, in the above reaction process, the amount of propylene oxide added satisfies the above reaction pressure (i.e., propylene oxide is charged into the reactor and pressurized to a preset reaction pressure, and propylene oxide can be fed continuously or intermittently). In specific implementation, propylene oxide is introduced into the reaction system of step S1, and the temperature is maintained at a reaction temperature of 130 to 160°C, and the pressure in the reactor is 0.2 to 0.3Mpa. When the feed amount of propylene oxide reaches the theoretical value, the feed valve is closed, and the temperature is maintained at the reaction temperature for a certain period of time (e.g., 1 to 2 hours) until the pressure in the reactor no longer decreases (e.g., the pressure drops to a negative pressure and no longer changes).

[0035] In some specific examples, in step S3, unreacted ethylene oxide and propylene oxide are removed by vacuum. During the removal process, the pressure is not limited and can be under vacuum, for example, 0 MPa, the temperature is 80-90°C, and the time is 15-30 min. Specifically, the temperature can be 80°C, 82°C, 84°C, 86°C, 88°C, 100°C or a range between any two of them, and the time can be 15 min, 17 min, 20 min, 22 min, 25 min, 28 min, 30 min or a range between any two of them.

[0036] In some specific examples, the acid neutralization in step S3 is specifically performed to a pH value of 6 to 8, such as 6, 7, 8, etc. The acid is selected from one or more of acetic acid and phosphoric acid, preferably phosphoric acid.

[0037] In a third aspect, the present invention provides the use of the aforementioned p-aminophenol polyether polyol in polyurethane foam, especially in a fully water-foamed polyurethane open-cell system, and can be used as the main polyether of the fully water-foamed polyurethane open-cell system.

[0038] In a fourth aspect, the present invention provides a polyurethane rigid foam, which is prepared by foaming a combined polyether and an isocyanate; wherein the mass ratio of the combined polyether to the isocyanate is 100:130 to 160, including but not limited to 100:130, 100:135, 100:140, 100:145, 100:150, 100:155, 100:160 or a range consisting of any two thereof, preferably 100:140 to 150;

[0039] The combined polyether comprises a polyether polyol combination, a flame retardant, a surfactant, a composite catalyst and water, and the mass ratio thereof is 100:(5-21):(1-5):(1.5-4.5):(8-13), including but not limited to 100:(5, 8, 10, 12, 15, 18, 20, etc.):(1, 2, 3, 4, 5, etc.):(1.5, 2, 3, 4, 4.5, etc.):(8, 8.5, 9, 9.5, 10, etc.) or a range consisting of any two thereof, preferably 100:(10-15):(1.5-3):(1.8-3):(9-9.5);

[0040] The polyether polyol combination comprises the p-aminophenol polyether polyol described above, or the p-aminophenol polyether polyol prepared by the method described in the full text.

[0041] In a specific embodiment, the polyether polyol combination comprises the following components:

[0042] Polyether polyol A, with a hydroxyl value of 375-445 mgKOH / g, including but not limited to 375 mgKOH / g, 385 mgKOH / g, 395 mgKOH / g, 405 mgKOH / g, 415 mgKOH / g, 425 mgKOH / g, 435 mgKOH / g, 445 mgKOH / g or a range between any two thereof, with a functionality of 6-7, prepared by addition reaction of sucrose as an initiator with propylene oxide;

[0043] Polyether polyol B, the p-aminophenol polyether polyol;

[0044] Polyether polyol C, with a hydroxyl value of 20 to 75 mgKOH / g, including but not limited to 20 mgKOH / g, 30 mgKOH / g, 40 mgKOH / g, 50 mgKOH / g, 60 mgKOH / g, 70 mgKOH / g, 75 mgKOH / g or a range between any two thereof, a functionality of 2 to 3, prepared by an addition reaction of propylene glycol as an initiator with propylene oxide;

[0045] Polyether polyol D, with a hydroxyl value of 180-250 mgKOH / g, including but not limited to 180 mgKOH / g, 190 mgKOH / g, 200 mgKOH / g, 210 mgKOH / g, 220 mgKOH / g, 230 mgKOH / g, 240 mgKOH / g, 250 mgKOH / g or a range between any two thereof, with a functionality of 3-4, prepared by an addition reaction of propylene oxide with glycerol as an initiator;

[0046] As a preferred embodiment, the mass fractions of the components in the polyether polyol combination are as follows:

[0047] Polyether polyol A is 10 to 40 parts, preferably 20 to 30 parts;

[0048] Polyether polyol B is 10 to 30 parts, preferably 15 to 20 parts;

[0049] Polyether polyol C is 5 to 20 parts, preferably 10 to 15 parts;

[0050] Polyether polyol D is 5 to 15 parts, preferably 5 to 10 parts;

[0051] Specifically, the polyether polyol A can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts or a range consisting of any two parts thereof;

[0052] The polyether polyol B may be 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts or a range consisting of any two parts thereof;

[0053] The polyether polyol C may be 5 parts, 7 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts or a range consisting of any two parts thereof;

[0054] The polyether polyol D can be 5 parts, 7 parts, 9 parts, 10 parts, 12 parts, 14 parts, 15 parts, 15 parts, 15 parts, 15 parts or a range consisting of any two thereof.

[0055] The raw materials of the composite polyether of the present invention also include flame retardants, surfactants, and composite catalysts, which are conventionally selected in the field without special requirements. For example, the flame retardant can be TCPP, the surfactant can be Maitu Y16368, and the composite catalyst includes a foaming catalyst, a gel catalyst, and a trimerization catalyst, wherein the mass ratio of the foaming catalyst to the gel catalyst and the trimerization catalyst is (0-1): (1-5): (0.2-2), preferably (0-1): (1-4): (0.5-2). Preferably, the foaming catalyst is one or more of pentamethyldiethylenetriamine, tetramethylhexanediamine, and bis-dimethylaminoethyl ether, the gel catalyst is one or more of methylimidazole, N-methylpyrrolidone, and PT303, and the trimerization catalyst is TMR-2 and / or potassium acetate. Specifically, commercially available composite catalyst finished products can be directly used.

[0056] In a specific embodiment, the isocyanate is polymeric MDI (polymethylene polyphenyl polyisocyanate), preferably polymeric MDI with an NCO content of 30 to 32%; more preferably, it is one or more of polymeric MDI Wanhua PM-200, polymeric MDI Wanhua PM-2010 and polymeric MDI Wanhua PM-400.

[0057] In a fifth aspect, the present invention provides a method for preparing the above-mentioned polyurethane rigid foam, comprising the following steps:

[0058] 1) uniformly mixing a polyether polyol combination, a flame retardant, a surfactant, a composite catalyst and water to obtain a composite polyether;

[0059] 2) The combined polyether of step 1) is mixed with isocyanate, and mechanically stirred and foamed to obtain a polyurethane rigid foam.

[0060] Preferably, the material temperature during the foaming process is 20-22°C.

[0061] Compared with the prior art, the technical solution of the present invention has the following beneficial effects:

[0062] The p-aminophenol polyether polyol prepared by using p-aminophenol as a starting material contains a benzene ring in its structure, has good compatibility with polymer polyether and flame retardant TCPP, and contains an ether bond, and has good compatibility with water. At the same time, the benzene ring structure has certain rigidity, which can provide certain strength for the full water low-density polyurethane open-cell foam.

[0063] The p-aminophenol polyether polyol provided by the present invention can be used as the main polyether of the all-water foaming polyurethane open-cell system. Compared with the traditional all-water foaming polyurethane open-cell system, it has the advantages of good compatibility, high tolerance, high hardness, low cost and the like. DETAILED DESCRIPTION

[0064] In order to explain the present invention more clearly, the present invention is further described below in conjunction with preferred embodiments. It should be understood by those skilled in the art that the following specific description is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0065] The experimental methods in the following examples without specifying specific conditions are usually measured according to national standards. If there is no corresponding national standard, it is carried out according to the general international standards, conventional conditions, or the conditions recommended by the manufacturer. Unless otherwise specified, all parts are parts by weight, all percentages are weight percentages, and the polymer molecular weight is the number average molecular weight.

[0066] Unless otherwise defined or indicated, all professional and scientific terms used herein have the same meanings as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to those described herein can be applied to the method of the present invention.

[0067] In the present invention, the sources of the main raw materials used are as follows. Other raw materials and reagents, unless otherwise specified, were purchased from commercial sources and were of AR pure quality unless otherwise specified:

[0068] Isocyanate: Wanhua Chemical;

[0069] Surfactant: Y16368, Momentive High-Tech Materials Co., Ltd.;

[0070] Flame retardant: tris(2-chloropropyl) phosphate (TCPP for short);

[0071] Catalyst: composite catalyst, Air Chemicals;

[0072] Polyether polyol B (p-aminophenol polyether polyol): prepared by the example of the present invention;

[0073] Polyether polyol A (sucrose polyether polyol): sucrose as initiator, hydroxyl value of 445 mgKOH / g, functionality of 6.3; or hydroxyl value of 430 mgKOH / g, functionality of 6.7; or hydroxyl value of 375 mg KOH / g, functionality of 6.1; or hydroxyl value of 410 mgKOH / g, functionality of 6.5; Wanhua Chemical (Ningbo) Rongwei;

[0074] Polyether polyol C (propylene glycol polyether polyol): propylene glycol as initiator, hydroxyl value of 56 mgKOH / g, functionality 2; or hydroxyl value of 28 mgKOH / g, functionality 2; Wanhua Chemical (Ningbo) Rongwei;

[0075] Polyether polyol D (glycerol polyether polyol): glycerol is the initiator, the hydroxyl value is 178 mgKOH / g, the functionality is 3.3; or the hydroxyl value is 240 mgKOH / g, the functionality is 3.6; or the hydroxyl value is 245 mgKOH / g, the functionality is 4.0. Wanhua Chemical (Ningbo) Rongwei.

[0076] The main method used in the polyurethane foam performance test of the present invention is:

[0077] Foam core density test according to standard: GB / T 6343-2009;

[0078] Foam thermal conductivity test is in accordance with the standard: GB / T 10295-2008;

[0079] Foam compression strength test according to standard: GB / T 8813-2008;

[0080] Foam dimensional stability test is in accordance with the standard: GB / T 8811-2008;

[0081] The hydroxyl value test method is the phthalic anhydride esterification method.

[0082] Nuclear magnetic resonance: Bruker 400MHz NMR spectrometer AVANCE NEO 400M, test conditions: spectrum is 1H spectrum, solvent is deuterated reagent, reference substance is TMS, sample amount is 5mg, scanning circle number is 8-32.

[0083] Example 1

[0084] Preparation method of p-aminophenol polyether polyol:

[0085]

[0086] Preparation Example 1

[0087] Add p-aminophenol (1090g, 10mol) and KOH (12.8g) to the reactor, replace the air in the reactor with nitrogen, heat to 100℃, vacuum dehydrate for 1h, introduce EO (10560g, 240mol), control the reaction temperature to 140℃, the pressure in the reactor to 0.3MPa, react for 1h, until the pressure in the reactor drops to negative pressure and no longer changes. Add PO (3480g, 60mol), control the reaction temperature to 140℃, the pressure in the reactor to 0.3MPa, react for 2h, until the pressure in the reactor drops to negative pressure and no longer changes. Cool to 80℃, vacuum for 15min, remove a small amount of unreacted EO and PO, add appropriate amount of phosphoric acid to neutralize to pH 6.8, and obtain the final product p-aminophenol polyether polyol (n=8, m=2), with a hydroxyl value of 115mgKOH / g and a functionality of 3.

[0088] The NMR data are as follows:

[0089] 1H NMR (400MHz, CDCl3)6.73(d,J=6.8Hz,2H),6.65(d,J=6.8Hz,2H),5.37(d,J=6.8Hz,3H),4.35-4.27(m,2H),4.22-4 .14(m,4H),3.94-3.86(m,3H),3.60-3.52(m,99H),3.42-3.34(m,6H),1.32(d,J=6.8Hz,9H),1.11(d,J=6.8Hz,9H),

[0090] Preparation Example 2

[0091] Add p-aminophenol (1090g, 10mol) and KOH (12.7g) to the reactor, replace the air in the reactor with nitrogen, heat to 110℃, vacuum dehydrate for 1h, introduce EO (7920g, 180mol), control the reaction temperature to 140℃, the pressure in the reactor to 0.3MPa, react for 1h, until the pressure in the reactor drops to negative pressure and no longer changes. Add PO (1740g, 30mol), control the reaction temperature to 140℃, the pressure in the reactor to 0.3MPa, react for 2h, until the pressure in the reactor drops to negative pressure and no longer changes. Cool to 80℃, vacuum for 15min, remove a small amount of unreacted EO and PO, add appropriate amount of phosphoric acid to neutralize to pH 6.9, and obtain the final product p-aminophenol polyether polyol (n=6, m=1), with a hydroxyl value of 155mgKOH / g and a functionality of 3.

[0092] Preparation Example 3

[0093] Add p-aminophenol (1090g, 10mol) and KOH (12.8g) to the reactor, replace the air in the reactor with nitrogen, heat to 110℃, vacuum dehydrate for 1h, introduce EO (9240g, 210mol), control the reaction temperature to 140℃, the pressure in the reactor to 0.3MPa, react for 1h, until the pressure in the reactor drops to negative pressure and no longer changes. Add PO (1740g, 30mol), control the reaction temperature to 140℃, the pressure in the reactor to 0.3MPa, react for 2h, until the pressure in the reactor drops to negative pressure and no longer changes. Cool to 80℃, vacuum for 15min, remove a small amount of unreacted EO and PO, add appropriate amount of phosphoric acid to neutralize to pH 7.2, and obtain the final product p-aminophenol polyether polyol (n=7, m=1), with a hydroxyl value of 140mgKOH / g and a functionality of 3.

[0094] Example 2

[0095] A fully water-foamed polyurethane open-cell system polyurethane rigid foam, the raw materials are as follows:

[0096] The mass ratio of the combined polyether to the polyisocyanate is 100:150, specifically:

[0097] The weight parts of the combined polyether are as follows: 72 parts of the polyether composition, 15 parts of the flame retardant, 2 parts of the surfactant, 2 parts of the composite catalyst, and 9 parts of distilled water;

[0098] Polyisocyanate: polymeric MDI, Wanhua PM-200 150 parts.

[0099] In the combined polyether:

[0100] The polyether composition is composed of 20 parts by weight of p-aminophenol polyether polyol (prepared by Preparation Example 1 of Example 1), 30 parts of sucrose polyether polyol (hydroxyl value is 410 mgKOH / g, functionality is 6.5), 12 parts of propylene glycol polyether polyol (hydroxyl value is 427 mgKOH / g, functionality is 2), and 10 parts of glycerol polyether polyol (hydroxyl value is 178 mgKOH / g, functionality is 3.3), a total of 72 parts;

[0101] Flame retardant: TCPP 15 parts;

[0102] Surfactant: 2 parts of silicone oil Y16368;

[0103] Composite catalyst: comprising a foaming catalyst of pentamethyldiethylenetriamine: a gelling catalyst of NN dimethylcyclohexylamine: a trimerization catalyst of potassium acetate = 0.3:0.7:1 (mass ratio), 2 parts.

[0104] The preparation method of polyurethane rigid foam comprises the following steps:

[0105] 1) uniformly mixing a polyether polyol combination, a flame retardant, a surfactant, a composite catalyst and water to obtain a composite polyether;

[0106] 2) The mixture of step 1) is mixed with isocyanate, and the mixture is mechanically stirred for foaming. The material temperature of the foaming process is 21° C. and the rotation speed is 4200 r / min to obtain a polyurethane rigid foam.

[0107] Example 3

[0108] A fully water-foamed polyurethane open-cell system polyurethane rigid foam, the raw materials are as follows:

[0109] The mass ratio of the combined polyether to the polyisocyanate is 100:150, specifically:

[0110] The composition of the combined polyether is as follows: 72 parts of the polyether composition, 15 parts of the flame retardant, 2 parts of the surfactant, 2 parts of the composite catalyst, and 9 parts of distilled water;

[0111] Polyisocyanate: polymeric MDI, Wanhua PM-200 150 parts.

[0112] In the combined polyether:

[0113] The polyether composition is composed of: 20 parts of p-aminophenol polyether polyol (prepared by Preparation Example 2 of Example 1), 30 parts of sucrose polyether polyol (hydroxyl value is 410 mgKOH / g, functionality is 6.5), 12 parts of propylene glycol polyether polyol (hydroxyl value is 427 mgKOH / g, functionality is 2), and 10 parts of glycerol polyether polyol (hydroxyl value is 178 mgKOH / g, functionality is 3.3);

[0114] Flame retardant: TCPP 15 parts

[0115] Surfactant: 2 parts of silicone oil Y16368 (Maitu).

[0116] Composite catalyst: the foaming catalyst is pentamethyldiethylenetriamine: the gelling catalyst is NN dimethylcyclohexylamine: the trimerization catalyst is potassium acetate = 0.3:0.7:1 (mass ratio).

[0117] The preparation method of polyurethane rigid foam comprises the following steps:

[0118] 1) uniformly mixing a polyether polyol combination, a surfactant, a composite catalyst and water to obtain a composite polyether;

[0119] 2) The mixture of step 1) is mixed with isocyanate, and mechanically stirred and foamed to obtain a polyurethane rigid foam.

[0120] Example 4

[0121] A fully water-foamed polyurethane open-cell system polyurethane rigid foam, the raw materials are as follows:

[0122] The mass ratio of the combined polyether to the polyisocyanate is 100:150, specifically:

[0123] The weight parts of the combined polyether are as follows: 72 parts of the polyether composition, 15 parts of the flame retardant, 2 parts of the surfactant, 2 parts of the composite catalyst, and 9 parts of distilled water;

[0124] Polyisocyanate: polymeric MDI, Wanhua PM-200 150 parts.

[0125] In the combined polyether:

[0126] The polyether composition is composed of 20 parts by weight of p-aminophenol polyether polyol (prepared by Preparation Example 3 of Example 1), 30 parts of sucrose polyether polyol (hydroxyl value is 410 mgKOH / g, functionality is 6.5), 12 parts of propylene glycol polyether polyol (hydroxyl value is 427 mgKOH / g, functionality is 2), and 10 parts of glycerol polyether polyol (hydroxyl value is 178 mgKOH / g, functionality is 3.3), a total of 72 parts;

[0127] Flame retardant: TCPP 15 parts;

[0128] Surfactant: 2 parts of silicone oil Y16368;

[0129] Composite catalyst: comprising a foaming catalyst of pentamethyldiethylenetriamine: a gelling catalyst of NN dimethylcyclohexylamine: a trimerization catalyst of potassium acetate = 0.3:0.7:1 (mass ratio), 2 parts.

[0130] The preparation method of polyurethane rigid foam comprises the following steps:

[0131] 1) uniformly mixing a polyether polyol combination, a flame retardant, a surfactant, a composite catalyst and water to obtain a composite polyether;

[0132] 2) The mixture of step 1) is mixed with isocyanate, and the mixture is mechanically stirred for foaming. The material temperature of the foaming process is 21° C. and the rotation speed is 4200 r / min to obtain a polyurethane rigid foam.

[0133] Comparative Example 1

[0134] A fully water-foamed polyurethane open-cell system polyurethane rigid foam, the raw materials are as follows:

[0135] The mass ratio of the combined polyether to the polyisocyanate is 100:150, specifically:

[0136] Combined polyether: Competitor O2228 in Vietnam's wave board market

[0137] Polyisocyanate: polymeric MDI, Wanhua PM-200 150 parts.

[0138] The preparation method of polyurethane rigid foam comprises the following steps:

[0139] 1) uniformly mixing a polyether polyol combination, a surfactant, a composite catalyst and water to obtain a composite polyether;

[0140] 2) The mixture of step 1) is mixed with isocyanate, and mechanically stirred and foamed to obtain a polyurethane rigid foam.

[0141] Comparative Example 2

[0142] A fully water-foamed polyurethane open-cell system polyurethane rigid foam, the raw materials are as follows:

[0143] The mass ratio of the combined polyether to the polyisocyanate is 100:150, specifically:

[0144] Combined polyether: K6690, a competitor in the Vietnamese surfboard market

[0145] Polyisocyanate: polymeric MDI, Wanhua PM-200 150 parts.

[0146] The preparation method of polyurethane rigid foam comprises the following steps:

[0147] 1) uniformly mixing a polyether polyol combination, a surfactant, a composite catalyst and water to obtain a composite polyether;

[0148] 2) The mixture of step 1) is mixed with isocyanate, and mechanically stirred and foamed to obtain a polyurethane rigid foam.

[0149] Comparative Example 3

[0150] A fully water-foamed polyurethane open-cell system polyurethane rigid foam was prepared with reference to Example 2, except that p-aminophenol polyether polyol was not added to the raw material composition, and other raw materials and operations remained unchanged.

[0151] The performance parameters of polyurethane rigid foam of Examples 2-3 and Comparative Examples 1-2 are shown in Table 1:

[0152] Table 1 Performance parameters of polyurethane rigid foam of Examples 2-3 and Comparative Examples 1-2

[0153]

[0154] Note: Foam density, compression strength and thermal conductivity are all measured according to national standards:

[0155] Foam core density test according to standard: GB / T 6343-2009;

[0156] Foam thermal conductivity test is in accordance with the standard: GB / T 10295-2008;

[0157] Foam compression strength test according to standard: GB / T 8813-2008;

[0158] Dimensional stability test according to standard: GB / T 8811-2008;

[0159] By comparing Example 2 with Example 3, compared with traditional sucrose polyether, the application of p-aminophenol polyether polyol in the full water foamed polyurethane open-cell system has the advantages of good compatibility, high compression strength, low thermal conductivity, good dimensional stability and low consumption per meter of board.

[0160] By comparing Example 2 with Comparative Examples 1 and 2, the fully water-opened pore system containing p-aminophenol polyether polyol has the advantages of good compatibility, high compression strength, low thermal conductivity, good dimensional stability and low consumption per meter of board compared with competing products on the Vietnamese corrugated board market.

[0161] The above is only a preferred embodiment of the present invention, and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment, it is not used to limit the present invention. Any technician familiar with this patent can make some changes or modify the technical contents suggested above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the solution of the present invention.

Claims

1. A p-aminophenol polyether polyol having a structure as shown in formula (1): in, n is each independently an integer from 5 to 10, preferably an integer from 6 to 8; m is each independently an integer from 1 to 5, preferably an integer from 1 to 3.

2. p-Aminophenol polyether polyol according to claim 1, characterized in that, The hydroxyl value is 100 to 180 mgKOH / g, preferably 120 to 160 mgKOH / g; and / or The functionality is 3 to 4.

3. A method for preparing p-aminophenol polyether polyol according to claim 1 or 2, characterized in that: Using p-aminophenol as a starting material, reacting with olefin oxide in the presence of a catalyst to prepare p-aminophenol polyether polyol as shown in formula (1); Preferably, the oxidized olefin is ethylene oxide and / or propylene oxide; Preferably, the molar ratio of p-aminophenol to olefin oxide is 1:18-45.

4. The preparation method according to claim 3, characterized in that: The following steps are involved: S1: mixing p-aminophenol and a catalyst, heating to a reaction temperature, and introducing ethylene oxide to react until the pressure stops decreasing; S2: Propylene oxide is introduced to react until the pressure stops decreasing; S3: removing unreacted ethylene oxide and propylene oxide in vacuo, adding acid for neutralization, and obtaining the p-aminophenol polyether polyol.

5. The preparation method according to claim 4, characterized in that: Step S1 includes a dehydration process after the p-aminophenol and the catalyst are mixed; preferably, during the dehydration process, the temperature is 100 to 120° C. and the time is 0.5 to 1 h under vacuum; and / or The catalyst in step S1 is selected from alkaline hydroxides, preferably one or more of sodium hydroxide and potassium hydroxide, more preferably potassium hydroxide; Preferably, the amount of the catalyst is 1 to 3 wt% of the mass of p-aminophenol; and / or The molar ratio of p-aminophenol to ethylene oxide in step S1 is 1:15 to 30, preferably 1:18 to 24; and / or The reaction in step S1 is carried out at a temperature of 130 to 160° C., preferably 140 to 150° C., and a reaction pressure of 0.2 to 0.3 MPa.

6. The method according to claim 4, characterized in that: The molar ratio of p-aminophenol to propylene oxide in step S2 is 1:3 to 15, preferably 1:3 to 9; and / or The reaction in step S2 is carried out at a temperature of 130 to 160° C., preferably 140 to 150° C., and a reaction pressure of 0.2 to 0.3 MPa; and / or In step S3, unreacted ethylene oxide and propylene oxide are removed by vacuum at a temperature of 80 to 90° C. for 15 to 30 minutes; and / or In step S3, the acid is neutralized to a pH value of 6 to 8; preferably, the acid is selected from one or more of acetic acid and phosphoric acid, more preferably phosphoric acid.

7. Use of the p-aminophenol polyether polyol according to claim 1 or 2, or the p-aminophenol polyether polyol prepared by the method according to any one of claims 3 to 6 in polyurethane foam, particularly suitable for all-water foamed polyurethane open-cell system.

8. A polyurethane rigid foam, characterized in that: The polyurethane rigid foam is prepared by combining polyether and isocyanate through foaming reaction; wherein the mass ratio of the combined polyether to isocyanate is 100:130-160, preferably 100:140-150; The composite polyether comprises a polyether polyol combination, a flame retardant, a surfactant, a composite catalyst and water, and the mass ratio thereof is 100:(5-21):(1-5):(1.5-4.5):(8-13), preferably 100:(10-15):(1.5-3):(1.8-3):(9-9.5); The polyether polyol combination comprises the p-aminophenol polyether polyol according to claim 1 or 2, or the p-aminophenol polyether polyol prepared by the method according to any one of claims 3-6.

9. The polyurethane rigid foam according to claim 8, characterized in that: The polyether polyol combination comprises the following components: Polyether polyol A, with a hydroxyl value of 375-445 mgKOH / g and a functionality of 6-7, is prepared by an addition reaction of sucrose as an initiator with propylene oxide; Polyether polyol B, the p-aminophenol polyether polyol according to claim 1 or 2, or the p-aminophenol polyether polyol prepared by the method according to any one of claims 3 to 6; Polyether polyol C, with a hydroxyl value of 20 to 75 mgKOH / g and a functionality of 2 to 3, is prepared by an addition reaction between propylene glycol and propylene oxide as an initiator; Polyether polyol D, with a hydroxyl value of 180-250 mgKOH / g and a functionality of 3-4, is prepared by an addition reaction of propylene oxide with glycerol as an initiator; Preferably, the mass proportion of each component in the polyether polyol combination is as follows: polyether polyol A is 10 to 40 parts, preferably 20 to 30 parts; polyether polyol B is 10 to 30 parts, preferably 15 to 20 parts; polyether polyol C is 5 to 20 parts, preferably 10 to 15 parts; polyether polyol D is 5 to 15 parts, preferably 5 to 10 parts.

10. A method for preparing the polyurethane rigid foam according to claim 8 or 9, characterized in that: The following steps are involved: 1) uniformly mixing a polyether polyol combination, a flame retardant, a surfactant, a composite catalyst and water to obtain a composite polyether; 2) The mixture of step 1) is mixed with isocyanate, and mechanically stirred and foamed to obtain a polyurethane rigid foam.

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