A polyether ester polyol, a method for preparing the same, and use thereof

Abstract

The present application provides a kind of polyether ester polyols, its preparation method, and the cell opener comprising the polyether ester polyols, and the purposes of polyether ester polyols in the preparation of slow rebound polyurethane foam.The polyether ester polyols include (i) the compound represented, the compound represented by formula (ii), and the optional compound represented by formula (iii).The polyether ester polyols according to the present application can provide good hydrophobic hole breaking effect, effectively improve the drawbacks of slow rebound foam closed hole, achieve the effect of foam opening, ensure that the slow rebound foam prepared has excellent air permeability,

Description

Technical Field

[0001] This invention specifically relates to a polyether ester polyol for slow rebound pore-opening agents, its preparation method, and its application. Background Technology

[0002] Slow rebound polyurethane foam, also known as viscoelastic foam or memory foam, is widely used in home furnishings such as slow rebound mattresses and pillows due to its shape memory and energy absorption cushioning properties. It helps relieve pressure on the body and promotes blood circulation. Currently, there are two main types of slow rebound foam products on the market. The first type is a glycerol-based, high-proportion ethylene oxide and low-proportion propylene oxide ring-opening polymerization-prepared gas-expanding polyether product. This type of slow rebound foam has drawbacks such as poor fatigue resistance, poor flexibility, and poor slow rebound effect, making it unsuitable for high-end home furnishings. The second type is a glycerol-based, propylene oxide ring-opening polymerization-prepared small-molecule polyether product. This type of slow rebound foam has excellent physical properties but suffers from poor air permeability and needs to be used in conjunction with a slow rebound cell opener. However, currently available cell opener products all have corresponding problems, such as… Defoamers such as paraffin wax or silicone have a very narrow operational tolerance and can easily disrupt the foam stability of the sponge before it fully expands, resulting in uneven foam structure, large pores, and even foam collapse. Inorganic fillers, such as calcium carbonate and barium sulfate, have poor opening effects; increasing their dosage can damage the sponge structure, leading to a decrease in physical and mechanical properties such as tensile strength and tear strength. Additionally, there are high molecular weight polyether polyols with homopolymer structures of propylene oxide or butane oxide. These opener agents can achieve good opening efficiency in low-density sponges, but their effectiveness diminishes when the sponge density exceeds 60 kg / m³. 3 The effect of post-opening is minimal. Therefore, developing an opening agent product that has excellent opening effect without affecting the physical properties of slow rebound sponge is currently a challenge in this field.

[0003] CN102336900B discloses an application of polyether polyols or polyether polyesters as opening agents for slow-rebound polyurethane foams. The method uses a low molecular weight polyether polyol as an initiator and DMC as a catalyst to perform ring-opening of epoxides to prepare an opening agent with a polyether polyol structure. Alternatively, it uses a low molecular weight polyether polyol as an initiator and DMC as a catalyst to perform ring-opening of epoxides, followed by esterification with a low molecular weight acid to prepare an opening agent with a polyether polyester structure. However, the opening agent prepared by this method is a polyether polyol or polyether polyester, with only ether bonds or ether bonds as the main component and a very small amount of ester bonds at the ends. When applied to slow-rebound foams, the opening effect is generally poor and it does not improve the mechanical properties of the slow-rebound foam. Summary of the Invention

[0004] To address the problems existing in the prior art, the present invention aims to provide a polyether ester polyol, wherein the cell opener containing the polyether ester polyol has excellent cell opening effect and can improve the mechanical properties of slow rebound polyurethane foam.

[0005] Another objective of this invention is to provide a method for preparing the polyether ester polyol, wherein a small molecule polyether polyol containing a double benzene ring structure is used as an initiator, and a hydrophobic epoxy alkane (propylene oxide, butane oxide, etc.) is subjected to ring-opening polymerization, and the end is modified by esterification with a long-chain fatty acid to further enhance the hydrophobic properties of the product, thereby preparing a polyether ester polyol for cell opening, which is beneficial for foam opening and improving the mechanical properties of the foam when used in slow rebound polyurethane foam.

[0006] Another object of the present invention is to provide a pore-opening agent comprising the polyether ester polyol described in the present invention.

[0007] Another object of the present invention is to provide the use of the polyether ester polyol according to the present invention in the preparation of slow-rebound polyurethane foam.

[0008] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0009] According to a first aspect of the invention, a polyether ester polyol is provided, comprising a compound represented by formula (i), a compound represented by formula (ii), and optionally a compound represented by formula (iii):

[0010]

[0011] Where each m is the same or different, and each n is the same or different, and 0≤n≤60, 10≤m≤150;

[0012] R is:

[0013] R1 is a long-chain fatty acid residue with the following general structural formula: Wherein, X1 is an alkylene group or an alkylene group containing an unsaturated double bond, X2 is a hydroxyl group or a methyl group, and the total number of carbon atoms in the long-chain fatty acid is greater than or equal to 10, preferably 10 to 20.

[0014] In the polyether ester polyol, the molar percentage of the compound represented by formula (i) is 50% to 100%; the molar percentage of the compound represented by formula (ii) is 0% to 50%, preferably 5% to 50%; and the molar percentage of the compound represented by formula (iii) is less than 5%.

[0015] According to a second aspect of the present invention, a method for preparing the polyether ester polyol is provided, comprising the following steps:

[0016] Step 1): Using a substance containing a double benzene ring structure as initiator 1 and epoxide alkane 1 as a polymerization monomer, a polymerization reaction is carried out under the action of a catalyst to obtain polyether polyol prepolymer A;

[0017] Step 2): The polyether polyol prepolymer A from Step 1) is purified to obtain polyether polyol prepolymer B;

[0018] Step 3): Using polyether polyol prepolymer B from step 2) as initiator 2 and epoxide alkane 2 as polymerization monomer, the polymerization reaction is carried out under the catalysis of DMC (bimetallic cyanide) to obtain polyether polyol C;

[0019] Step 4): Mix polyether polyol C with long-chain fatty acids evenly, and esterify them under the action of a catalyst to obtain the polyether ester polyol.

[0020] Preferably, the initiator 1 in step 1) includes, but is not limited to, bisphenol A, bisphenol S, etc.

[0021] Preferably, when n is 0, alkylene oxide 1 is butane oxide and alkylene oxide 2 is butane oxide; when n is not 0, alkylene oxide 1 is propylene oxide or propylene oxide and butane oxide added sequentially, and alkylene oxide 2 is butane oxide, wherein the sequential addition of propylene oxide and butane oxide indicates that butane oxide is added after the propylene oxide reaction is completed.

[0022] Preferably, the catalyst in step 1) includes, but is not limited to, alkali metal hydroxides, alkaline earth metal hydroxides, such as potassium hydroxide, sodium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydride, etc.

[0023] Preferably, the reaction temperature in step 1) is 90–130°C.

[0024] Preferably, the feeding time of epoxide alkane 1 in step 1) is 1 to 10 hours.

[0025] Preferably, the mass ratio of initiator 1 to epoxide alkane 1 in step 1) is 1:1 to 30.

[0026] Preferably, the weight of the catalyst in step 1) is 0.1% to 1% of the total mass of the initiator 1 and the epoxide alkane 1.

[0027] Preferably, in step 1), when the epoxide alkane 1 is propylene oxide and epoxide butane added sequentially, the mass ratio of propylene oxide to epoxide butane is 1:0.1 to 10.

[0028] Preferably, the purification in step 2) includes acid neutralization, adsorption with an adsorbent, vacuum dehydration, and filtration.

[0029] Preferably, the acid in step 2) is selected from, but is not limited to, phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, lactic acid, acetic acid, or oxalic acid.

[0030] Preferably, in step 2), the pH of the system is neutralized to 4-5 using acid.

[0031] Preferably, the adsorbent in step 2) is selected from, but not limited to, magnesium silicate, aluminum silicate, magnesium aluminum silicate, diatomaceous earth, or clay.

[0032] Preferably, the amount of adsorbent used in step 2) is 0.1-5% of the mass of polyether polyol prepolymer A.

[0033] Preferably, the acid neutralization temperature in step 2) is 20–100°C.

[0034] Preferably, the adsorption temperature in step 2) is 80–120°C.

[0035] Preferably, the dehydration temperature in step 2) is 100–120°C.

[0036] Preferably, the dehydration time in step 2) is 1 to 10 hours.

[0037] Preferably, the dehydration pressure in step 2) is -0.095 MPa to 0 MPa.

[0038] Preferably, the filter in step 2) is selected from, but is not limited to, candle filters, sintered filter cartridge filters, plate and frame filters, etc.

[0039] Preferably, the reaction temperature in step 3) is 120–160°C.

[0040] Preferably, the feeding time of the alkyl epoxide in step 3) is 1 to 10 hours.

[0041] Preferably, the mass ratio of polyether polyol prepolymer B to epoxy alkane in step 3) is 1:1 to 20.

[0042] Preferably, the amount of DMC (bimetallic cyanide) used in step 3) is 0.002% to 0.1% of the mass of polyether polyol prepolymer B.

[0043] Preferably, the long-chain fatty acid in step 4) has the following structure:

[0044]

[0045] Wherein X1 is an alkylene group or an alkylene group containing an unsaturated double bond, X2 is a hydroxyl group or a methyl group, and the total number of carbon atoms of the long-chain fatty acid is greater than or equal to 10, preferably 10 to 20; more preferably, the long-chain fatty acid is selected from, but not limited to, one or more of ricinoleic acid, linolenic acid, linoleic acid, arachidic acid, tung oil acid, 12,13-epoxyoleic acid and oleic acid.

[0046] Preferably, the catalyst in step 4) includes, but is not limited to, isobutyl titanate, isopropyl titanate, n-butyl titanate, triethylamine, trimethylamine, etc.

[0047] Preferably, the reaction temperature in step 4) is 180–260°C.

[0048] Preferably, the molar ratio of polyether polyol C to long-chain fatty acid in step 4) is 1:0.5 to 1.

[0049] Preferably, the mass ratio of long-chain fatty acids to catalyst in step 4) is 1:0.001 to 0.1.

[0050] It should be noted that in this application, polyether polyol prepolymer A, polyether polyol prepolymer B, and polyether polyol C are all intermediate products of the final product of the present invention, polyether ester polyol. Those skilled in the art can determine its structure based on the final product polyether ester polyol and the reaction steps.

[0051] Specifically, polyether polyol prepolymer A and polyether polyol prepolymer B have the same structure.

[0052] When n is 0, the structural formulas of polyether polyol prepolymer A and polyether polyol prepolymer B are H-(OC4H8). p -R-(C4H8O) p -H; The structural formula of polyether polyol C is H-(OC4H8). m -R-(C4H8O) m -H;

[0053] When n is not 0, the structural formulas of polyether polyol prepolymer A and polyether polyol prepolymer B are H-(OC4H8). k -(OC3H6) n -R-(C3H6O) n -(C4H8O) k -H, the structural formula of polyether polyol C is H-(OC4H8). m -(OC3H6) n -R-(C3H6O) n -(C4H8O) m -H;

[0054] R, n, and m are defined as described above, p is 1 to 10 and p is less than m; k is 0 to 10 and k is less than m.

[0055] According to a third aspect of the invention, a pore-opening agent is provided, comprising the polyether ester polyol described in the invention.

[0056] According to a fourth aspect of the invention, the use of the polyether ester polyol according to the invention in the preparation of slow-rebound polyurethane foam is provided.

[0057] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0058] The slow-rebound cell opener polyether ester polyol of this invention contains a biphenyl ring structure, which provides sufficient rigidity when applied in slow-rebound foam, effectively increasing the mechanical properties (tear strength, tensile strength, etc.) of the slow-rebound foam. In the preparation of slow-rebound foam, the maximum amount of commercially available slow-rebound cell opener polyether polyol added relative to 100 parts by weight of raw material is 5 parts by weight. If the amount is further increased, the mechanical properties of the slow-rebound foam will significantly decrease. However, the slow-rebound cell opener polyether ester polyol of this invention can not only be added in larger quantities, but also improves the mechanical properties of the prepared slow-rebound foam.

[0059] The slow-rebound opening agent polyether ester polyol of the present invention contains superhydrophobic fatty acid segments in its terminal structure. When applied in slow-rebound foam, it can provide a good hydrophobic breaking effect, effectively improving the drawback of severe closed-cell structure in slow-rebound foam, achieving the effect of foam opening, and ensuring that the prepared slow-rebound foam has excellent air permeability. When applied in home furnishing fields such as slow-rebound U-shaped pillows, butterfly pillows, and mattresses, it provides consumers with good comfort and health. Detailed Implementation

[0060] To better understand the technical solution of the present invention, the following embodiments will further illustrate the method provided by the present invention. However, the present invention is not limited to the listed embodiments, but should also include any other known modifications within the scope of the claims of the present invention.

[0061] It should be noted that in the embodiments and comparative examples of the present invention, since the conversion rate of the etherification reaction in the alkali or DMC catalyst is as high as 99% to 100%, the values ​​of n and m in the polyether ester compound can be roughly calculated based on the feed ratio.

[0062] Example 1

[0063] 500g of bisphenol A and 15g of potassium hydroxide were added to a high-pressure reactor, and the reactor was fully purged with nitrogen 10 times. 2500g of propylene oxide was continuously introduced over 5 hours at 120℃ and the reactor was matured for 1 hour to prepare polyether polyol prepolymer A. Phosphoric acid was added to the reactor, and the reactor was stirred at 80℃ for 1 hour to adjust the pH to 4-5. 25g of magnesium silicate was added, and the reactor was stirred at 90℃ for 1 hour. The temperature was raised to 110℃, and the reactor was dehydrated under vacuum at -0.095MPa for 5 hours. The prepolymer was then filtered through a candle filter to obtain refined polyether polyol prepolymer B.

[0064] 2000g of polyether polyol prepolymer B and 1g of DMC catalyst were added to a high-pressure reactor. The reactor was fully purged with nitrogen 10 times. At 160°C, with stirring, 10000g of epoxide was continuously introduced over 10 hours and the reactor was matured for 1 hour to prepare polyether polyol C.

[0065] 436 g of ricinoleic acid and 43.6 g of isobutyl titanate were added to a reactor and esterified at 260 °C for 10 h. The reactor was then maintained at 260 °C and dehydrated under vacuum at -0.095 MPa for 2 h to prepare a slow-rebound pore-opening polyether ester polyol. The hydroxyl value was determined to be 13.98 mg KOH / g. NMR analysis showed that the molar percentage of polyether polyols capped on only one side by ricinoleic acid residues was 89.2%, the molar percentage of polyether polyols not capped on either side by ricinoleic acid residues was 7.7%, and the molar percentage of polyether polyols capped on both sides by ricinoleic acid residues was 3.1%.

[0066] Example 2

[0067] 500g of bisphenol S and 15g of sodium hydroxide were added to a high-pressure reactor. The reactor was fully purged with nitrogen 10 times. 500g of propylene oxide was continuously introduced over 2 hours at 130°C for 10 minutes of maturation. Then, 500g of butane oxide was continuously introduced over 2 hours for 1 hour of maturation to prepare polyether polyol prepolymer A. Sulfuric acid was added to the reactor and stirred over 1 hour at 50°C. The pH was adjusted to 4-5. 30g of diatomaceous earth was added and stirred over 1 hour at 80°C. The temperature was raised to 120°C and dehydrated under vacuum at -0.080MPa for 8 hours. The purified polyether polyol prepolymer B was obtained by filtration through a plate and frame filter.

[0068] 750g of polyether polyol prepolymer B and 0.75g of DMC catalyst were added to a high-pressure reactor. After 10 complete nitrogen purgings, 11250g of epoxide was continuously introduced over 5 hours at 150°C with stirring. The mixture was then matured for 1 hour to prepare polyether polyol C.

[0069] 168 g of linolenic acid and 8.4 g of triethylamine were added to a reactor and esterified at 240 °C for 10 h. The reaction was then carried out under vacuum at -0.095 MPa for 2 h to prepare a slow-rebound pore-opening polyether ester polyol. The hydroxyl value was determined to be 6.87 mg KOH / g. NMR analysis showed that the molar percentage of polyether polyols capped on only one side by linolenic acid residues was 57.3%, the molar percentage of polyether polyols not capped on either side by linolenic acid residues was 41.8%, and the molar percentage of polyether polyols capped on both sides by linolenic acid residues was 0.9%.

[0070] Example 3

[0071] 500g of bisphenol A and 15g of potassium hydroxide were added to a high-pressure reactor. The reactor was purged with nitrogen 10 times. 2500g of epoxide was continuously introduced over 5 hours at 120°C and the reactor was matured for 1 hour to prepare polyether polyol prepolymer A. Phosphoric acid was added to the reactor and stirred at 90°C for 1 hour to adjust the pH to 4-5. 25g of magnesium silicate was added and stirred at 100°C for 1 hour. The temperature was raised to 110°C and the reactor was dehydrated under vacuum at -0.095MPa for 5 hours. The mixture was then filtered through a candle filter to obtain refined polyether polyol prepolymer B.

[0072] 2000g of polyether polyol prepolymer B and 1g of DMC catalyst were added to a high-pressure reactor. The reactor was fully purged with nitrogen 10 times. At 160°C, with stirring, 10000g of epoxide was continuously introduced over 10 hours and the reactor was matured for 1 hour to prepare polyether polyol C.

[0073] 400 g of ricinoleic acid and 35.0 g of isobutyl titanate were added to a reactor and esterified at 260 °C for 10 h. The reactor was then maintained at 260 °C and dehydrated under vacuum at -0.095 MPa for 2 h to prepare a slow-rebound pore-opening polyether ester polyol. The hydroxyl value was determined to be 14.10 mg KOH / g. NMR analysis showed that the molar percentage of polyether polyols capped on only one side by ricinoleic acid residues was 88.3%, the molar percentage of polyether polyols not capped on either side by ricinoleic acid residues was 10.2%, and the molar percentage of polyether polyols capped on both sides by ricinoleic acid residues was 1.5%.

[0074] Example 4

[0075] 500g of bisphenol A and 15g of potassium hydroxide were added to a high-pressure reactor, and the reactor was fully purged with nitrogen 10 times. 1500g of epoxide was continuously introduced over 5 hours at 120℃ and the reactor was matured for 1 hour to prepare polyether polyol prepolymer A. Phosphoric acid was added to the reactor, and the reactor was stirred at 90℃ for 1 hour to adjust the pH to 4-5. 25g of magnesium silicate was added, and the reactor was stirred at 100℃ for 1 hour. The temperature was raised to 110℃, and the reactor was dehydrated under vacuum at -0.095MPa for 5 hours. The mixture was then filtered through a candle filter to obtain polyether polyol prepolymer B.

[0076] 1000g of polyether polyol prepolymer B and 0.8g of DMC catalyst were added to a high-pressure reactor. The reactor was fully purged with nitrogen 10 times. At 150°C, with stirring, 1000g of epoxide was continuously introduced over 1 hour and the reactor was matured for 1 hour to prepare polyether polyol C.

[0077] 326 g of ricinoleic acid and 26.0 g of isobutyl titanate were added to a reactor and esterified at 260 °C for 10 h. The reaction was then carried out at 240 °C under vacuum at -0.095 MPa for 2 h to prepare a slow-rebound pore-opening polyether ester polyol. The hydroxyl value was determined to be 53.18 mg KOH / g. NMR analysis showed that the molar percentage of polyether polyols capped on only one side by ricinoleic acid residues was 87.6%, the molar percentage of polyether polyols not capped on either side by ricinoleic acid residues was 7.7%, and the molar percentage of polyether polyols capped on both sides by ricinoleic acid residues was 4.7%.

[0078] Example 5

[0079] 500g of bisphenol A and 50.75g of potassium hydroxide were added to a high-pressure reactor. The reactor was purged with nitrogen 10 times. 14000g of propylene oxide was continuously introduced over 10 hours at 100°C and allowed to mature for 1 hour to prepare polyether polyol prepolymer A. Phosphoric acid was added to the reactor and stirred at 90°C for 1 hour. The pH was adjusted to 4-5. 145g of magnesium silicate was added and stirred at 100°C for 1 hour. The temperature was raised to 110°C and the reactor was dehydrated under vacuum at -0.095MPa for 5 hours. The mixture was then filtered through a candle filter to obtain polyether polyol prepolymer B.

[0080] 661g of polyether polyol prepolymer B and 0.17g of DMC catalyst were added to a high-pressure reactor. After purging with nitrogen 10 times, 2091g of epoxide was continuously introduced over 10 hours at 150°C with stirring. The mixture was then matured for 1 hour to prepare polyether polyol C.

[0081] 21 g of ricinoleic acid and 2.1 g of isobutyl titanate were added to a reactor and esterified at 260 °C for 10 h. The reactor was then maintained at 260 °C and dehydrated under vacuum at -0.095 MPa for 2 h to prepare a slow-rebound pore-opening polyether ester polyol. The hydroxyl value was determined to be 4.08 mg KOH / g. NMR analysis showed that the molar percentage of polyether polyols capped on only one side by ricinoleic acid residues was 65.2%, the molar percentage of polyether polyols not capped on either side by ricinoleic acid residues was 33.6%, and the molar percentage of polyether polyols capped on both sides by ricinoleic acid residues was 1.2%.

[0082] Comparative Example 1

[0083] The synthesis method was the same as in Example 1, except that polyether polyol C was prepared without esterification modification using ricinoleic acid. The product had a hydroxyl value of 14.52 mgKOH / g, and NMR analysis showed that the molar percentage of polyether polyol without ricinoleic acid residues on both sides was 100%.

[0084] Comparative Example 2

[0085] In Example 1, the initiator bisphenol A was replaced with polyether WANOL PPG230 (produced by Wanhua Chemical Group Co., Ltd., functionality 2, hydroxyl value 490 mg KOH / g), with all other conditions remaining unchanged. The product was measured to have a hydroxyl value of 13.23 mg KOH / g. NMR analysis showed that the molar percentage of polyether polyols capped on only one side by ricinoleic acid residues was 90.3%, the molar percentage of polyether polyols not capped on either side by ricinoleic acid residues was 6.5%, and the molar percentage of polyether polyols capped on both sides by ricinoleic acid residues was 3.2%.

[0086] Comparative Example 3

[0087] Except for replacing the amount of ricinoleic acid added in Example 1 with 850g, all other conditions remained unchanged. The hydroxyl value was determined to be 13.82mgKOH / g. NMR analysis showed that the molar percentage of polyether polyols capped on only one side by ricinoleic acid residues was 5.3%, the molar percentage of polyether polyols not capped on either side by ricinoleic acid residues was 1.2%, and the molar percentage of polyether polyols capped on both sides by ricinoleic acid residues was 93.5%.

[0088] Comparative Example 4

[0089] 500g of bisphenol A and 15g of potassium hydroxide were added to a high-pressure reactor, and the reactor was fully purged with nitrogen 10 times. 2500g of propylene oxide was continuously introduced over 5 hours at 120℃ and the reactor was matured for 1 hour to prepare polyether polyol prepolymer A. Phosphoric acid was added to the reactor, and the reactor was stirred at 80℃ for 1 hour to adjust the pH to 4-5. 25g of magnesium silicate was added, and the reactor was stirred at 90℃ for 1 hour. The temperature was raised to 110℃, and the reactor was dehydrated under vacuum at -0.095MPa for 5 hours. The prepolymer was then filtered through a candle filter to obtain refined polyether polyol prepolymer B.

[0090] 600 g of ricinoleic acid and 30.5 g of isobutyl titanate were added to a reactor and esterified at 260 °C for 10 h. The reactor was then maintained at 260 °C and dehydrated under vacuum at -0.095 MPa for 2 h to prepare a slow-rebound pore-opening polyether ester polyol. The hydroxyl value was determined to be 68.9 mg KOH / g. NMR analysis showed that the molar percentage of polyether polyols capped on only one side by ricinoleic acid residues was 85.3%, the molar percentage of polyether polyols not capped on either side by ricinoleic acid residues was 12.0%, and the molar percentage of polyether polyols capped on both sides by ricinoleic acid residues was 2.7%.

[0091] Application performance testing:

[0092] Slow-rebound polyurethane foam was prepared using the following components:

[0093] MDI (diphenylmethane diisocyanate, produced by Wanhua Chemical Group Co., Ltd.);

[0094] POP 2045 (Polymer polyol, manufactured by Wanhua Chemical Group Co., Ltd.)

[0095] WANOL S3007 (polyether polyol, produced by Wanhua Chemical Group Co., Ltd.);

[0096] WANOL F3156D (polyether polyol, produced by Wanhua Chemical Group Co., Ltd.);

[0097] Polyurethane foaming aids include: silicone oils HW0193 and Y10366, catalysts A33 and T9, and demineralized water;

[0098] Slow rebound pore opener SKC1900 (manufactured by SK Group of South Korea).

[0099] The process of making slow rebound foam is as follows:

[0100] Add the following ingredients sequentially to a beaker: polyether polyol, polymer polyol, cell opener (polyether ester polyol prepared in the examples or comparative examples), water, silicone oil additive, and foaming catalyst, as shown in Table 1. Maintain the material temperature at 22-25℃ and stir thoroughly using an electric stirrer at 4000 rpm. At room temperature (20-30℃), rapidly add isocyanate and stir for 6-8 seconds. Pour the mixture into a foaming chamber for free foaming. Prepare foam with dimensions of 45cm × 45cm × 20cm for property testing. Tests are conducted after curing at room temperature for 72 hours.

[0101] Table 1: Slow rebound polyurethane foam formulations and properties are as follows:

[0102]

[0103]

[0104] Note: The test methods for the physical properties of slow rebound polyurethane foam are as follows: Tensile strength: Test reference GB 6344-2008;

[0105] Tear strength: Tested according to GB 10808-2006;

[0106] Elongation at break: Tested according to GB 6344-2008;

[0107] 65% indentation hardness: Test reference GB 10807-2006;

[0108] Compression set: Test reference GB 6669-2008;

[0109] Air permeability: Tested according to GB / T 5453-1997;

[0110] Slow rebound time: After the foam is compressed to its lowest height and the external force is removed, the foam recovery time is recorded.

[0111] As can be seen from the table above, the slow rebound polyurethane foam prepared using the embodiments of the present invention has significant advantages in mechanical properties (tensile strength, tear strength, elongation at break, etc.) and air permeability compared to the slow rebound foam prepared by the comparative example and commercially available cell opener products. This indicates that the slow rebound cell opener polyether ester polyol synthesized by the present invention has good practical value in the field of slow rebound polyurethane foam.

[0112] Although the present invention has been described in detail through the preferred embodiments described above, it should be understood that the above description should not be considered as a limitation of the present invention. Those skilled in the art will understand that modifications or adjustments can be made to the present invention based on the teachings of this specification. These modifications or adjustments should also be within the scope defined by the claims of the present invention.

Claims

1. A polyether ester polyol comprising a compound represented by formula (i), a compound represented by formula (ii), and a compound represented by formula (iii): in, Each m may be the same or different, and each n may be the same or different, and 0≤n≤60, 10≤m≤150; R is: R1 is a long-chain fatty acid residue with the following general structural formula: Wherein, X1 is an alkylene group or an alkylene group containing an unsaturated double bond, X2 is a hydroxyl or methyl group, the total number of carbon atoms of the long-chain fatty acid is 10 to 20, the molar percentage of the compound represented by formula (i) is 50% to 100%, and not 100%; the molar percentage of the compound represented by formula (ii) is 5% to 50%, and the molar percentage of the compound represented by formula (iii) is less than 5%.

2. A method for preparing the polyether ester polyol of claim 1, comprising the following steps: Step 1): Using a substance containing a double benzene ring structure as initiator 1 and epoxide alkane 1 as a polymerization monomer, a polymerization reaction is carried out under the action of a catalyst to obtain polyether polyol prepolymer A; Step 2): The polyether polyol prepolymer A from Step 1) is purified to obtain purified polyether polyol prepolymer B. Step 3): Using polyether polyol prepolymer B from step 2) as initiator 2 and epoxy alkane 2 as polymerization monomer, the polymerization reaction is carried out under the catalysis of bimetallic cyanide to obtain polyether polyol C. Step 4): Mix polyether polyol C with long-chain fatty acids evenly, and esterify them under the action of a catalyst to obtain the polyether ester polyol.

3. The method for preparing polyether ester polyols according to claim 2, wherein, Initiator 1 in step 1) is bisphenol A or bisphenol S; and / or When n is 0, alkylene oxide 1 is butane oxide and alkylene oxide 2 is butane oxide; when n is not 0, alkylene oxide 1 is propylene oxide or propylene oxide and butane oxide added sequentially, and alkylene oxide 2 is butane oxide, wherein the sequential addition of propylene oxide and butane oxide indicates that butane oxide is added after the propylene oxide reaction is complete; and / or The catalyst in step 1) is an alkali metal hydroxide or an alkaline earth metal hydroxide; and / or The reaction temperature in step 1) is 90–130°C; and / or The feeding time for alkyl epoxide 1 in step 1) is 1–10 h; and / or In step 1), the mass ratio of initiator 1 to epoxide 1 is 1:1 to 30; and / or In step 1), the weight percentage of the catalyst relative to the sum of the masses of the initiator 1 and the epoxide alkane 1 is 0.1% to 1%; and / or In step 1), when propylene oxide and butane oxide are added sequentially as alkylene oxide 1, the mass ratio of propylene oxide to butane oxide is 1:0.1 to 10; and / or The refining process in step 2) includes acid neutralization, adsorption with an adsorbent, vacuum dehydration, and filtration.

4. The method for preparing polyether ester polyols according to claim 3, wherein, The catalyst in step 1) is potassium hydroxide, sodium hydroxide, cesium hydroxide, magnesium hydroxide, or calcium hydride.

5. The method for preparing polyether ester polyols according to claim 3, wherein, The acid in step 2) is selected from phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, lactic acid, acetic acid, or oxalic acid; and / or In step 2), the system is neutralized with acid to a pH of 4–5; and / or The adsorbent in step 2) is selected from magnesium silicate, aluminum silicate, magnesium aluminum silicate, diatomaceous earth, or clay; and / or The amount of adsorbent used in step 2) is 0.1% to 5% of the mass of polyether polyol prepolymer A; and / or The acid neutralization temperature in step 2) is 20–100°C; and / or The adsorption temperature in step 2) is 80–120 °C; and / or The dehydration temperature in step 2) is 100–120°C; and / or The dehydration time in step 2) is 1–10 hours; and / or The dehydration pressure in step 2) is from -0.095 MPa to 0 MPa; and / or The filter used in step 2) is selected from candle filter, sintered cartridge filter and plate and frame filter.

6. The method for preparing polyether ester polyols according to any one of claims 3 to 5, wherein, The reaction temperature in step 3) is 120–160°C; and / or In step 3), the feeding time for epoxide 2 is 1–10 h; and / or In step 3), the mass ratio of polyether polyol prepolymer B to epoxy alkane 2 is 1:1 to 20; and / or The amount of bimetallic cyanide used in step 3) is 0.002% to 0.1% of the mass of polyether polyol prepolymer B.

7. The method for preparing polyether ester polyols according to any one of claims 3 to 5, wherein... The long-chain fatty acid in step 4) has the following structure: in, X1 is an alkylene group or an alkylene group containing an unsaturated double bond, X2 is a hydroxyl or methyl group, and the total number of carbon atoms in the long-chain fatty acid is 10 to 20; and / or The catalyst in step 4) is selected from isobutyl titanate, isopropyl titanate, n-butyl titanate, triethylamine, or trimethylamine; and / or The reaction temperature in step 4) is 180–260 °C; and / or In step 4), the molar ratio of polyether polyol C to long-chain fatty acid is 1:0.5–1; and / or In step 4), the mass ratio of long-chain fatty acids to catalyst is 1:0.001 to 0.

1.

8. The method for preparing polyether ester polyols according to claim 7, wherein... The long-chain fatty acids are selected from one or more of the following: ricinoleic acid, linolenic acid, linoleic acid, arachidic acid, tung oil acid, 12,13-epoxyoleic acid, and oleic acid.

9. A pore-opening agent comprising the polyether ester polyol according to claim 1.

10. Use of the polyether ester polyol according to claim 1 in the preparation of slow-rebound polyurethane foam.

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