Phenolic ketone resin based polyether polyol mixture as well as preparation method and application thereof

Abstract

The invention relates to a phenolic ketone resin-based polyether polyol mixture as well as a preparation method and application thereof, and mainly solves the problem of environmental pollution caused by post-treatment of a byproduct phenolic ketone resin generated in a bisphenol A production process in the prior art. The preparation method comprises the following steps: preheating a reaction kettle, adding the phenolic ketone resin and a catalyst, adding alkylene oxide for reaction, controlling the temperature in the kettle to be 110-130 DEG C and the reaction pressure to be less than or equal to 0.45 Mpa, controlling the internal pressure to be 2-4 hours after the reaction is finished, and cooling to room temperature to obtain the mixture of the polyether polyol prepared from the phenolic ketone resin. After the pressure in the reaction kettle is reduced and stabilized, obtaining crude ether of polyether polyol; the method comprises the following steps: adding 5-10% by mass of water and 0.5-1.5% by mass of acid into crude ether of polyether polyol, stirring, adding 0.2-1% by mass of an adsorbent, stirring, carrying out vacuum-pumping negative pressure dehydration, and filtering to obtain a phenolic ketone resin-based polyether polyol mixture, so that the problem is well solved, and the method can be applied to the industrial application of rigid polyurethane foam. Such as large bubbles, electric water heaters, refrigerators and spraying.

Description

Technical Field

[0001] The invention relates to a mixture of phenol-ketone resin-based polyether polyols, and a preparation method and application thereof. Background Art

[0002] Bisphenol A, also known as BPA, is an organic compound with a molecular formula of C 15 H 16 O2, in industry, bisphenol A is used to synthesize materials such as polycarbonate (PC) and epoxy resin. Bisphenol A is one of the most widely used industrial compounds in the world, mainly used to produce polycarbonate, epoxy resin, polysulfone resin, polyphenylene ether resin, unsaturated polyester resin and other polymer materials. It can also be used to produce fine chemical products such as plasticizers, flame retardants, antioxidants, heat stabilizers, rubber antioxidants, pesticides, coatings, etc. In the manufacturing process of plastic products, adding bisphenol A can make it colorless, transparent, durable, lightweight and outstanding impact resistance, especially to prevent acidic vegetables and fruits from corroding metal containers from the inside. Therefore, it is widely used in the packaging of canned foods and beverages, milk bottles, water bottles, sealants used for dental fillings, eyeglasses and hundreds of other daily necessities.

[0003] Phenolic resin is commonly known as bisphenol A residue, which is the bisphenol A residue product after catalytic cracking of bisphenol A mother liquor and recovery of phenol and isopropenylphenol during industrial production of bisphenol A. Currently, almost all bisphenol A manufacturers incinerate it as solid waste, which not only wastes energy but also creates environmental problems such as dioxins. Comprehensive utilization of bisphenol A residue not only solves environmental problems but also generates economic benefits. Summary of the invention

[0004] One of the technical problems to be solved by the present invention is the problem of environmental pollution caused by the post-processing of the by-product phenolic ketone resin produced in the bisphenol A polycarbonate industry in the prior art. A mixture of phenolic ketone resin-based polyether polyols is provided, which not only solves the problem of environmental pollution but also maximizes the utilization of waste.

[0005] The second technical problem to be solved by the present invention is to provide a method for preparing a mixture of phenolic ketone resin-based polyether polyols corresponding to the first technical problem to be solved.

[0006] The third technical problem to be solved by the present invention is to provide an application of a mixture of phenolic ketone resin-based polyether polyols corresponding to the first technical problem to be solved.

[0007] To solve one of the above technical problems, the technical solution adopted by the present invention is as follows: a mixture of phenolic resin-based polyether polyols, including compounds of the following five general structural formulas, calculated in mass percentage: 70 to 95 parts of general structural formula I, 2 to 10 parts of general structural formula II, 5 to 9 parts of general structural formula III, 5 to 9 parts of general structural formula IV, and 5 to 9 parts of general structural formula V.

[0008]

[0009] Among them, n1, n2, m1, m2, e, and f are integers.

[0010] To solve the second technical problem, the technical solution adopted by the present invention is as follows: a method for preparing a mixture of phenolic ketone resin-based polyether polyols, comprising the following steps in sequence:

[0011] (1) After preheating the reactor, add phenolic ketone resin and catalyst, add alkylene oxide to react, control the temperature in the reactor to 110-130° C., the reaction pressure ≤ 0.45 MPa, and maintain the internal pressure for 2-4 hours after the reaction is completed. After the pressure in the reactor drops and stabilizes, the crude ether of polyether polyol is obtained;

[0012] (2) In the crude ether of polyether polyol, 5-10% of water and 0.5-1.5% of acid are added, based on the mass percentage of the crude ether of polyether polyol, and after stirring for 1-2 hours, 0.2-1% of adsorbent is added, and after stirring for 1-2 hours, vacuum negative pressure dehydration is performed for 3-4 hours, and filtration is performed to obtain a mixture of phenolic resin-based polyether polyols including structural formula I and structural formula II.

[0013] In the above technical scheme, the bisphenol A content of the phenolic ketone resin in step (1) is 80% to 90%, the hydroxyl value is 380 to 420 mgKOH / g, the melting point is 80 to 100°C, and the functionality is 1 to 3;

[0014] In the above technical solution, the catalyst in step (1) is an alkali metal catalyst selected from one or two of potassium hydroxide, sodium hydroxide, cesium hydroxide and potassium methoxide;

[0015] In the above technical scheme, the phenolic resin, catalyst and alkylene oxide in step (1) are respectively, by mass percentage, phenolic resin: 45% to 50%, catalyst: 0.15% to 0.35%, and alkylene oxide: 50% to 55%.

[0016] In the above technical solution, the preheating temperature of the reactor in step (1) is 100-120° C.; the reaction pressure in step (1) is 0.01-0.30 MPa.

[0017] In the above technical solution, the acid in step (2) is selected from one or two of phosphoric acid, acetic acid, lactic acid, and sulfuric acid; the adsorbent in step (2) is selected from one or a combination of magnesium silicate, aluminum silicate, or magnesium aluminum silicate.

[0018] In the above technical solution, the dehydration temperature in step (2) is 110-130°C.

[0019] In the above technical solution, the hydroxyl value of the mixture of phenolic ketone resin-based polyether polyols is 100 to 300 mgKOH / g.

[0020] To solve the third of the above technical problems, the technical solution adopted by the present invention is as follows: application of a mixture of phenolic ketone resin-based polyether polyols in polyurethane rigid foam.

[0021] The present invention provides a mixture of phenolic ketone resin-based polyether polyols, a preparation method and application thereof. The phenolic ketone resin, which is a byproduct in the bisphenol A polycarbonate industry, is recovered and reacted with alkylene oxide under the action of a catalyst to prepare a phenolic ketone resin-based polyether polyol, which is then applied to a polyurethane rigid foam formulation. The inventor surprisingly found that the performance data of the prepared polyurethane rigid foam not only did not deteriorate, but improved in terms of thermal conductivity, dimensional stability and the like, thereby achieving good technical results. DETAILED DESCRIPTION

[0022] The following are only preferred implementations of the present invention, and are not intended to limit the scope of protection of the present invention. All technical solutions within the scope of the present invention should fall within the scope of protection of the present invention. For professional and technical personnel in this technical field, minor improvements and modifications to the present invention without departing from the principles of the present invention should also fall within the scope of protection of the present invention.

[0023] Table 1 List of raw materials

[0024] Raw material name Brand and manufacturer Polyester polyols SKR-240B, Shandong Linyi Skorui Polyurethane Materials Co., Ltd. Polyether polyol A 6305C, 310, Jurong Ningwu New Materials Co., Ltd. Polyether polyol B TD405, Guodu Chemical (Kunshan) Co., Ltd. Silicone oil AK8805, Nanjing Meside New Materials Co., Ltd. Foaming agent CP, Wanhua Chemical catalyst PC5, PC8, PC41, Evonik Specialty Chemicals GmbH Flame retardants TCPP, Shandong Ruixing Flame Retardant Technology Co., Ltd. Isocyanate M20S, BASF Shanghai New Materials Co., Ltd.

[0025] Example 1

[0026] (1) preheating a reactor to 100° C., adding 450 g of phenolic resin and 3.5 g of potassium hydroxide, adding 333 g of ethylene oxide and 166 g of propylene oxide for polymerization reaction, controlling the temperature in the reactor to be 110° C., the reaction pressure to be 0.01 MPa, and the internal pressure to be 2 h after the reaction is completed, and obtaining the crude ether of polyether polyol after the pressure in the reactor drops and stabilizes;

[0027] (2) The crude ether of the polyether polyol was transferred to a glass reactor, 101 g of water and 4 g of phosphoric acid were added, and the mixture was stirred for 2 h. Then, 10 g of magnesium aluminum silicate was added and stirred for 2 h. The mixture was vacuum dehydrated at a temperature of 120° C. for 3 h, and a mixture of phenolic resin-based polyether polyols having a hydroxyl value of 105.6 mg KOH / g was obtained by filtration.

[0028] Example 2

[0029] (1) preheating the reactor to 105° C., adding 990 g of phenolic resin and 7.72 g of sodium hydroxide, adding 733 g of ethylene oxide and 365 g of propylene oxide to carry out polymerization reaction, controlling the temperature in the reactor to be 115° C., the reaction pressure to be 0.05 MPa, and the internal pressure to be maintained for 2 hours after the reaction is completed, and obtaining the crude ether of polyether polyol after the pressure in the reactor drops and stabilizes;

[0030] (2) The crude ether of the polyether polyol was transferred to a glass reactor, 212 g of water and 8.3 g of lactic acid were added, and the mixture was stirred for 2 h. Then, 21 g of magnesium aluminum silicate was added and stirred for 2 h. The mixture was vacuum dehydrated at a temperature of 115° C. for 3 h, and the mixture was filtered to obtain a mixture of phenolic resin-based polyether polyols having a hydroxyl value of 203 mg KOH / g.

[0031] Example 3

[0032] (1) preheating the reactor to 105° C., adding 1000 g of phenolic resin and 7.77 g of cesium hydroxide, adding 554 g of ethylene oxide and 554 g of propylene oxide for polymerization reaction, controlling the temperature in the reactor to be 120° C., the reaction pressure to be 0.01 MPa, and the internal pressure to be 2 h after the reaction is completed, and obtaining the crude ether of polyether polyol after the pressure in the reactor drops and stabilizes;

[0033] (2) The crude ether of the polyether polyol was transferred to a glass reactor, 238 g of water and 9.3 g of acetic acid were added, and the mixture was stirred for 2 h. Then, 22 g of magnesium silicate was added and stirred for 2 h. The mixture was vacuum dehydrated at a negative pressure of 110° C. for more than 3 h, and the mixture was filtered to obtain a mixture of phenolic resin-based polyether polyols having a hydroxyl value of 240.1 mgKOH / g.

[0034] Example 4

[0035] (1) preheating the reactor to 110° C., adding 1000 g of phenolic resin and 5.27 g of potassium methoxide, adding 369 g of ethylene oxide and 738 g of propylene oxide for polymerization reaction, controlling the temperature in the reactor to be 114° C., the reaction pressure to be 0.03 MPa, and the internal pressure to be 3 h after the reaction is completed, and obtaining the crude ether of polyether polyol after the pressure in the reactor drops and stabilizes;

[0036] (2) The crude ether of the polyether polyol was transferred to a glass reactor, 105 g of water and 9.25 g of sulfuric acid were added, and the mixture was stirred for 2 h. Then, 20 g of aluminum silicate was added and stirred for 2 h. The mixture was vacuum dehydrated at a negative pressure of 120° C. for more than 3 h to obtain a mixture of phenolic resin-based polyether polyols having a hydroxyl value of 199.1 mg KOH / g.

[0037] Example 5

[0038] (1) Preheat the reactor to 105° C., add 6040 g of phenolic resin and 24.3 g of sodium hydroxide, add 3617 g of ethylene oxide and 3617 g of propylene oxide to carry out polymerization reaction, control the temperature in the reactor to 112° C., the reaction pressure to 0.02 MPa, and after the reaction is completed, the internal pressure is maintained for 3 hours, and the crude ether of polyether polyol is obtained after the pressure in the reactor decreases and stabilizes;

[0039] (2) The crude ether of the polyether polyol was transferred to a glass reactor, 665 g of water and 42.5 g of phosphoric acid were added, and the mixture was stirred for 2 h. Then, 134 g of magnesium silicate was added and stirred for 2 h. The mixture was vacuum dehydrated at a negative pressure of 115° C. for more than 3 h, and the mixture was filtered to obtain a mixture of phenolic resin-based polyether polyols having a hydroxyl value of 198 mg KOH / g.

[0040] Example 6

[0041] (1) Prepare the components according to Table 2 (phenolic ketone resin-based polyether polyol is prepared in Example 1);

[0042] (2) Stir the components in a mixer at a rotation speed of 3500 rpm for 5 to 10 seconds, quickly pour them into a mold, and then mature them for 12 hours to obtain a polyurethane foam.

[0043] Embodiments 7 to 10

[0044] Examples 7 to 10 are carried out according to the steps in Example 6, except that the phenolic resin-based polyether polyol in the formula is prepared by Examples 2 to 5, and the mass fractions of each component are specifically shown in Table 2; the performance index data of the obtained polyurethane foam used in polyurethane electric water heaters are shown in Table 4.

[0045] Embodiment 11

[0046] (1) Prepare the components according to Table 3 (phenolic ketone resin-based polyether polyol is prepared in Example 1);

[0047] (2) Stir the components in a mixer at a rotation speed of 3500 rpm for 5 to 10 seconds, quickly pour them into a mold, and then mature them for 12 hours to obtain a polyurethane foam.

[0048] Embodiments 12 to 15

[0049] Examples 12 to 15 are carried out according to the steps in Example 11, except that the phenolic resin-based polyether polyol in the formula is prepared by Examples 2 to 5, and the mass fraction of each component is specifically shown in Table 3; the performance index data of the obtained polyurethane foam used in polyurethane refrigerators are shown in Table 5.

[0050] Comparative Example 1

[0051] (1) Prepare the components according to Table 2;

[0052] (2) Stir the components in a mixer at a rotation speed of 3500 rpm for 5 to 10 seconds, quickly pour them into a mold, and then mature them for 12 hours to obtain a polyurethane foam.

[0053] Comparative Example 2

[0054] (1) Prepare the components according to Table 3;

[0055] (2) Stir the components in a mixer at a rotation speed of 3500 rpm for 5 to 10 seconds, quickly pour them into a mold, and then mature them for 12 hours to obtain a polyurethane foam.

[0056] Table 2 Mass fractions of each component in the polyurethane electric water heater formulations of Examples 7 to 10 and Comparative Example 1

[0057]

[0058] Note: PC8 is used to adjust the reaction activity so that the examples and comparative examples can be compared under the same conditions.

[0059] Table 3 Weight parts of each component applied to the polyurethane refrigerator formula of Examples 11 to 15 and Comparative Example 2

[0060]

[0061] Note: PC8 is used to adjust the reaction activity, and CP is used to adjust the density, so that the examples and comparative examples can be compared under the same conditions.

[0062] Table 4 Test data of polyether polyols prepared in Examples 6 to 10 and Comparative Example 2 applied to polyurethane electric water heater formulations

[0063]

[0064] Table 5 Test data of polyether polyols prepared in Examples 11 to 15 and Comparative Example 2 applied to polyurethane refrigerator formulations

[0065]

[0066] It can be seen from Tables 4 and 5 that when the mixture of phenolic resin-based polyether polyols is applied to the polyurethane electric water heater formulation, under the condition that other properties remain unchanged, the thermal conductivity, demoulding properties and dimensional stability of Examples 1 to 5 are better than those of the comparative example; the smaller the thermal conductivity, the better the thermal insulation performance and the smaller the heat loss; the demoulding property is good, which improves the production efficiency and increases the production capacity; when the mixture of phenolic resin-based polyether polyols is applied to the polyurethane refrigerator formulation, under the condition that other properties remain unchanged, the thermal conductivity, the compressive strength parallel to the rising direction of the foam and the dimensional stability of Examples 1 to 5 are better than those of the comparative example; the greater the compressive strength, the greater the pressure that can be withstood.

[0067] In summary, the present invention prepares a mixture of phenolic resin-based polyether polyols from a by-product produced in the bisphenol A polycarbonate industry, namely, phenolic resin, and applies the mixture to a polyurethane rigid foam formula. The prepared polyurethane rigid foam has improved thermal conductivity, dimensional stability, and other aspects while other properties remain unchanged. The mixture of phenolic resin-based polyether polyols provided by the present invention can not only replace the polyester component in the polyurethane rigid foam formula, thereby reducing the cost, but also improve the performance of the polyurethane rigid foam, while also solving the environmental problems caused by the by-product phenolic resin, and has the advantages of protecting the environment and maximizing waste utilization.

Claims

1. A mixture of phenolic resin-based polyether polyols, comprising compounds of the following five general structural formulas, in mass percentage: 70 to 95 parts of general structural formula I, 2 to 10 parts of general structural formula II, 5 to 9 parts of general structural formula III, 5 to 9 parts of general structural formula IV, and 5 to 9 parts of general structural formula V. in, n1, n2, m1, m2, e, f are integers.

2. The method for preparing a mixture of phenolic ketone resin-based polyether polyols according to claim 1, comprising the following steps: (1) After preheating the reactor, add phenolic ketone resin and catalyst, add alkylene oxide to react, control the temperature in the reactor to 110-130° C., the reaction pressure ≤ 0.45 MPa, and maintain the internal pressure for 2-4 hours after the reaction is completed. After the pressure in the reactor drops and stabilizes, the crude ether of polyether polyol is obtained; (2) Add 5-10% of water and 0.5-1.5% of acid to the crude ether of polyether polyol, based on the mass percentage of the crude ether of polyether polyol, stir for 1-2 hours, then add 0.2-1% of adsorbent, stir for 1-2 hours, perform vacuum dehydration for 3-4 hours, and filter to obtain a mixture of phenolic resin-based polyether polyols.

3. The method for preparing a mixture of phenolic ketone resin-based polyether polyols according to claim 2, characterized in that: The bisphenol A content of the phenolic ketone resin in the step (1) is 80% to 90%, the hydroxyl value is 380 to 420 mgKOH / g, the melting point is 80 to 100° C., and the functionality is 1 to 3.

4. The method for preparing a mixture of phenolic ketone resin-based polyether polyols according to claim 2, characterized in that: The catalyst in step (1) is an alkali metal catalyst, selected from one or two of potassium hydroxide, sodium hydroxide, cesium hydroxide and potassium methoxide.

5. The method for preparing a mixture of phenolic ketone resin-based polyether polyols according to claim 2, characterized in that: The phenolic resin, catalyst and alkylene oxide in the step (1) are respectively in the following mass percentages: phenolic resin: 45% to 50%, catalyst: 0.15% to 0.35%, and alkylene oxide: 50% to 55%.

6. The method for preparing a mixture of phenolic ketone resin-based polyether polyols according to claim 2, characterized in that: The preheating temperature of the reactor in the step (1) is 90-120° C.; the reaction pressure in the step (1) is 0.01-0.30 MPa.

7. The method for preparing a mixture of phenolic ketone resin-based polyether polyols according to claim 2, characterized in that: The acid in step (2) is selected from one or two of phosphoric acid, acetic acid, lactic acid and sulfuric acid; the adsorbent in step (2) is selected from one or a combination of magnesium silicate, aluminum silicate or magnesium aluminum silicate.

8. The method for preparing a mixture of phenolic ketone resin-based polyether polyols according to claim 2, characterized in that: The dehydration temperature in step (2) is 100-130°C.

9. A mixture of phenolic ketone resin-based polyether polyols according to claim 1, characterized in that: The hydroxyl value of the mixture of phenolic ketone resin-based polyether polyols is 100-300 mgKOH / g.

10. Use of the mixture of phenolic ketone resin-based polyether polyols according to claim 1 in polyurethane rigid foam.

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