4-isopropyl benzyl alcohol polyether polyol as well as preparation method and application thereof
By using 4-isopropylbenzyl alcohol polyether polyol and optimized monomer combination and catalytic system, a polyurethane hard foam with low thermal conductivity and high flow performance was prepared, which solved the problem that polyurethane foam in the prior art was difficult to take into account both thermal conductivity, fluidity and strength, and achieved a high-performance foam material suitable for different models of boxes.
Patent Information
- Application Number
- CN202510000263.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-02
- Publication Date
- 2025-04-15
AI Technical Summary
When existing polyurethane foams meet the needs of low thermal conductivity and high fluidity, they are difficult to take into account both strength and performance, and cannot meet the filling needs of different models of boxes.
Using 4-isopropylbenzyl alcohol polyether polyol as the key monomer, polyurethane hard bubbles with low thermal conductivity and high flow performance were prepared by optimizing the monomer combination and catalytic system. The bisbenzene ring structure of the polyether polyol is not easy to rotate during thermal conduction, reducing thermal conductivity, and at the same time, the low functionality avoids the formation of crosslinked structures and improves fluidity and strength.
It achieves the balance of low thermal conductivity, high fluidity and strength performance of polyurethane foam, which can meet the filling needs of different models of boxes, reduces energy consumption and saves costs.
Smart Images
Figure CN119823366A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of new materials and relates to a polyether polyol and a polyurethane rigid foam, and specifically relates to a 4-isopropylbenzyl alcohol polyether polyol, a polyurethane rigid foam and a preparation method thereof. Background Art
[0002] As a polymer thermal insulation material, rigid polyurethane foam has a high closed-cell rate, low density, and thermal conductivity, and is widely used in the field of thermal insulation.
[0003] For a long time, with the continuous development of the home appliance (refrigerator and freezer) industry, product requirements have been continuously improved, and low-cost, high-performance products have become the driving force for enterprises to compete for development. The quality of polyether polyol combination materials (white materials) directly affects the performance of polyurethane foam. With the continuous improvement of people's awareness of environmental protection and the continuous improvement of energy consumption requirements for refrigerators, the home appliance (refrigerator and freezer) industry is also constantly developing to meet the higher needs of customers. The types and models of refrigerators are also constantly increasing. Many large models such as double-door refrigerators and air-cooled refrigerators are gradually being launched on the market. At the same time, it also puts forward requirements for lower thermal conductivity and higher fluidity for foaming material manufacturers to meet the filling problems of different models of boxes. Generally speaking, low-functionality monomers can improve fluidity, but will lose strength properties. Summary of the invention
[0004] In view of the above-mentioned deficiencies in the prior art, the present invention provides a 4-isopropylbenzyl alcohol polyether polyol and a CP system polyurethane foam with low thermal conductivity and high fluidity.
[0005] The first aspect of the present invention provides a 4-isopropylbenzyl alcohol polyether polyol, the structural formula of which is as follows:
[0006]
[0007] Wherein, X is 2 to 12, and R is H or CH3.
[0008] Furthermore, the 4-isopropylbenzyl alcohol polyether polyol has a hydroxyl value of 80 to 240 mgKOH / g and a functionality of 1.0 to 1.4.
[0009] On the other hand, the present invention provides a method for preparing 4-isopropylbenzyl alcohol polyether polyol, comprising the following steps: using 4-isopropylbenzyl alcohol as a starting material and subjecting it to an addition reaction with an olefin oxide to prepare the 4-isopropylbenzyl alcohol polyether polyol.
[0010] The reaction formula is:
[0011]
[0012] Preferably, the olefin oxide is selected from one or both of propylene oxide and ethylene oxide; the molar ratio of the 4-isopropylbenzyl alcohol to the olefin oxide is 1:2-12, preferably 1:4-8.
[0013] In a specific embodiment, the preparation method of the 4-isopropylbenzyl alcohol polyether polyol comprises the following steps:
[0014] 1) Mixing 4-isopropylbenzyl alcohol solution with part of oxidized olefins, autocatalytically reacting at 70-90° C. for 1-6 hours, and then heating to 80-120° C. for aging reaction for 1-4 hours;
[0015] 2) adding potassium hydroxide aqueous solution to the system in step 1), then vacuum dehydrating for 2 to 6 hours, then adding the remaining olefin oxide, continuing the reaction for 1 to 6 hours, and then heating to 120 to 160° C. and reacting for 1 to 4 hours;
[0016] 3) adding phosphoric acid aqueous solution to the system in step 2) to obtain 4-isopropylbenzyl alcohol polyether polyol.
[0017] Furthermore, in the above preparation method, the oxidized olefin is added to the reaction system twice in step 1) and step 2), and the mass ratio of the oxidized olefin in step 1) to the oxidized olefin in step 2) is 1:1-1.4, preferably 1:1.1-1.3.
[0018] Furthermore, in the above preparation method, the concentration of the potassium hydroxide aqueous solution in step 2) is 30 to 70 wt%.
[0019] Furthermore, in the above preparation method, the concentration of the phosphoric acid aqueous solution in step 3) is 20 to 70 wt%.
[0020] Furthermore, in the above preparation method, the molar ratio of 4-isopropylbenzyl alcohol to potassium hydroxide and phosphoric acid is 20-50:(0.8-1.2):1.
[0021] Finally, the present invention provides a polyurethane rigid foam with low thermal conductivity and high fluidity. The raw materials for preparing the polyurethane rigid foam include combined polyether, cyclopentane and polyisocyanate, and the mass ratio of the combined polyether to CP and polyisocyanate is 100:12-25:130-160.
[0022] The combined polyether comprises 100 parts of a polyether composition, 1.0-5.0 parts of a surfactant, 2.0-5.0 parts of a composite catalyst and 1-3 parts of water; the polyether composition comprises 4-isopropylbenzyl alcohol polyether polyol.
[0023] The polyether composition comprises 5 to 30 parts by weight of 4-isopropylbenzyl alcohol polyether polyol, 15 to 50 parts by weight of sucrose and glycerol polyether polyol, 5 to 45 parts by weight of sorbitol polyether polyol and 10 to 45 parts by weight of o-toluenediamine polyether polyol; preferably, the composition comprises 10 to 25 parts by weight of 4-isopropylbenzyl alcohol polyether polyol, 20 to 40 parts by weight of sucrose and glycerol polyether polyol, 10 to 35 parts by weight of sorbitol polyether polyol and 10 to 40 parts by weight of o-toluenediamine polyether polyol.
[0024] Preferably, the sucrose and glycerol polyether polyol is prepared by using sucrose and glycerol as starting materials and reacting with propylene oxide via an addition reaction, and has a hydroxyl value of 380-440 mgKOH / g and a functionality of 5.0-6.0.
[0025] Preferably, the sorbitol polyether polyol is prepared by taking sorbitol as a starting material and reacting it with propylene oxide via an addition reaction, and has a hydroxyl value of 400 to 460 mgKOH / g and a functionality of 5.0 to 6.4.
[0026] Preferably, the o-toluenediamine polyether polyol is prepared by taking o-toluenediamine as a starting material and reacting it with propylene oxide via an addition reaction, and has a hydroxyl value of 380 to 460 mgKOH / g and a functionality of 3.6 to 4.4.
[0027] Preferably, the surfactant is a silicon surfactant, more preferably an organosilicon surfactant, most preferably at least one of silicone oil B8525, silicone oil B8545, and silicone oil L6863;
[0028] Preferably, the composite catalyst comprises 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 preferably 1:4-10:1-5;
[0029] Preferably, the foaming catalyst is a mixture of one or more of tetramethylhexanediamine, pentamethyldiethylenetriamine and bis-dimethylaminoethyl ether in any proportion;
[0030] Preferably, the gel catalyst is a mixture of one or more of dimethylbenzylamine, pentamethyldiethylenetriamine and triethylenediamine in any proportion;
[0031] Preferably, the trimerization catalyst is one or both of hexahydrotriazine and potassium acetate.
[0032] Furthermore, the polyisocyanate is polymeric MDI (polymethylene polyphenyl polyisocyanate), preferably polymeric MDI with an NCO content of 30 to 32%; most preferably, it is one or more of polymeric MDI Wanhua PM-200, polymeric MDI Wanhua PM-400 and polymeric MDI Wanhua PM-700.
[0033] The method for preparing the low-conductivity and high-flowability polyurethane rigid foam of the present invention comprises the following steps:
[0034] 1) Weighing various raw materials according to the proportion, mixing the polyether composition, surfactant, composite catalyst and water evenly, and cooling to below 25° C. to obtain a composite polyether;
[0035] 2) Control the foaming agent at below 25° C., add it to the combined polyether in step 1), stir for 0.5-3 hours, and mix well;
[0036] 3) mixing the mixture in step 2) with polyisocyanate, and performing high-pressure foaming using a high-pressure foaming machine to obtain the polyurethane rigid foam.
[0037] Furthermore, the high pressure foaming process in step 3) is carried out under the following conditions: material temperature 17-21° C., pressure 100-150 bar (gauge pressure).
[0038] Furthermore, in the foaming process, the filling coefficient of the polyurethane rigid foam in the mold is 1.1-1.4, and the demoulding time is ≤240s.
[0039] The low thermal conductivity and high fluidity polyurethane rigid foam of the present invention is used in thermal insulation materials, preferably in the thermal insulation layer of a refrigerator or freezer.
[0040] The beneficial effects of the technical solution of the present invention are:
[0041] 1) The present invention uses 4-isopropylbenzyl alcohol polyether polyol, which has only one functionality, so it is not easy to form a grid-like cross-linked structure during the reaction process, so that the viscosity of the polyurethane reaction process increases slowly, which is conducive to the flow of foam, and combined with the optimization of monomer combination and catalytic system, the fluidity of the polyurethane foam is improved. The product can meet the filling requirements of boxes of different volumes and sizes, greatly improving the applicability of polyurethane products.
[0042] 2) The double benzene ring structure in the 4-isopropylbenzyl alcohol polyether polyol molecule is not easy to rotate during heat conduction, so it can effectively slow down heat transfer and achieve the effect of reducing heat conduction. Using it in the refrigerator foaming system can reduce energy consumption and effectively achieve the purpose of energy saving.
[0043] 3) The double benzene ring structure of 4-isopropylbenzyl alcohol polyether polyol is a good rigid structure. Compared with conventional low-functionality monomers, it has good strength performance and can reduce the amount of polyurethane foam used to achieve the purpose of cost saving. DETAILED DESCRIPTION
[0044] The technical solution of the present invention is further illustrated by specific embodiments below, but the protection scope of the present invention is not limited thereto. Within the technical scope disclosed in the present invention, changes or replacements of the same or similar technical features should be covered within the protection scope of the present invention.
[0045] The sources of the main materials and reagents of the embodiments of the present invention are shown in Table 1:
[0046]
[0047] Polyether polyol A: 4-isopropylbenzyl alcohol polyether polyol is prepared by addition reaction of 4-isopropylbenzyl alcohol as an initiator with propylene oxide, with a hydroxyl value of 138 mgKOH / g, a functionality of 1.2, and a molecular weight of 488.
[0048] Polyether polyol B: Sucrose and glycerol polyether polyol is prepared by addition reaction of propylene oxide with sucrose and glycerol as initiators. It has a hydroxyl value of 420 mgKOH / g, a functionality of 5.8, and a molecular weight of 775.
[0049] Polyether polyol C: Sorbitol polyether polyol is prepared by addition reaction of sorbitol as an initiator with propylene oxide, with a hydroxyl value of 438 mgKOH / g, a functionality of 5.2 and a molecular weight of 666.
[0050] Polyether polyol D: o-toluenediamine polyether polyol is prepared by addition reaction of o-toluenediamine as an initiator with propylene oxide. It has a hydroxyl value of 425 mgKOH / g, a functionality of 3.9, and a molecular weight of 514.
[0051] Polyether polyol A1: Glycerol polyether polyol, prepared by addition reaction of propylene oxide with glycerol as initiator, with hydroxyl value of 223 mgKOH / g, functionality of 2.4 and molecular weight of 603.
[0052] Composite catalyst 1: bis-dimethylaminoethyl ether, dimethylcyclohexylamine, and potassium acetate are arranged in an array in a weight ratio of 1:4:1.5.
[0053] Composite catalyst 2: bis-dimethylaminoethyl ether, dimethylcyclohexylamine, and potassium acetate are arranged in a weight ratio of 1:5:1.
[0054] Example 1
[0055] Preparation of 4-isopropylbenzyl alcohol polyether polyol
[0056] 1) Add water (130 g) and 4-isopropylbenzyl alcohol (600 g) into a reactor, replace with nitrogen, maintain pressure, start stirring, add 645 g of propylene oxide, autocatalytic reaction for 1 h, heat to 100 ° C and age for 2 h;
[0057] 2) Add 15 g of potassium hydroxide aqueous solution (50 wt%) to the system in step 1), vacuum dehydrate for 3 h, then add 775 g of propylene oxide, react for 1 h, then heat to 125° C., and react for 2 h;
[0058] 3) Adding 26 g of phosphoric acid aqueous solution (50 wt%) to the system in step 2) to remove K ions, 4-isopropylbenzyl alcohol polyether polyol was obtained, the hydroxyl value was 138 mgKOH / g, the functionality was 1.2, and x in the structural formula of the corresponding 4-isopropylbenzyl alcohol polyether polyol was 7.
[0059] The NMR characterization is as follows:
[0060] 1H NMR (400MHz, CDCl3) δ=7.40-7.32(m,8H),7.12-7.04(m,2H),5.37(s,1H),3.94-3.88(m,1H),3.64-3.60(m,9H),3.40 -3.30(m,8H),3.10-3.04(m,2H),1.54-1.48(m,2H),1.38-1.32(m,12H),1.24(d,J=6.8Hz,3H),1.11(d,J=6.8Hz,3H).
[0061] Example 2
[0062] 1) Add water (175 g) and cumene alcohol (600 g) into a reactor, replace with nitrogen, maintain pressure, start stirring, add 480 g of propylene oxide, autocatalytically react for 4 h, heat to 80 ° C, and age for 2 h;
[0063] 2) Add 15 g of potassium hydroxide aqueous solution (50 wt%) to the system in step 1), vacuum dehydrate for 3 h, then add 528 g of propylene oxide, react for 3 h, then heat to 120° C., and react for 2 h;
[0064] 3) Add 26 g of phosphoric acid aqueous solution to the system in step 2) to remove K ions (50 wt%) to obtain 4-isopropylbenzyl alcohol polyether polyol with a hydroxyl value of 210 mgKOH / g and a functionality of 1.3.
[0065] Examples 3-7, Comparative Examples 1-2
[0066] The preparation process of polyurethane rigid foam is as follows:
[0067] 1) Weighing various raw materials according to the proportion, mixing the polyether composition, surfactant, composite catalyst and water evenly, and cooling to below 25° C. to obtain a composite polyether;
[0068] 2) Control the blowing agent at below 25° C., add it to the combined polyether in step 1), stir for 1 hour, and mix well;
[0069] 3) mixing the mixture in step 2) with polyisocyanate, and foaming the mixture using a high-pressure foaming machine to obtain the polyurethane rigid foam.
[0070] The conditions of the high pressure foaming process are: material temperature 20°C, pressure 135 bar (gauge pressure). In the foaming process, the filling factor of the polyurethane rigid foam in the mold is 1.20, and the demoulding time is 210s.
[0071] The specific raw materials and proportions (parts by weight) of the embodiments and comparative examples are shown in Table 2.
[0072] Table 2: Polyurethane rigid foam raw material composition (weight parts) and performance parameters
[0073]
[0074]
[0075] It can be seen from the data in the above table that the rigid polyurethane foam prepared by the present invention has the characteristics of fluidity and low thermal conductivity.
[0076] Comparison between Comparative Example 2 and Comparative Example 3 shows that although the fluidity is improved, the intensity gradually decreases with the use of conventional low-functionality monomers.
[0077] By comparing Example 6 with Comparative Example 2, it can be seen that compared with the traditional low-functionality monomers, after using the monomers of the present invention, the strength and thermal conductivity of the system are improved.
Claims
1. A 4-isopropylbenzyl alcohol polyether polyol, the structural formula of which is as follows; in, X is 2-12, and R is H or CH3.
2. The method for preparing 4-isopropylbenzyl alcohol polyether polyol according to claim 1, comprising the following steps: using 4-isopropylbenzyl alcohol as a starting material, and preparing the 4-isopropylbenzyl alcohol polyether polyol by addition reaction with an olefin oxide; preferably, the olefin oxide is selected from one or both of propylene oxide and ethylene oxide; the molar ratio of the 4-isopropylbenzyl alcohol to the olefin oxide is 1:2 to 12, preferably the molar ratio is 1:4 to 8.
3. The preparation method according to claim 2, characterized in that: The preparation method of the 4-isopropylbenzyl alcohol polyether polyol comprises the following steps: 1) Mixing 4-isopropylbenzyl alcohol solution with part of oxidized olefins, autocatalytically reacting at 70-90° C. for 1-6 hours, and then heating to 80-120° C. for aging reaction for 1-4 hours; 2) adding potassium hydroxide aqueous solution to the system in step 1), then vacuum dehydrating for 2 to 6 hours, then adding the remaining olefin oxide, continuing the reaction for 1 to 6 hours, and then heating to 120 to 160° C. and reacting for 1 to 4 hours; 3) adding phosphoric acid aqueous solution to the system in step 2) to obtain 4-isopropylbenzyl alcohol polyether polyol.
4. The preparation method according to claim 3, characterized in that: The mass ratio of the oxidized olefin in step 1) to the oxidized olefin in step 2) is 1:1-1.4, preferably 1:1.1-1.3; and / or, the concentration of the potassium hydroxide aqueous solution in step 2) is 30-70wt%; and / or, the concentration of the phosphoric acid aqueous solution in step 3) is 20-70wt%; and / or, the molar ratio of 4-isopropylbenzyl alcohol to potassium hydroxide and phosphoric acid is 20-50:(0.8-1.2):
1.
5. A polyurethane rigid foam with low thermal conductivity and high fluidity, wherein the raw materials for preparing the polyurethane rigid foam include a combined polyether, cyclopentane and polyisocyanate, wherein the mass ratio of the combined polyether to CP and polyisocyanate is 100:12-25:130-160; the combined polyether comprises 100 parts of a polyether composition, 1.0-5.0 parts of a surfactant, 2.0-5.0 parts of a composite catalyst and 1-3 parts of water; and the polyether composition comprises 4-isopropylbenzyl alcohol polyether polyol.
6. The low thermal conductivity, high fluidity polyurethane rigid foam according to claim 5, characterized in that: The polyether composition comprises 5 to 30 parts by weight of 4-isopropylbenzyl alcohol polyether polyol, 15 to 50 parts by weight of sucrose and glycerol polyether polyol, 5 to 45 parts by weight of sorbitol polyether polyol and 10 to 45 parts by weight of o-toluenediamine polyether polyol; preferably, the composition comprises 10 to 25 parts by weight of 4-isopropylbenzyl alcohol polyether polyol, 20 to 40 parts by weight of sucrose and glycerol polyether polyol, 10 to 35 parts by weight of sorbitol polyether polyol and 10 to 40 parts by weight of o-toluenediamine polyether polyol.
7. The polyurethane rigid foam with low thermal conductivity and high fluidity as claimed in claim 5 or 6, characterized in that: The surfactant is a silicon surfactant, more preferably an organosilicon surfactant, most preferably at least one of silicone oil B8525, silicone oil B8545, and silicone oil L6863; and / or, 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 preferably 1:4-10:1-5.
8. The polyurethane rigid foam with low thermal conductivity and high fluidity according to any one of claims 5 to 7, characterized in that: The foaming catalyst is a mixture of one or more of tetramethylhexanediamine, pentamethyldiethylenetriamine and bis-dimethylaminoethyl ether in any proportion; and / or, the gel catalyst is a mixture of one or more of dimethylbenzylamine, pentamethyldiethylenetriamine and triethylenediamine in any proportion; and / or, the trimerization catalyst is one or two of hexahydrotriazine and potassium acetate; and / or, the polyisocyanate is polymeric MDI (polymethylene polyphenyl polyisocyanate), preferably polymeric MDI with an NCO content of 30 to 32%; most preferably, it is one or more of polymeric MDI Wanhua PM-200, polymeric MDI Wanhua PM-400 and polymeric MDI Wanhua PM-700.
9. The method for preparing a polyurethane rigid foam with low thermal conductivity and high fluidity according to any one of claims 5 to 8, comprising: 1) Weighing various raw materials according to the proportion, mixing the polyether composition, surfactant, composite catalyst and water evenly, and cooling to below 25° C. to obtain a composite polyether; 2) Control the foaming agent at below 25° C., add it to the combined polyether in step 1), stir for 0.5-3 hours, and mix well; 3) mixing the mixture in step 2) with polyisocyanate, and performing high-pressure foaming using a high-pressure foaming machine to obtain the polyurethane rigid foam.
10. Use of the low thermal conductivity, high fluidity polyurethane rigid foam according to any one of claims 5 to 8 or the low thermal conductivity, high fluidity polyurethane rigid foam prepared by the preparation method according to claim 9 in thermal insulation materials, preferably in the thermal insulation layer of a refrigerator or freezer.