Process for the preparation of a coarse-pored polyether for polyurethane rigid foam

Abstract

The application belongs to the technical field of organic synthesis and relates to a preparation method of coarse-pore polyether for polyurethane rigid foam. First, phenolic substances, glucose and an acidic catalyst are subjected to an acetalization reaction to obtain a phenyl glycoside, then the phenyl glycoside, diisopropanolamine and triisopropanolamine are used as a composite initiator, potassium hydroxide is used as a catalyst, and an alkylene oxide is grafted to form a polymer with a molecular weight of 500-800, and after neutralization, adsorption, dehydration and filtration, an intermediate is obtained, then the intermediate is put into a polymerization kettle, a double-metal cyanide complex catalyst is used as a reaction catalyst, and quantitative propylene oxide is continuously grafted, and after removal of low-boiling impurities, the coarse-pore polyether is obtained. The polyurethane rigid foam prepared from the coarse-pore polyether has uniform and relatively coarse pores, and the foam compression strength is obviously improved while maintaining good heat preservation performance.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic synthesis, and particularly relates to a preparation method of a coarse-pore polyether for polyurethane rigid foam. BACKGROUND

[0002] Polyurethane rigid foam is prepared by mixing hard foam polyether, silicone oil, catalyst, flame retardant, foaming agent and other additives to obtain white material, and then mixing the white material with isocyanate (commonly known as black material) to generate chemical reaction. The polyurethane rigid foam is mostly closed-cell structure, has good heat insulation effect, light weight, large specific strength, convenient construction and other excellent characteristics, and is widely used as an insulation material for the box body of a refrigerator, freezer, cold storage vehicle, building, storage tank and pipeline.

[0003] The polyurethane foam synthesized by conventional rigid foam polyether has good heat insulation performance due to the fine and dense closed-cell pores, but in the field of liquefied natural gas (LNG) cold preservation, the fine and dense pores will cause the insulation layer to be perforated or broken due to thermal expansion and cold contraction, thereby losing the insulation effect because the normal use temperature is about -161.5℃.

[0004] CN112341616A adopts a small molecule alcohol to react with an alkylene oxide under the action of a catalyst A to obtain a hydrophilic intermediate, then the alkyl glycoside and the hydrophilic intermediate are mixed uniformly with water, and the emulsion intermediate is prepared by dehydration under reduced pressure, and finally the emulsion intermediate reacts with an alkylene oxide under the action of a catalyst B to obtain an oil-modified alkyl glycoside polyether polyol. The invention combines the advantages of plant oil and alkyl glycoside, has good skin compatibility, is non-toxic, non-irritating, biocompatible, acid and alkali resistant, hard water resistant, green and environmentally friendly, and widens the application range of polyether polyol, and achieves good results in the fields of surfactants, sealants and lubricating oils. However, the product of the invention will cause the phenomenon of foam collapse when it is used to replace rigid foam polyether for polyurethane foam synthesis, which is very similar to the phenomenon of using lubricating oil to replace rigid foam polyether for polyurethane foam synthesis.

[0005] CN113308019A, CN112279991A, CN110628009A, CN106117538A and (Development of Hard Polyurethane Foam Open Cell Agent GK-501) in the Proceedings of the Eighth Polyether (Propylene Oxide) Scientific Research, Production and Technical Exchange Conference all adopt the method of providing an open cell agent or open cell polyether to make the polyurethane foam open, but the insulation performance of the foam will be greatly reduced after the foam is opened.

[0006] CN109503824A adopts C8~20 fatty alcohol, glucose and acid catalyst to mix and carry out acetalization reaction, obtains transparent reaction liquid, adjusts the pH value of the transparent reaction liquid to 6~7 with potassium hydroxide, then carries out secondary evaporation with a thin film evaporator in a distillation kettle to remove excess fatty alcohol, obtains alkyl glycoside crude product, then mixes the crude product and catalyst, dehydrates, and then passes into ethylene oxide to react to the end, after aging, cooling, and pH adjustment, obtains alkyl glycoside polyether. The invention has the advantages of good water solubility, good hard water resistance, low surface tension, and high foaming power in hard water, but the product of the above invention will cause the cells to be finer when used to replace part of the hard foam in the synthesis of polyurethane hard foam. SUMMARY

[0007] The present application aims to provide a preparation method of a coarse-cell polyether for polyurethane hard foam, which can make the prepared polyurethane foam have good thermal insulation performance, coarse and uniform cells, and high foam compression strength, so as to solve the problems in the above background art.

[0008] To achieve the above technical purposes, the technical scheme of the present application is as follows:

[0009] A preparation method of a coarse-cell polyether for polyurethane hard foam, comprising the following steps:

[0010] (1) mixing a phenolic substance, glucose and an acid catalyst, and carrying out acetalization reaction under the condition of 110~140℃ and -0.10MPa to obtain a transparent reaction liquid, adjusting the pH value of the transparent reaction liquid to 6~7 with potassium hydroxide, and distilling to remove residual phenolic substances to obtain a phenyl glycoside; the reaction equation is as follows:

[0011]

[0012] (2) putting the phenyl glycoside, diisopropanolamine and triisopropanolamine into a polymerization kettle, adding an alkali metal catalyst, starting stirring, replacing with nitrogen gas for 3 times, vacuumizing again to -0.10MPa, increasing the temperature to 100~115℃, maintaining the reaction pressure at 0.10~0.30MPa, and then putting in an alkylene oxide, after the putting-in is completed, aging at 120℃ for 2h, vacuumizing at -0.10MPa for 1h, and then cooling to 80℃ and conveying to a neutralization kettle;

[0013] (3) adding 85%wt phosphoric acid aqueous solution to the neutralization kettle while stirring to adjust the pH value to 5~6, then adding a magnesium silicate adsorbent, increasing the temperature to 120~125℃, maintaining the temperature, vacuumizing and dehydrating at -0.10MPa, after the water content is less than 0.05%, cooling to 80℃, and then filtering to obtain an intermediate polyether;

[0014] (4) adding the intermediate polyether into a polymerization kettle, putting in a bimetallic catalyst, starting stirring, replacing 3 times by nitrogen after vacuumizing, vacuumizing again to-0.10MPa, increasing temperature to 115~135℃, putting in propylene oxide, after putting in, controlling temperature 130℃ to age 2h, vacuumizing again for 1h under-0.10MPa, decreasing temperature to 60℃, obtaining the crude porous polyether, the structural general formula of the crude porous polyether is:

[0015] R[(CH3CHCH2O) m (CH2CH2O) n (CH3CHCH2O) x OH] y

[0016] wherein: R represents phenyl glycoside, diisopropanolamine and triisopropanolamine, m, n respectively represent the number of propylene oxide and ethylene oxide in the polyether molecule in random copolymerization, x represents the number of propylene oxide in the polyether molecule in the bimetallic catalysis stage, y represents the functionality of the phenyl glycoside, diisopropanolamine and triisopropanolamine complex initiator.

[0017] Preferably, m=1~10, n=1~13, x=55~198, y=3~10.

[0018] As an improvement, in step (1), the phenolic substance is one or more than two kinds of mixture of phenol, p-methyl phenol and 2,6-di-tert-butyl-p-methyl phenol; the acidic catalyst is one or mixture of p-methyl benzene sulfonic acid, benzene sulfonic acid and ethyl benzene sulfonic acid.

[0019] The final product prepared by using alkyl glycoside does not have the characteristic of coarse pores, while the final product prepared by using phenolic substance containing phenyl as raw material has the characteristic of coarse pores.

[0020] As an improvement, in step (1), the molar ratio of the phenolic substance to the glucose is 2~9:1; the mass ratio of the acidic catalyst to the total mass of the phenolic substance and the glucose is 1:50~300.

[0021] As an improvement, in step (2), the feeding mass ratio of the phenyl glycoside, diisopropanolamine and triisopropanolamine is 1~5:1~5:1~5.

[0022] Phenyl glycoside is solid at low temperature, and the addition of diisopropanolamine and triisopropanolamine can improve the compatibility of phenyl glycoside in oxyalkylene and polyether, making it more convenient to graft oxyalkylene later.

[0023] As an improvement, in step (2), the alkali metal catalyst is sodium hydroxide, potassium hydroxide, sodium methoxide or potassium methoxide, and the amount of the alkali metal catalyst is 0.2-0.5% of the mass of the intermediate polyether.

[0024] As an improvement, in step (2), the alkylene oxide is a mixture of one or both of ethylene oxide and propylene oxide.

[0025] Adding an appropriate amount of ethylene oxide or propylene oxide can improve the hydrophilicity of the coarse-pored polyether of the present application, and the coarse-pored polyether can be used in hydrophilic formulations, thereby expanding the application field of the present application.

[0026] As an improvement, in step (3), the molecular weight of the intermediate polyether is 500-800.

[0027] The bimetallic catalyst has very poor initiation effect on small molecule alcohols, and after the intermediate polyether with a molecular weight of 500-800 is synthesized, the bimetallic catalyst is used to initiate the ring-opening grafting of propylene oxide, and the effect is good.

[0028] As an improvement, in step (4), the bimetallic catalyst is a cyanide complex containing cobalt, iron, zinc or nickel elements, such as zinc hexacyanocobaltate, zinc hexacyanoferrate, nickel hexacyanocobaltate, nickel hexacyanoferrate, etc., and the amount of the bimetallic catalyst is 20-100 ppm of the mass of the intermediate polyether.

[0029] As an improvement, in step (4), the molecular weight of the coarse-pored polyether is 4000-12000.

[0030] When the molecular weight of the coarse-pored polyether of the present application is less than 4000, the foamed cells are uniform and fine or slightly coarse. When the molecular weight is greater than 12000, the coarse-pored polyether prepared is in a solid state and is inconvenient to use. Therefore, the molecular weight range of the present application is preferably 4000-12000.

[0031] Due to the use of the above technical solutions, the present application has the following advantages:

[0032] The present application is a kind of rough pore polyether polyol, which is prepared by using phenyl glycoside, diisopropanolamine and triisopropanolamine as composite initiator, potassium hydroxide as catalyst, grafting with alkylene oxide to form polymer with molecular weight of 500-800, and then neutralizing, adsorbing, dehydrating and filtering to obtain intermediate, and then grafting with a certain amount of propylene oxide in a polymerization kettle using double metal cyanide complex catalyst as reaction catalyst, and removing low boiling point impurities to obtain the rough pore polyether polyol. The rough pore polyether polyol of the present application is a kind of polyether polyol with phenyl glycoside structure. When the molecular weight of the intermediate grafted with a certain amount of propylene oxide is greater than 4000, it will interfere with the silicone foam stabilizer in the foam, making the foam become rough, but the pore wall will not be broken. The polyurethane rigid foam prepared by the rough pore polyether polyol of the present application has uniform and relatively rough cell, and the foam compression strength is significantly improved while maintaining good thermal insulation performance. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 is a cross-sectional view of polyurethane foam prepared by using the rough pore polyether polyol of Example 1 of the present application;

[0034] Figure 2 is a cross-sectional view of polyurethane foam prepared by using comparative polyether 4110. DETAILED DESCRIPTION

[0035] The present application will be further described below in conjunction with specific embodiments and drawings.

[0036] Example 1

[0037] 9 mol of p-methylphenol and 1 mol of glucose were mixed, 0.4% of benzene sulfonic acid by mass was added, stirring was performed, and the temperature was raised to 140 DEG C. Vacuum was applied until the pressure in the kettle was -0.10 MPa, and acetalization reaction was started. After a transparent reaction liquid was obtained, the pH of the reaction liquid was adjusted to 6.0 using potassium hydroxide, and then residual phenols were removed by distillation to obtain phenyl glycoside.

[0038] Phenyl glycoside, diisopropanolamine and triisopropanolamine were mixed according to a mass ratio of 2:2:2, 0.2% of sodium hydroxide catalyst by mass of the intermediate polyether was added, stirring was started, and vacuum nitrogen replacement was performed three times. Vacuum was applied again until the pressure was -0.10 MPa, the temperature was raised to 100 DEG C, the reaction pressure was maintained at 0.10 MPa, and ethylene oxide was added. The molecular weight of the intermediate polyether was controlled to be 500, and after the addition was completed, aging was performed at 120 DEG C for 2 hours, vacuum was applied at -0.10 MPa for 1 hour, the temperature was lowered to 80 DEG C, and then the intermediate polyether was transferred to a neutralization kettle. Stirring was started in the neutralization kettle, a certain amount of 85% wt phosphoric acid aqueous solution was added to the neutralization kettle to adjust the pH of the product to 5.5, and then magnesium silicate adsorbent was added. The temperature was raised to 120 DEG C, vacuum was applied at -0.10 MPa to remove water, and after the water content of the product was less than 0.05%, the temperature was lowered to 80 DEG C, and then the intermediate polyether was filtered to obtain the product.

[0039] The intermediate polyether is added to the polymerization kettle, 20 ppm of the bimetallic catalyst zinc hexacyanocobaltate is added to the coarse hole polyether, the stirring is started, the nitrogen is replaced for 3 times under vacuum, the vacuum is extracted again to -0.10 MPa, the temperature is raised to 115 ℃, the propylene oxide is added, the molecular weight of the coarse hole polyether is controlled to be 4000, after the addition is completed, the temperature is controlled to be 130 ℃ for aging for 2 h, the vacuum is extracted for 1 h under the condition of -0.10 MPa, the temperature is lowered to 60 ℃, the discharge is packaged, and the target product is obtained.

[0040] Example 2

[0041] 2 mol of phenol and 1 mol of glucose are mixed, 2% of p-toluenesulfonic acid by mass is added, the stirring is started, the temperature is raised to 110 ℃, the pressure in the kettle is extracted to -0.10 MPa under vacuum, the acetalization reaction is started, after the transparent reaction liquid is obtained, the pH of the reaction liquid is adjusted to 6.5 by using potassium hydroxide, and after the residual phenol is removed by distillation, the phenyl glycoside is obtained.

[0042] The phenyl glycoside, diisopropanolamine and triisopropanolamine are added according to the mass ratio of 5:2:2, the catalyst potassium hydroxide is added to the intermediate polyether at 0.2% by mass, the stirring is started, the nitrogen is replaced for 3 times under vacuum, the vacuum is extracted again to -0.10 MPa, the temperature is raised to 110 ℃, the reaction pressure is maintained at 0.20 MPa, the propylene oxide is added, the molecular weight of the intermediate polyether is controlled to be 800, after the addition is completed, the temperature is controlled to be 120 ℃ for aging for 2 h, the vacuum is extracted for 1 h under the condition of -0.10 MPa, the temperature is lowered to 80 ℃, and the delivery is sent to the neutralization kettle. The stirring of the neutralization kettle is started, the 85% wt phosphoric acid aqueous solution is added to the neutralization kettle in a certain amount, the pH of the product is adjusted to 6.0, the magnesium silicate adsorbent is added, the temperature is raised to 125 ℃, the temperature is maintained, the vacuum is extracted under the condition of -0.10 MPa, the water content of the product is less than 0.05%, the temperature is lowered to 80 ℃, and the filtration is started, and the intermediate polyether is obtained.

[0043] The intermediate polyether is added to the polymerization kettle, 100 ppm of the bimetallic catalyst zinc hexacyanocobaltate is added to the coarse hole polyether, the stirring is started, the nitrogen is replaced for 3 times under vacuum, the vacuum is extracted again to -0.10 MPa, the temperature is raised to 135 ℃, the propylene oxide is added, the molecular weight of the coarse hole polyether is controlled to be 12000, after the addition is completed, the temperature is controlled to be 130 ℃ for aging for 2 h, the vacuum is extracted for 1 h under the condition of -0.10 MPa, the temperature is lowered to 60 ℃, the discharge is packaged, and the target product is obtained.

[0044] Example 3

[0045] Mix 4 moles of 2,6-di-tert-butyl-p-cresol and 1 mole of glucose, add mixed mass 1% of ethylbenzenesulfonic acid, stir to warm to 125°C, vacuum to a pressure of -0.10 MPa in the kettle, start the acetalization reaction, after a transparent reaction liquid is obtained, adjust the pH of the reaction liquid to 7.0 with potassium hydroxide, after removing the residual phenols by distillation, obtain the phenyl glycoside.

[0046] Mix the phenyl glycoside, diisopropanolamine and triisopropanolamine according to a mass ratio of 1:5:2, add 0.5% of the intermediate polyether mass of catalyst potassium methoxide, start stirring, vacuum nitrogen replacement 3 times, vacuum to -0.10 MPa again, warm to 115°C, maintain the reaction pressure at 0.30 MPa, add propylene oxide, control the intermediate polyether molecular weight to be 700, after the addition is complete, age at 120°C for 2 h, vacuum at -0.10 MPa for 1 h, cool to 80°C, and transfer to the neutralization kettle. Start stirring in the neutralization kettle, add 85% wt aqueous phosphoric acid to the neutralization kettle, adjust the pH of the product to 5.0, add a fixed amount of magnesium silicate adsorbent, warm to 125°C, maintain the temperature, vacuum dehydrate at -0.10 MPa, after the product moisture is <0.05%, cool to 80°C and filter to obtain the intermediate polyether.

[0047] Add the intermediate polyether to the polymerization kettle, add 60 ppm of the bimetallic catalyst nickel hexacyanocobaltate of the coarse-pored polyether mass, start stirring, vacuum nitrogen replacement 3 times, vacuum to -0.10 MPa again, warm to 130°C, add propylene oxide, control the coarse-pored polyether molecular weight to be 9000, after the addition is complete, control the temperature to 130°C and age for 2 h, vacuum at -0.10 MPa for 1 h, cool to 60°C, discharge and package to obtain the target product.

[0048] Example 4

[0049] Mix 5 moles of phenol and 1 mole of glucose, add 1.5% of p-toluenesulfonic acid of the mixed mass, stir to warm to 120°C, vacuum to a pressure of -0.10 MPa in the kettle, start the acetalization reaction, after a transparent reaction liquid is obtained, adjust the pH of the reaction liquid to 6.5 with potassium hydroxide, after removing the residual phenols by distillation, obtain the phenyl glycoside.

[0050] The phenyl glycoside, diisopropanolamine and triisopropanolamine are added according to the mass ratio of 1:5:5, the catalyst sodium methoxide of 0.2% of the mass of the intermediate polyether is added, stirring is started, vacuum nitrogen replacement is performed for 3 times, vacuum is again drawn to -0.10 MPa, the temperature is raised to 110°C, the reaction pressure is maintained at 0.20 MPa, the mixture of the mass ratio of 1:1 of ethylene oxide and propylene oxide is added, the molecular weight of the intermediate polyether is controlled to be 600, after the addition is completed, aging is performed at 120°C for 2 h, vacuum is drawn at -0.10 MPa for 1 h, the temperature is lowered to 80°C, and the product is transported to the neutralization kettle. The neutralization kettle is started to stir, 85%wt phosphoric acid aqueous solution is added to the neutralization kettle, the pH of the product is adjusted to be 5.5, after the magnesium silicate adsorbent is added, the temperature is raised to 125°C, the temperature is maintained, vacuum dehydration is performed under the condition of -0.10 MPa, after the water content of the product is less than 0.05%, the temperature is lowered to 80°C for filtration, and the intermediate polyether is obtained.

[0051] The intermediate polyether is added to the polymerization kettle, the bimetallic catalyst nickel hexacyanoferrate of 50 ppm of the mass of the coarse-pored polyether is added, stirring is started, vacuum nitrogen replacement is performed for 3 times, vacuum is again drawn to -0.10 MPa, the temperature is raised to 125°C, propylene oxide is added, the molecular weight of the coarse-pored polyether is controlled to be 11000, after the addition is completed, the temperature is controlled to be 130°C for aging for 2 h, vacuum is again drawn at -0.10 MPa for 1 h, the temperature is lowered to 60°C, the product is discharged and packaged, and the target product is obtained.

[0052] Example 5

[0053] 4 moles of p-methyl phenol and 1 mole of glucose are mixed, 1.0% of p-toluene sulfonic acid by mass is added, stirring is started, the temperature is raised to 130°C, vacuum is drawn to the pressure in the kettle to be -0.10 MPa, acetalization reaction is started, after the transparent reaction liquid is obtained, the pH of the reaction liquid is adjusted to be 6.0 by using potassium hydroxide, and after the residual phenol is removed by distillation, the phenyl glycoside is obtained.

[0054] The phenyl glycoside, diisopropanolamine and triisopropanolamine are added according to the mass ratio of 5:2:1, the catalyst potassium hydroxide of 0.25% of the mass of the intermediate polyether is added, stirring is started, vacuum nitrogen replacement is performed for 3 times, vacuum is again drawn to -0.10 MPa, the temperature is raised to 115°C, the reaction pressure is maintained at 0.25 MPa, the mixture of the mass ratio of 2:1 of ethylene oxide and propylene oxide is added, the molecular weight of the intermediate polyether is controlled to be 700, after the addition is completed, aging is performed at 120°C for 2 h, vacuum is drawn at -0.10 MPa for 1 h, the temperature is lowered to 80°C, and the product is transported to the neutralization kettle. The neutralization kettle is started to stir, 85%wt phosphoric acid aqueous solution is added to the neutralization kettle, the pH of the product is adjusted to be 5.5, after the magnesium silicate adsorbent is added, the temperature is raised to 125°C, the temperature is maintained, vacuum dehydration is performed under the condition of -0.10 MPa, after the water content of the product is less than 0.05%, the temperature is lowered to 80°C for filtration, and the intermediate polyether is obtained.

[0055] The intermediate polyether is added to the polymerization kettle, 40 ppm of double metal catalyst zinc hexacyanocobalt is added to the coarse hole polyether, the stirring is started, the nitrogen is replaced for 3 times under vacuum, the vacuum is extracted again to-0.10 MPa, the temperature is raised to 120℃, the propylene oxide is added, the molecular weight of the coarse hole polyether is controlled to be 8000, after the addition is completed, the temperature is controlled to be 130℃ for aging for 2 h, the vacuum is extracted for 1 h under the condition of-0.10 MPa, the temperature is lowered to 60℃, the discharge is packaged, and the target product is obtained.

[0056] Example 6

[0057] 3 mol of phenol and 1 mol of glucose are mixed, 1.3% of p-toluenesulfonic acid is added, the stirring is started, the temperature is raised to 120℃, the pressure in the kettle is extracted to-0.10 MPa, the acetalization reaction is started, after the transparent reaction liquid is obtained, the pH of the reaction liquid is adjusted to 6.0 by using potassium hydroxide, and after the residual phenol is removed by distillation, the phenyl glycoside is obtained.

[0058] The phenyl glycoside, diisopropanolamine and triisopropanolamine are added according to the mass ratio of 5:5:5, the catalyst potassium hydroxide is added to the intermediate polyether with the mass of 0.25%, the stirring is started, the nitrogen is replaced for 3 times under vacuum, the vacuum is extracted again to-0.10 MPa, the temperature is raised to 100℃, the reaction pressure is maintained at 0.20 MPa, the propylene oxide is added, the molecular weight of the intermediate polyether is controlled to be 800, after the addition is completed, the temperature is controlled to be 120℃ for aging for 2 h, the vacuum is extracted for 1 h under the condition of-0.10 MPa, the temperature is lowered to 80℃ and is transported to the neutralization kettle. The stirring of the neutralization kettle is started, the 85% wt phosphoric acid aqueous solution is added to the neutralization kettle, the pH of the product is adjusted to 6.0, the magnesium silicate adsorbent is added, the temperature is raised to 125℃, the temperature is maintained, the vacuum is extracted under the condition of-0.10 MPa for dehydration, after the water content of the product is less than 0.05%, the temperature is lowered to 80℃ for filtration, and the intermediate polyether is obtained.

[0059] The intermediate polyether is added to the polymerization kettle, 60 ppm of double metal catalyst nickel hexacyanocobalt is added to the coarse hole polyether, the stirring is started, the nitrogen is replaced for 3 times under vacuum, the vacuum is extracted again to-0.10 MPa, the temperature is raised to 130℃, the propylene oxide is added, the molecular weight of the coarse hole polyether is controlled to be 12000, after the addition is completed, the temperature is controlled to be 130℃ for aging for 2 h, the vacuum is extracted for 1 h under the condition of-0.10 MPa, the temperature is lowered to 60℃, the discharge is packaged, and the target product is obtained.

[0060] The coarse hole polyether sample of the above example is prepared into polyurethane white material according to the formula of Table 1, the polynuclear polymeric methyl polyisocyanate PM200 of Wanhua Chemical is used as black material, the coarse hole polyurethane foam is prepared by reacting the white material and the black material according to the mass ratio of 1:1 under the condition of 20℃, the performance is tested after the curing for 48 h, and the performance is shown in Table 2.

[0061] Table 1 White material formula for coarse hole foam evaluation

[0062] Trade name Parts by mass Polyether 635 30 Polyether 450 40 Example polyether / Comparative polyether 4110 30 Foam stabilizer CGY-6885 2.0 Complex amine catalyst 3.5 141b foaming agent 16.5 Water 1.2 Flame retardant TCPP 25

[0063] Table 2 Test results of coarse cell polyurethane foam

[0064]

[0065] From the results of Table 2, it can be seen that the polyurethane foam made with the coarse cell polyether of the present application has much higher foam density and compressive strength than the polyurethane foam made with the comparative polyether, the polyurethane foam made with the coarse cell polyether of the present application has coarse appearance, and the foam has no abnormality after being placed at -160°C for 48 hours, while the polyurethane foam made with the comparative polyether has fine and uniform appearance, and the foam shrinks after being placed at -160°C for 48 hours.

[0066] From Figure 1 and Figure 2 it can be seen that the polyurethane foam made with the coarse cell polyether of Example 1 of the present application is coarse cell foam, while the polyurethane foam made with the comparative polyether is fine and uniform foam.

[0067] The above described specific embodiments of the present application do not constitute a limitation on the scope of protection of the present application. Any various other corresponding changes and modifications made according to the technical concept of the present application shall be included in the scope of protection of the claims of the present application.

Claims

1. A process for the preparation of a coarse-pored polyether for polyurethane rigid foam, characterized in that, The method comprises the following steps: (1) mixing phenolic substance, glucose and acidic catalyst, acetalization reaction under the condition of 110-140℃ and -0.10MPa, obtaining transparent reaction liquid, adjusting the pH value of the transparent reaction liquid to 6-7 by potassium hydroxide, and distilling the residual phenolic substance to obtain phenyl glycoside; (2) putting phenyl glycoside, diisopropanolamine and triisopropanolamine into a polymerization kettle, the mass ratio of the phenyl glycoside, diisopropanolamine and triisopropanolamine being 1-5:1-5:1-5, adding alkali metal catalyst, starting stirring, vacuum nitrogen replacement for 3 times, vacuumizing again to -0.10MPa, heating to 100-115℃, maintaining the reaction pressure of 0.10-0.30MPa, putting in alkylene oxide which is a mixture of one or two of ethylene oxide and propylene oxide, aging for 2h at 120℃ after the completion of putting in, vacuumizing for 1h under the condition of -0.10MPa, cooling to 80℃, and conveying to a neutralization kettle; (3) adding 85wt% phosphoric acid aqueous solution to the neutralization kettle while stirring, adjusting the pH value to 5-6, adding magnesium silicate adsorbent, heating to 120-125℃, maintaining the temperature, vacuumizing and dehydrating under the condition of -0.10MPa, cooling to 80℃ after the water content is less than 0.05%, and filtering to obtain intermediate polyether; (4) adding the intermediate polyether into the polymerization kettle, putting in bimetallic catalyst, starting stirring, vacuum nitrogen replacement for 3 times, vacuumizing again to -0.10MPa, heating to 115-135℃, putting in propylene oxide, controlling the temperature to 130℃ for aging for 2h after the completion of putting in, vacuumizing for 1h under the condition of -0.10MPa, cooling to 60℃, and obtaining crude-pore polyether, the molecular weight of the crude-pore polyether being 4000-12000, and the structural general formula of the crude-pore polyether being: R[(CH3CHCH2O) m (CH2CH2O) n (CH3CHCH2O) X OH] y wherein R represents phenyl glycoside, diisopropanolamine or triisopropanolamine, m and n respectively represent the number of propylene oxide and ethylene oxide in the polyether molecule in random copolymerization, x represents the number of propylene oxide in the polyether molecule in the bimetallic catalysis stage, and y represents the functionality of the phenyl glycoside, diisopropanolamine and triisopropanolamine complex initiator.

2. The method for preparing a coarse-cell polyether for polyurethane rigid foam according to claim 1, characterized by, In step (1), the phenolic substance is one or a mixture of two or more of phenol, p-methyl phenol and 2,6-di-tert-butyl-p-methyl phenol; and the acidic catalyst is one or a mixture of p-methyl benzenesulfonic acid, benzene sulfonic acid and ethyl benzene sulfonic acid.

3. The method for preparing a coarse-cell polyether for polyurethane rigid foam according to claim 1, characterized by, In step (1), the molar ratio of the phenolic substance to the glucose is 2-9:1; and the total mass ratio of the acidic catalyst to the phenolic substance and the glucose is 1:50-300.

4. The method for preparing a coarse-cell polyether for polyurethane rigid foam according to claim 1, characterized by, The alkali metal catalyst is sodium hydroxide, potassium hydroxide, sodium methoxide or potassium methoxide, and the amount of the alkali metal catalyst is 0.2-0.5% of the mass of the intermediate polyether.

5. The method of preparing a coarse-cell polyether for polyurethane rigid foam according to claim 1, characterized by, In step (3), the molecular weight of the intermediate polyether is 500-800.

6. The method of claim 1, wherein the polyurethane rigid foam coarse-cell polyether is prepared by the steps of: In step (4), the bimetallic catalyst is a cyanide complex containing cobalt, iron, zinc or nickel element, and the amount of the bimetallic catalyst is 20-100ppm of the mass of the intermediate polyether.

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