CN112538150A - High-resilience polyurethane foam and preparation method thereof - Google Patents
High-resilience polyurethane foam and preparation method thereof Download PDFInfo
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- CN112538150A CN112538150A CN202011328441.6A CN202011328441A CN112538150A CN 112538150 A CN112538150 A CN 112538150A CN 202011328441 A CN202011328441 A CN 202011328441A CN 112538150 A CN112538150 A CN 112538150A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/18—Block or graft polymers
- C08G64/183—Block or graft polymers containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a preparation method of high-resilience polyurethane foam, which is prepared from materials comprising a polymer component and isocyanate; the polymer component includes: 5 to 100 wt% of a block poly (ether-carbonate) polyol; 95-0 wt% of polyether polyol. The invention provides a preparation method of high-resilience polyurethane foam, which is obtained by reacting block poly (ether-carbonate) polyalcohol component polymer with isocyanate, and because the block poly (ether-carbonate) polyalcohol is easier to be mixed with polyether polyalcohol to form a stable mixed system, the block poly (ether-carbonate) polyalcohol is more convenient for industrial transportation and storage, and simultaneously the components are more uniform, the prepared polyurethane foam has excellent mechanical property and low hysteresis rate property, can meet the national requirements on seats such as automobiles, airplanes and high-speed rails, and simultaneously utilizes carbon dioxide, reduces the cost and has wide application market. The invention also provides high-resilience polyurethane foam.
Description
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to high-resilience polyurethane foam and a preparation method thereof.
Background
Polyurethane (PU) soft foam has the characteristics of light weight, high resilience, good comfort, durability, high sound insulation and shock absorption and the like, and is widely applied to seats, backrests, headrests, handrails, sound insulation and vibration isolation systems, furniture sofas and mattresses of automobiles. High resilience polyurethane foam, as one of polyurethane soft foam, gets into people's field of vision more and more, its seat that mainly is applied to the transportation field is as car, aircraft, high-speed railway etc. steeps cotton. With the rapid development of economy and the gradual improvement of the living standard of people, the requirement of people on the comfort of vehicles such as automobiles is higher and higher, the comfort of seats of vehicles such as automobiles is concerned more and more, and the foam serving as an important component of the seats of automobiles undoubtedly bears important responsibility. Generally, polyurethane foams are made by polymerizing a polyol, an isocyanate, in the presence of a catalyst, a blowing agent, a crosslinking agent, a surfactant (e.g., silicone oil), and other auxiliaries. The mechanical properties, especially the low hysteresis rate, of the polyurethane foam prepared by the prior art are still to be further improved.
Disclosure of Invention
In view of the above, the present invention provides a high resilience polyurethane foam and a preparation method thereof, and the method provided by the present invention uses block poly (ether-carbonate) polyol to prepare polyurethane foam, and the obtained polyurethane foam has good performance.
The invention provides a preparation method of high-resilience polyurethane foam, which is prepared from materials comprising a polymer component and isocyanate;
the polymer component includes:
5 to 100 wt% of a block poly (ether-carbonate) polyol;
95-0 wt% of polyether polyol.
Preferably, the method of preparing the block poly (ether-carbonate) polyol comprises:
under the action of a catalyst and a chain transfer agent, carrying out polymerization reaction on an epoxy compound to obtain a polymerization product;
and (c) continuing to copolymerize the polymerization product with carbon dioxide and an epoxy compound to obtain the block poly (ether-carbonate) polyol.
Preferably, the epoxy compound is selected from one or more of ethylene oxide, propylene oxide, epichlorohydrin, butylene oxide, styrene oxide and cyclohexene oxide.
Preferably, the number average molecular weight of the block poly (ether-carbonate) polyol is 600 to 10000 g/mol; the carbonate content in the block poly (ether-carbonate) polyol is 0-99 wt%; the functionality of the block poly (ether-carbonate) polyol is 2-8.
Preferably, the chain transfer agent is selected from one or more of C1-C10 alcohol compounds, hydroxyl-containing polymers with the molecular weight of less than 2000g/mol and carboxylic acid compounds.
Preferably, the mass ratio of the total epoxy compounds to the chain transfer agent in the polymerization reaction process is (2-50): 1;
the mass ratio of the catalyst to the total epoxy compound in the polymerization reaction process is 1 (300-200000).
Preferably, the temperature of the copolymerization reaction is 10-130 ℃; the time of the copolymerization reaction is 1-48 hours; the pressure of the copolymerization reaction is 0-15 MPa.
Preferably, the number average molecular weight of the polyether polyol is 600-10000 g/mol; the functionality of the polyether polyol is 2-8.
Preferably, the isocyanate is selected from one or more of hexamethylene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, 4-diphenyl diisocyanate, p-phenylene diisocyanate, polymethylene polyphenyl polyisocyanate, 3, 5-dimethyl 4, 4-diphenyl diisocyanate, 2, 4-ethylbenzene diisocyanate, 3-dimethoxy 4, 4-diphenyl diisocyanate, toluene diisocyanate dimer, isophorone diisocyanate, xylylene diisocyanate, 1, 5-naphthalene diisocyanate and tetramethylxylylene diisocyanate.
The invention provides high-resilience polyurethane foam prepared by the method in the technical scheme.
The invention provides a preparation method of high-resilience polyurethane foam, which is obtained by reacting block poly (ether-carbonate) polyalcohol component polymer with isocyanate, and because the block poly (ether-carbonate) polyalcohol is easier to be mixed with polyether polyalcohol to form a stable mixed system, the block poly (ether-carbonate) polyalcohol is more convenient for industrial transportation and storage, and simultaneously the components are more uniform, the prepared polyurethane foam has excellent mechanical property and low hysteresis rate performance, can meet the national requirements of the current countries on seats such as automobiles, airplanes and high-speed rails, and simultaneously utilizes carbon dioxide, reduces the cost and has wide application market.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other examples, which may be modified or appreciated by those of ordinary skill in the art based on the examples given herein, are intended to be within the scope of the present invention. It should be understood that the embodiments of the present invention are only for illustrating the technical effects of the present invention, and are not intended to limit the scope of the present invention. In the examples, the methods used were all conventional methods unless otherwise specified.
The invention provides a preparation method of high-resilience polyurethane foam, which is prepared from materials comprising a polymer component and isocyanate;
the polymer component includes:
5 to 100 wt% of a block poly (ether-carbonate) polyol;
95-0 wt% of polyether polyol.
In the present invention, the mass content of the block poly (ether-carbonate) polyol in the polymer component is preferably 10 to 90%, more preferably 20 to 80%, more preferably 30 to 60%, and most preferably 40 to 50%. In the invention, the number average molecular weight of the block poly (ether-carbonate) polyol is preferably 600-10000 g/mol, more preferably 800-10000 g/mol, more preferably 1500-8000 g/mol, and most preferably 3000-6000 g/mol; the mass content of the carbonate in the block poly (ether-carbonate) polyol is preferably 0-99 wt%, more preferably 10-99 wt%, more preferably 20-80 wt%, and most preferably 30-50 wt%; the functionality of the block poly (ether-carbonate) polyol is preferably 2-8, and more preferably 3-6; the hydroxyl value of the block poly (ether-carbonate) polyol is preferably 10-100 mg KOH/g, more preferably 20-80 mg KOH/g, and most preferably 25-60 mg KOH/g; the molar ratio of carbonate chain segments to ether chain segments in the block poly (ether-carbonate) polyol is preferably (1-9): 9-1, more preferably (3-7): 7-3, and most preferably (4-6): 6-4.
In the present invention, the method for preparing the block poly (ether-carbonate) polyol preferably comprises:
under the action of a catalyst and a chain transfer agent, carrying out polymerization reaction on an epoxy compound to obtain a polymerization product;
and (c) continuing to copolymerize the polymerization product with carbon dioxide and an epoxy compound to obtain the block poly (ether-carbonate) polyol.
In the present invention, the catalyst for the preparation of the block poly (ether-carbonate) polyol is preferably a rare earth doped Zn-based3〔Co(CN)6〕2The multi-metal catalyst of (1). The rare earth is doped based on Zn3〔Co(CN)6〕2The source of the multi-metal catalyst is not particularly limited, such as can be prepared according to the method disclosed in CN102617844 Chinese patent, the rare earth doped Zn-based3〔Co(CN)6〕2The preparation method of the multi-metal catalyst preferably comprises:
mixing tert-butyl alcohol, water, a zinc salt compound and a rare earth salt compound to obtain a mixed salt solution;
adding K to the mixed salt solution3〔Co(CN)6Solution, separation after stirring, washing and drying to obtain the rare earth doped Zn-based alloy3〔Co(CN)6〕2The multi-metal catalyst of (1).
In the present invention, the chain transfer agent is preferably one or more selected from the group consisting of C1-C10 alcohol compounds, hydroxyl group-containing polymers having a number average molecular weight of less than 2000g/mol, and carboxylic acid compounds.
In the present invention, the polyol compound having 1 to 10 is preferably one or more selected from the group consisting of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, decanediol, 1, 3-cyclopentanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, sucrose, starch and cellulose.
In the present invention, the hydroxyl group-containing polymer having a number average molecular weight of less than 2000g/mol preferably has a functionality of 2 to 8, more preferably 3 to 6.
In the present invention, the carboxylic acid-based compound is preferably one or more selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1, 3-acetonic acid, malic acid, citric acid, maleic acid, fumaric acid, itaconic acid, aconitic acid, trans-aconitic acid, 1, 2-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic diacetic acid, terephthalic acid, trimesic acid and pyromellitic acid.
In the present invention, the epoxy compound is preferably one or more selected from the group consisting of ethylene oxide, propylene oxide, epichlorohydrin, butylene oxide, styrene oxide and cyclohexene oxide.
In the invention, the mass ratio of the total epoxy compounds to the chain transfer agent in the polymerization reaction process is preferably (2-50): 1, more preferably (20-40): 1, most preferably (25-35): 1; the molar ratio of the catalyst to the total epoxy compounds in the polymerization reaction process is preferably 1 (300-200000), more preferably 1 (1000-150000), and most preferably 1 (10000-100000).
In the invention, the polymerization reaction temperature is preferably 60-90 ℃, more preferably 70-85 ℃, and most preferably 75 ℃; the time of the polymerization reaction is preferably 3 to 12 hours, and more preferably 8 hours.
The amount of the carbon dioxide used in the present invention is not particularly limited, and the carbon dioxide is preferably reacted in an excess amount.
In the present invention, the molar ratio of the epoxy compound used for the total reaction to the epoxy compound used for the block preparation reaction (i.e., the epoxy compound subjected to copolymerization with carbon dioxide) is preferably 1: (0.1 to 0.8), more preferably 1: (0.2 to 0.9), most preferably 1: (0.3-0.7).
In the invention, the temperature of the copolymerization reaction is preferably 10-130 ℃, more preferably 50-90 ℃, and most preferably 60-80 ℃; the time of the copolymerization reaction is preferably 1-48 hours, more preferably 4-40 hours, and most preferably 4-16 hours; the pressure of the copolymerization reaction is preferably 0 to 15MPa, more preferably 1 to 15MPa, and most preferably 3 to 7 MPa.
In the invention, the mass content of the polyether polyol in the polymer component is preferably 5-90%, more preferably 10-80%, more preferably 20-70%, more preferably 30-60%, and most preferably 40-50%. In the invention, the number average molecular weight of the polyether polyol is preferably 500-10000 g/mol, more preferably 2000-8000 g/mol, and most preferably 3000-6000 g/mol; the functionality of the polyether polyol is preferably 2-8, and more preferably 3-6.
In the present invention, the isocyanate is preferably one or more selected from the group consisting of hexamethylene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, 4-diphenyl diisocyanate, p-phenylene diisocyanate, polymethylene polyphenyl polyisocyanate, 3, 5-dimethyl-4, 4-diphenyl diisocyanate, 2, 4-ethylbenzene diisocyanate, 3-dimethoxy-4, 4-diphenyl diisocyanate, toluene diisocyanate dimer, isophorone diisocyanate, xylylene diisocyanate, 1, 5-naphthalene diisocyanate and tetramethylxylylene diisocyanate.
In the present invention, the mass ratio of the polymer component and the isocyanate is preferably 100: (75-125), more preferably 100: (80-110), most preferably 100: (90-100).
In the invention, the preparation material of the high resilience polyurethane foam preferably further comprises a chain extender and/or a cross-linking agent, the chain extender or the cross-linking agent is preferably a multifunctional compound with the number average molecular weight of 62-600 g/mol, more preferably 62-300 g/mol, especially a bifunctional compound and a trifunctional compound, such as dialkyl alcohol amine and trialkyl alcohol amine, and the chain extender or the cross-linking agent is preferably selected from ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, diethylene glycol, 1, 7-heptanediol, 1, 8-octanediol, glycerol, trimethylolpropane, 1, 4-cyclohexanediol, hydrogenated bisphenol A, diethanolamine, triethanolamine, methyldiethanolamine, 3-dichloro-4, 4-diphenylmethane, a, One or more of diethyl toluene diamine, 3, 5-dimethyl sulfur toluene diamine, alpha-glycerin allyl ether, glycidyl allyl ether and dicumyl peroxide. In the present invention, the mass ratio of the chain extender and/or the crosslinking agent to the polymer component is preferably (1-20): 100, and more preferably (3-10): 100.
In the invention, the preparation material of the high resilience polyurethane foam preferably also comprises a catalyst, and the catalyst for preparing the high resilience polyurethane foam is preferably selected from one or more of organic tin catalysts and organic amine catalysts. In the present invention, the mass ratio of the catalyst and the polymer component for preparing the high resilience polyurethane foam is preferably (0.05 to 0.5): 100, more preferably (0.1 to 0.4): 100, most preferably (0.2 to 0.3): 100.
in the present invention, the preparation material of the high resilience polyurethane foam preferably further comprises a foam stabilizer and/or a foam stabilizer, and the kind of the foam stabilizer or the foam stabilizer is not particularly limited in the present invention, and a foam stabilizer or a foam stabilizer for polyurethane preparation known to those skilled in the art may be used. In the present invention, the mass ratio of the foam stabilizer or foam stabilizer to the polymer component is preferably (0.05 to 1.5): 100, more preferably (0.1 to 1): 100, most preferably (0.3 to 0.6): 100.
in the present invention, the preparation material of the high resilience polyurethane foam preferably further comprises a foaming agent, the present invention preferably uses water or a combination of water and a physical foaming agent as the foaming agent, and the present invention has no particular limitation on the kind of the physical foaming agent, and the physical foaming agent known to those skilled in the art can be used. In the present invention, the mass ratio of the blowing agent to the polymer component is preferably (2.0 to 4.5): 100, more preferably (2.5 to 4): 100, most preferably (3-3.5): 100.
in the present invention, the preparation method of the high resilience polyurethane foam preferably comprises:
mixing a polymer component, a foaming agent, a chain extender, a catalyst and a foam stabilizer, heating, carrying out first stirring, and then cooling to room temperature to obtain a mixture;
and mixing isocyanate with the mixture, performing second stirring, pouring the mixture into a mold, and then opening the mold to obtain the high-resilience polyurethane foam.
In the present invention, the temperature rise is preferably: raising the temperature to 40-100 ℃ at a constant speed within 1 hour at room temperature, more preferably 50-80 ℃, and most preferably 60-70 ℃; the first stirring is preferably: the stirring speed is increased from 100r/min to 1000r/min for 2 hours.
In the invention, the stirring speed of the second stirring is preferably 1500-2500 r/min, more preferably 1800-2200 r/min, and most preferably 2000 r/min; the second stirring time is preferably 5-10 s, and more preferably 6-8 s; the pouring temperature is preferably 30-100 ℃, more preferably 40-80 ℃, and most preferably 50-60 ℃; in the process of pouring the casting mold, the mold is preferably closed and cured in the mold at 40-80 ℃ for 3-20 min, and more preferably for 5-15 min; and preferably, opening the die after 5-10 min after curing.
The invention also provides the high-resilience polyurethane foam prepared by the method in the technical scheme.
The invention provides a preparation method of high-resilience polyurethane foam, which is obtained by reacting block poly (ether-carbonate) polyalcohol component polymer with isocyanate, and because the block poly (ether-carbonate) polyalcohol is easier to be mixed with polyether polyalcohol to form a stable mixed system, the block poly (ether-carbonate) polyalcohol is more convenient for industrial transportation and storage, and simultaneously the components are more uniform, the prepared polyurethane foam has excellent mechanical property and low hysteresis rate property, can meet the national requirements on seats such as automobiles, airplanes and high-speed rails, and simultaneously utilizes carbon dioxide, reduces the cost and has wide application market.
The MMC catalyst in the following examples of the invention is prepared according to the method of example 1 disclosed in CN102617844 Chinese patent.
Comparative example 1
The weighing bottle was evacuated at 80 ℃ and filled with CO2Gas treatment for 2h (6 times of inflation) and cooling to room temperature; in CO2Adding 300.0mg of MMC catalyst and 80g of glycerol chain transfer agent into a weighing bottle under the protection of gas to obtain a mixture; the 500mL reaction kettle is pumped out and filled with CO at 80 DEG C2Treating for 2 hours (inflating for 6 times), cooling to room temperature, adding the mixture into the reaction kettle, then adding 400g of propylene oxide into the reaction kettle by means of communication of a catalyst weighing bottle, stirring at the rotating speed of 500rpm, simultaneously adding carbon dioxide, keeping the pressure at 3.5MPa, continuously adding 1600g of propylene oxide after the reaction is stable, maintaining the temperature at 80 ℃, and continuing to react for 4 hours; after the reaction was completed, unreacted carbon dioxide was gradually released, the reaction vessel used for the polymerization was cooled to room temperature in a cold water bath at 25 ℃ to distill off unreacted propylene oxide, and the residue was dried in a vacuum oven at 40 ℃ to constant weight to obtain 2461g of poly (carbonate-ether) polyol.
Analysis of the poly (carbonate-ether) polyol prepared in comparative example 1 by GPC: the number average molecular weight is 5500g/mol, the molecular weight distribution is 1.29; the H-NMR spectrum showed that the polymer prepared contained 65% by weight of carbonate units.
Comparative example 2
The weighing bottle was evacuated at 80 ℃ and filled with CO2Gas treatment for 2h (6 times of inflation) and cooling to room temperature; in CO2Adding 35.0mg of MMC catalyst and 15g of citric acid chain transfer agent into a weighing bottle under the protection of gas to obtain a mixture; 500mL of the reaction kettle is put at 80 ℃,by pumping out and charging in CO2Treating for 2 hours (inflating for 6 times), cooling to room temperature, adding the mixture into the reaction kettle, then adding 60g of propylene oxide into the reaction kettle by means of communication of a catalyst weighing bottle, stirring at the rotating speed of 500rpm, placing the reaction kettle into a constant-temperature bath for polymerization reaction, simultaneously adding carbon dioxide, keeping the pressure at 3.5MPa and the polymerization reaction temperature at 80 ℃, continuously adding 440g of propylene oxide after the polymerization is stable, maintaining the temperature at 75 ℃, and continuing to react for 5 hours; after the reaction was completed, unreacted carbon dioxide was gradually released, the reaction vessel used for the polymerization was cooled to room temperature in a cold water bath at 25 ℃ to distill off unreacted propylene oxide, and the residue was dried in a vacuum oven at 40 ℃ to constant weight to obtain 563.2g of poly (carbonate-ether) polyol.
Analysis of the poly (carbonate-ether) polyol prepared in comparative example 2 by GPC was performed: the number average molecular weight is 6100g/mol, the molecular weight distribution is 1.29; the H-NMR spectrum showed that the polymer prepared contained 65% by weight of carbonate units.
Example 1
The weighing bottle was evacuated at 80 ℃ and filled with CO2Gas treatment for 2h (6 times of inflation) and cooling to room temperature; in CO2Adding 35.0mg of MMC catalyst and 15g of citric acid chain transfer agent into a weighing bottle under the protection of gas to obtain a mixture; the 500mL reaction kettle is pumped out and filled with CO at 80 DEG C2After 2h of treatment (6 times with aeration) and cooling to room temperature, the mixture was added to the reactor, then 60g of propylene oxide was added to the reactor via the connection of a catalyst weighing bottle, the reactor was stirred at 500rpm and placed in a constant temperature bath for polymerization: the polymerization temperature is 85 ℃, and the polymerization time is 4 h; after the polymerization reaction is finished, adding carbon dioxide, keeping the pressure at 2.0MPa, continuously adding 440g of propylene oxide, keeping the temperature at 85 ℃, and continuing to react for 5 hours; after the reaction was completed, unreacted carbon dioxide was gradually released, the reaction vessel used for the polymerization was cooled to room temperature in a cold water bath at 25 ℃ to distill off unreacted propylene oxide, and the residue was dried in a vacuum oven at 40 ℃ to constant weight to obtain 531.6g of block poly (ether-carbonate) polyol.
The block poly (ether-carbonate) polyol prepared in example 1 was analyzed by GPC: the number average molecular weight is 6100g/mol, the molecular weight distribution is 1.21; the H-NMR spectrum showed that the polymer prepared contained 45% by weight of carbonate units.
Example 2
The weighing bottle was evacuated at 80 ℃ and filled with CO2Gas treatment for 2h (6 times of inflation) and cooling to room temperature; in CO2Adding 210.0mg of MMC catalyst and 100g of trans-aconitic acid chain transfer agent into a weighing bottle under the protection of gas to obtain a mixture; the 500mL reaction kettle is pumped out and filled with CO at 80 DEG C2After 2h of treatment (6 times with aeration) and cooling to room temperature, the mixture was added to the reactor, and subsequently 300g of propylene oxide were added to the reactor via the connection of a catalyst weighing bottle, stirring at 500rpm, and the reactor was placed in a constant temperature bath for polymerization: the polymerization temperature is 80 ℃, and the polymerization time is 4 h; after the polymerization reaction is finished, adding carbon dioxide, keeping the pressure at 4.0MPa, continuously adding 1700g of propylene oxide, keeping the temperature at 80 ℃, and continuing to react for 4 hours; after the reaction, the unreacted carbon dioxide was gradually released, the reaction vessel used for the polymerization was cooled to room temperature in a cold water bath at 25 ℃ to distill off the unreacted propylene oxide, and the residue was dried in a vacuum oven at 40 ℃ to constant weight to obtain 2600g/mol of block poly (ether-carbonate) polyol.
Analysis of the block poly (ether-carbonate) polyol prepared in example 2 by GPC: the number average molecular weight is 5600g/mol, the molecular weight distribution is 1.43; the H-NMR spectrum showed that the polymer prepared contained 50.2% by weight of carbonate units.
Example 3
The weighing bottle was evacuated at 80 ℃ and filled with CO2Gas treatment for 2h (6 times of inflation) and cooling to room temperature; in CO2Adding 300.0mg of MMC catalyst and 80g of glycerol chain transfer agent into a weighing bottle under the protection of gas to obtain a mixture; the 500mL reaction kettle is pumped out and filled with CO at 80 DEG C2Treating for 2h (aerating for 6 times), cooling to room temperature, adding the mixture into the reaction kettle, adding 400g of propylene oxide into the reaction kettle by virtue of the communication of a catalyst weighing bottle, stirring at the rotating speed of 500rpm, and placing the reaction kettle into a constant-temperature bath for polymerizationThe following steps are required: the polymerization temperature is 80 ℃, and the polymerization time is 4 h; after the polymerization reaction is finished, adding carbon dioxide, keeping the pressure at 4.0MPa, continuously adding 1600g of propylene oxide, keeping the temperature at 80 ℃, and continuing to react for 4 hours; after the reaction was completed, unreacted carbon dioxide was gradually released, the reaction vessel used for the polymerization was cooled to room temperature in a cold water bath at 25 ℃ to distill off unreacted propylene oxide, and the residue was dried in a vacuum oven at 40 ℃ to constant weight to obtain 2488.8g of block poly (ether-carbonate) polyol.
Analysis of the block poly (ether-carbonate) polyol prepared in example 3 by GPC: the number average molecular weight is 5500g/mol, and the molecular weight distribution is 1.39; the H-NMR spectrum showed that the polymer prepared contained 65% by weight of carbonate units.
Example 4
The weighing bottle was evacuated at 80 ℃ and filled with CO2Gas treatment for 2h (6 times of inflation) and cooling to room temperature; in CO2Adding 35.0mg of MMC catalyst and 15g of citric acid chain transfer agent into a weighing bottle under the protection of gas to obtain a mixture; the 500mL reaction kettle is pumped out and filled with CO at 80 DEG C2After 2h of treatment (6 times with aeration) and cooling to room temperature, the mixture was added to the reactor, then 60g of propylene oxide was added to the reactor via the connection of a catalyst weighing bottle, the reactor was stirred at 500rpm and placed in a constant temperature bath for polymerization: the polymerization temperature is 70 ℃, and the polymerization time is 4 h; after the polymerization reaction is finished, adding carbon dioxide, keeping the pressure at 3.0MPa, continuously adding 440g of propylene oxide, keeping the temperature at 75 ℃, and continuing to react for 5 hours; after the reaction, unreacted carbon dioxide was gradually released, the reaction vessel used for the polymerization was cooled to room temperature in a cold water bath at 25 ℃ to distill off unreacted propylene oxide, and the residue was dried in a vacuum oven at 40 ℃ to constant weight to obtain 586.7g of block poly (ether-carbonate) polyol.
Analysis of the block poly (ether-carbonate) polyol prepared in example 4 by GPC: the number average molecular weight is 6100g/mol, the molecular weight distribution is 1.19; the H-NMR spectrum showed that the polymer prepared contained 65% by weight of carbonate units.
Comparative examples 3 to 5 and examples 5 to 8 preparation of high resilience polyurethane foams
Comparative examples 3 to 5 and examples 5 to 8 polyurethane foams were prepared as follows:
accurately weighing a polymer component, a foaming agent, a chain extender, a catalyst and a foam stabilizer according to the components and the proportion in the table 1, adding the weighed materials into a mixing cup, uniformly heating the materials to 70 ℃ within 1 hour at room temperature, slowly heating the stirring speed from 100r/min to 1000r/min at the same time, uniformly mixing the materials for 2 hours, and cooling the materials to room temperature to obtain a component A; accurately weighing the isocyanate component into another mixing cup at room temperature to obtain a component B; mixing the component B and the component A, stirring for 8s at 2000r/min, pouring at 60 ℃, closing the mold in a mold at 60 ℃, curing for 10min, and opening the mold to obtain the polyurethane foam.
TABLE 1 preparation of polyurethane foams according to the inventive and comparative examples
Note:
polyether triol having a number average molecular weight of 3000g/mol, produced by F5511 Jilin resources chemical industries, Ltd;
polyether triol having a number average molecular weight of 6000g/mol, produced by F2831 Jilin resources chemical industries, Ltd
Modified MDI Wanhua PM 200;
TDI80 commercial toluene diisocyanate, which contains 80 wt% of 2,4-TDI and 20 wt% of 2, 6-TDI;
DEOA crosslinker diethanolamine;
TEDA 33 catalyst prepared from 33 wt% triethylenediamine and 67 wt% ethylene glycol from Tosoh corporation of Japan;
Niax-A1 U.S. Union carbon 70 wt% bis (dimethylaminoethyl) ether with 30 wt% dipropylene glycol;
t9 commercial stannous octoate catalyst;
L580A highly reactive polyurethane foam stabilizer from Meiji corporation, USA;
b8681 a polyurethane foam stabilizer with medium and high activity produced by German winning and creating company;
a high hydroxyl value polyurethane foam cell opener produced by F-1251 Jilin gathers resource chemical industry Co.
Performance detection
TABLE 2 method for testing the properties of the polyurethanes prepared in the examples of the present invention and comparative examples and the results thereof
The invention provides a preparation method of high-resilience polyurethane foam, wherein the poly (carbonate-ether) polyol and the universal polyether polyol used in the comparative example are not easy to mix, or are easy to phase separate after mixing, and are not beneficial to storage and transportation; the block poly (ether-carbonate) polyol is easier to mix with polyether polyol to form a stable mixed system, the components are more uniform, the prepared polyurethane foam has excellent mechanical property and low hysteresis rate, can meet the requirements of the current nation on seats such as automobiles, airplanes and high-speed rails, utilizes carbon dioxide, reduces the cost and has wide application market.
While only the preferred embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of high-resilience polyurethane foam is prepared from materials comprising a polymer component and isocyanate;
the polymer component includes:
5 to 100 wt% of a block poly (ether-carbonate) polyol;
95-0 wt% of polyether polyol.
2. The method of claim 1, wherein the block poly (ether-carbonate) polyol is prepared by a method comprising:
under the action of a catalyst and a chain transfer agent, carrying out polymerization reaction on an epoxy compound to obtain a polymerization product;
and (c) continuing to copolymerize the polymerization product with carbon dioxide and an epoxy compound to obtain the block poly (ether-carbonate) polyol.
3. The method according to claim 2, wherein the epoxy compound is selected from one or more of ethylene oxide, propylene oxide, epichlorohydrin, butylene oxide, styrene oxide and cyclohexene oxide.
4. The method of claim 1, wherein the block poly (ether-carbonate) polyol has a number average molecular weight of 600 to 10000 g/mol; the carbonate content in the block poly (ether-carbonate) polyol is 0-99 wt%; the functionality of the block poly (ether-carbonate) polyol is 2-8.
5. The method of claim 2, wherein the chain transfer agent is selected from one or more of C1-C10 alcohol compounds, hydroxyl-containing polymers with molecular weight less than 2000g/mol, and carboxylic acid compounds.
6. The preparation method according to claim 2, wherein the mass ratio of the total epoxy compounds to the chain transfer agent in the polymerization reaction process is (2-50): 1;
the mass ratio of the catalyst to the total epoxy compound in the polymerization reaction process is 1:
(300～200000)。
7. the method according to claim 2, wherein the temperature of the copolymerization reaction is 10 to 130 ℃; the time of the copolymerization reaction is 1-48 hours; the pressure of the copolymerization reaction is 0-15 MPa.
8. The method according to claim 1, wherein the polyether polyol has a number average molecular weight of 600 to 10000 g/mol; the functionality of the polyether polyol is 2-8.
9. The method of claim 1, wherein the isocyanate is selected from one or more of hexamethylene diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, 4-diphenyl diisocyanate, p-phenylene diisocyanate, polymethylene polyphenyl polyisocyanate, 3, 5-dimethyl 4, 4-diphenyl diisocyanate, 2, 4-ethylbenzene diisocyanate, 3-dimethoxy 4, 4-diphenyl diisocyanate, toluene diisocyanate dimer, isophorone diisocyanate, xylylene diisocyanate, 1, 5-naphthalene diisocyanate, and tetramethylxylylene diisocyanate.
10. A high resilience polyurethane foam prepared by the process of claim 1.
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