CN114249873B - Polyurethane soft foam and preparation method thereof - Google Patents

Polyurethane soft foam and preparation method thereof Download PDF

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Publication number
CN114249873B
CN114249873B CN202111586139.5A CN202111586139A CN114249873B CN 114249873 B CN114249873 B CN 114249873B CN 202111586139 A CN202111586139 A CN 202111586139A CN 114249873 B CN114249873 B CN 114249873B
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vegetable oil
polyol
soft foam
preparation
oil polyol
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CN114249873A (en
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蔡启宏
毋亭亭
张莉春
曹志亮
俞杰
邓健能
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GUANGZHOU HAIRMA CHEMICAL (GZ) Ltd
Nantong Haierma Technology Co ltd
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GUANGZHOU HAIRMA CHEMICAL (GZ) Ltd
Nantong Haierma Technology Co ltd
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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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • 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
    • 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
    • C08G2101/00—Manufacture of cellular products
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention belongs to the technical field of polyurethane materials, and particularly relates to a polyurethane soft foam and a preparation method thereof. The preparation method comprises the steps of firstly mixing a first vegetable oil polyol and isocyanate to obtain a prepolymer; the molar ratio of-OH on the first vegetable oil polyol to-NCO on the isocyanate is 1:6 to 17; performing second mixing on the second vegetable oil polyol, the polyether polyol, the foam stabilizer, the foaming agent and the catalyst to obtain a premix; thirdly mixing the prepolymer with the premix, and foaming to obtain the polyurethane soft foam; the mass ratio of the mass sum of the first vegetable oil polyol and the second vegetable oil polyol to the mass ratio of the polyurethane soft foam is (50-70): (95.8-143.5). The polyurethane soft foam obtained by the preparation method provided by the invention has high bio-base content, can obviously reduce the dependence on petrochemical products, and is environment-friendly.

Description

Polyurethane soft foam and preparation method thereof
Technical Field
The invention belongs to the technical field of polyurethane materials, and particularly relates to a polyurethane soft foam and a preparation method thereof.
Background
The polyurethane soft foam is a soft polyurethane foam plastic with certain elasticity. Polyurethane soft foam can be classified into common soft foam, super soft foam, high-bearing soft foam and high-rebound soft foam according to the difference of softness and hardness, namely load resistance; according to different production processes, polyurethane soft foam can be divided into block soft foam and molding soft foam. The polyurethane soft foam is of an open-cell structure, has low density, good elastic recovery, sound absorption, ventilation and heat preservation performances, is mainly used as furniture cushion materials, mattresses, vehicle seat cushions and other cushion materials, and is also used as a filtering material, a sound insulation material, a vibration-proof material, a decorative material, a packaging material, a heat insulation material and the like in industry and civil use.
At present, the polyol raw material for producing the polyurethane soft foam mainly adopts petroleum derived products, has high dependence on non-renewable and non-biodegradable petroleum resources, and causes irreversible damage to the environment. The natural grease is currently recognized as the only renewable petroleum substitute, wherein the performance of the vegetable oil is the most ideal, and natural polymers which can be decomposed by microorganisms can be introduced into the polyurethane soft foam material through the reaction between vegetable oil polyol prepared by taking the vegetable oil as a raw material and isocyanate, so that the problems of petroleum resource shortage, environmental pollution and the like can be solved, and the added value of a vegetable oil product can be improved; meanwhile, the mechanical properties of the vegetable oil-based polyurethane material are comparable with those of polyurethane materials synthesized by petrochemical-based polyol, and the vegetable oil-based polyurethane material has excellent hydrolytic stability, thermal decomposition resistance, thermal oxidation performance and weather resistance. However, the existing vegetable oil-based polyurethane soft foam still has the defect of low bio-base content, if a large amount of vegetable oil polyol is added in the preparation process based on the purpose of improving the bio-base content, the reaction activity of the vegetable polyol is low, and the reaction between a large amount of vegetable oil polyol and isocyanate is incomplete in the foaming process, so that the surface of the obtained polyurethane soft foam is oil-flooded, and the practical application of the polyurethane soft foam is affected.
Disclosure of Invention
The invention aims to provide a polyurethane soft foam and a preparation method thereof, the polyurethane soft foam with high bio-based content can be obtained by adopting the preparation method provided by the invention, and the phenomenon of oil bleeding on the surface of the obtained polyurethane soft foam can be avoided.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of polyurethane soft foam, which comprises the following steps:
first mixing a first vegetable oil polyol and isocyanate to obtain a prepolymer; the molar ratio of-OH on the first vegetable oil polyol to-NCO on the isocyanate is 1:6 to 17;
performing second mixing on the second vegetable oil polyol, the polyether polyol, the foam stabilizer, the foaming agent and the catalyst to obtain a premix;
thirdly mixing the prepolymer with the premix, and foaming to obtain the polyurethane soft foam;
the mass ratio of the mass sum of the first vegetable oil polyol and the second vegetable oil polyol to the mass ratio of the polyurethane soft foam is (50-70): (95.8-143.5).
Preferably, the hydroxyl value of the first vegetable oil polyol and the second vegetable oil polyol is independently 60-220 mgKOH/g, and the functionality is independently 2-5.
Preferably, the isocyanate comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate.
Preferably, the polyether polyol comprises a slow rebound polyether polyol.
Preferably, the catalyst comprises an amine catalyst;
the foam stabilizer comprises silicone oil;
the foaming agent comprises water.
Preferably, the mass ratio of the first vegetable oil polyol to the isocyanate is 3-6: 10.
preferably, the mass ratio of the second vegetable oil polyol, the polyether polyol, the foam stabilizer, the foaming agent and the catalyst is (40-60): (40-60): (0.5-2.0): (1.5-3.5): (1.8-4.0).
Preferably, the mass ratio of the prepolymer to the premix is 4-6: 10.
preferably, the temperature of the first mixing is 65-85 ℃ and the time is 1-3 h;
the first mixing is performed under an inert atmosphere.
The invention also provides the polyurethane soft foam prepared by the preparation method of the technical scheme, and the bio-based content of the polyurethane soft foam is 30% -60%.
The invention provides a preparation method of polyurethane soft foam, which comprises the following steps: first mixing a first vegetable oil polyol and isocyanate to obtain a prepolymer; the molar ratio of-OH on the first vegetable oil polyol to-NCO on the isocyanate is 1:6 to 17; performing second mixing on the second vegetable oil polyol, the polyether polyol, the foam stabilizer, the foaming agent and the catalyst to obtain a premix; thirdly mixing the prepolymer with the premix, and foaming to obtain the polyurethane soft foam; the mass ratio of the mass sum of the first vegetable oil polyol and the second vegetable oil polyol to the mass ratio of the polyurethane soft foam is (50-70): (95.8-143.5). According to the invention, the first vegetable oil polyol and isocyanate are prepolymerized, so that the vegetable oil polyol with lower activity can participate in the reaction preferentially, and the content of the vegetable oil polyol in the polyurethane soft foam is improved through the fixation of the isocyanate; meanwhile, the second vegetable oil polyol, polyether polyol and other components are mixed and then mixed with the prepolymer for foaming, so that the problem of insufficient reaction of the vegetable oil polyol due to low activity under a higher adding proportion can be solved, the occurrence of oil precipitation phenomenon is avoided, and the bio-based content in the polyurethane soft foam is further improved. According to the test results of the examples, the bio-based content of the polyurethane soft foam obtained by the preparation method provided by the invention is 30-60%.
Detailed Description
The invention provides a preparation method of polyurethane soft foam, which comprises the following steps:
first mixing a first vegetable oil polyol and isocyanate to obtain a prepolymer; the molar ratio of-OH on the first vegetable oil polyol to-NCO on the isocyanate is 1:6 to 17;
performing second mixing on the second vegetable oil polyol, the polyether polyol, the foam stabilizer, the foaming agent and the catalyst to obtain a premix;
thirdly mixing the prepolymer with the premix, and foaming to obtain the polyurethane soft foam;
the mass ratio of the mass sum of the first vegetable oil polyol and the second vegetable oil polyol to the mass ratio of the polyurethane soft foam is (50-70): (95.8-143.5).
In the present invention, all the preparation materials are commercially available products well known to those skilled in the art unless specified otherwise.
The preparation method comprises the steps of firstly mixing a first vegetable oil polyol and isocyanate to obtain a prepolymer; the molar ratio of-OH on the first vegetable oil polyol to-NCO on the isocyanate is 1:6 to 17.
In the present invention, the hydroxyl value of the first vegetable oil polyol is preferably 60 to 220mgKOH/g, more preferably 70 to 210mgKOH/g, still more preferably 80 to 200mgKOH/g; the functionality is preferably 2 to 5, more preferably 3 to 4.
In the present invention, the first vegetable oil polyol is preferably one or more of soybean oil polyol, cottonseed oil polyol, palm oil polyol, rapeseed oil polyol and sunflower oil polyol; when the vegetable oil polyol is two or more of the above specific choices, the ratio of the specific substances is not particularly limited in the present invention, and the vegetable oil polyol may be mixed in any ratio.
In the present invention, the isocyanate includes one or more of toluene diisocyanate, diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate; when the isocyanate is two or more of the above specific choices, the proportion of the specific substances is not particularly limited, and the isocyanate may be mixed in any proportion.
In the present invention, the first vegetable oil polyol is preferably prepared by a preparation method preferably comprising the steps of:
and mixing the epoxy vegetable oil, water and an acidic reagent, and then performing a ring-opening reaction to obtain the first vegetable oil polyol.
In the invention, the epoxidized vegetable oil preferably comprises one or more of epoxidized soybean oil, epoxidized cottonseed oil, epoxidized palm oil, epoxidized rapeseed oil and epoxidized sunflower oil; when the epoxidized vegetable oil is two or more of the above specific choices, the ratio of the specific substances is not particularly limited and may be mixed in any ratio. In the present invention, the epoxy value (percentage of oxygen atoms) of the epoxidized vegetable oil is preferably 3 to 7%, more preferably 3.5 to 6.5%, and still more preferably 4 to 6%.
In the present invention, the acidic reagent preferably includes one or more of concentrated hydrochloric acid, concentrated sulfuric acid, concentrated phosphoric acid, fluoroboric acid and p-toluenesulfonic acid; when the acidic reagent is two or more of the above specific choices, the ratio of the specific substances is not particularly limited, and the acidic reagent may be mixed in any ratio. In the invention, the mass fraction of the concentrated hydrochloric acid is preferably 36%; the mass fraction of the concentrated sulfuric acid is 98%; the mass fraction of the concentrated phosphoric acid is preferably 85%; the mass fraction of the fluoboric acid is preferably 30%; the mass fraction of the p-toluenesulfonic acid is 99%.
In the present invention, the water preferably includes deionized water.
In the invention, the mass ratio of the epoxidized vegetable oil, the acidic reagent and the water is preferably 1: (0.0005-0.003): (0.04 to 0.35), more preferably 1: (0.0008 to 0.0028): (0.1 to 0.3), more preferably 1: (0.001-0.0025): (0.15-0.28).
The mixing process is not particularly limited and may be employed as is well known to those skilled in the art. In the present invention, the temperature of the ring-opening reaction is preferably 90 to 130 ℃, more preferably 95 to 125 ℃, still more preferably 100 to 120 ℃; the time is preferably 2 to 5 hours, more preferably 2.5 to 4.5 hours, still more preferably 3 to 4 hours; the pressure is preferably 0.1 to 0.4MPa, more preferably 0.15 to 0.35MPa, and still more preferably 0.2 to 0.3MPa. In the present invention, the ring-opening reaction is preferably carried out in an autoclave.
After the ring-opening reaction is completed, the invention also preferably comprises post-treatment of the product obtained by the reaction; the post-treatment preferably comprises distillation under reduced pressure and filtration, which are carried out sequentially.
The process of the reduced pressure distillation is not particularly limited, and may be employed as is well known to those skilled in the art. The process of the filtration is not particularly limited and may be employed as is well known to those skilled in the art. In the present invention, the reduced pressure distillation is capable of removing excess moisture and acidic reagents.
In the invention, the mass ratio of the first vegetable oil polyol to the isocyanate is preferably 3-6: 10, more preferably 3.5 to 5.5:10, more preferably 4.0 to 5.0:10. in the present invention, the molar ratio of-OH on the first vegetable oil polyol to-NCO on the isocyanate is preferably 1:6 to 17, more preferably 1:7 to 16, more preferably 1: 8-15.
In the present invention, the first mixing is preferably performed under stirring. In the present invention, the rotation speed of the stirring is preferably 100 to 300r/min, more preferably 120 to 280r/min, and still more preferably 150 to 250r/min. In the present invention, the temperature of the first mixing is preferably 65 to 85 ℃, more preferably 70 to 80 ℃, still more preferably 72 to 78 ℃; the time is preferably 1 to 3 hours, more preferably 1.5 to 2.8 hours, and still more preferably 1.8 to 2.5 hours. In the present invention, the first mixing is preferably performed under an inert atmosphere; the inert atmosphere is preferably nitrogen. In the present invention, the first mixing is preferably performed in a reaction vessel.
In the present invention, the first mixing preferably includes the steps of: adding isocyanate into a reaction kettle filled with inert gas, and preheating under stirring; then adding the first vegetable oil polyol into a reaction kettle under stirring for heating and prepolymerization, and cooling to obtain a prepolymer.
In the present invention, the temperature of the preheating is preferably 40 to 60 ℃, more preferably 42 to 58 ℃, and even more preferably 45 to 55 ℃. In the present invention, the first vegetable oil polyol is preferably added at a rate of 20 to 30g/min, more preferably 22 to 28g/min, and still more preferably 24 to 27g/min. In the present invention, the heated temperature is preferably the temperature of the first mixture; the time of heating is preferably the time of the first mixing. The cooling process is not particularly limited, and may be employed as is well known to those skilled in the art.
The invention carries out second mixing on a second vegetable oil polyol, a polyether polyol, a foam stabilizer, a foaming agent and a catalyst to obtain a premix.
In the present invention, the hydroxyl value, functionality and preparation method of the second vegetable oil polyol are the same as those of the first vegetable oil polyol, and are not described herein.
In the present invention, the polyether polyol preferably includes a slow rebound polyether polyol, and further preferably includes one or more of polyether 330N, polyether 3050 and polyether 5041; when the polyether polyol is two or more of the above specific choices, the proportion of the specific substances in the present invention is not particularly limited, and the polyether polyol may be mixed in any proportion.
In the present invention, the catalyst preferably includes an amine catalyst, and further preferably includes one or more of triethanolamine, triethylenediamine and tetramethyldiethylenetriamine; when the catalyst is two or more of the above specific choices, the proportion of the specific substances is not particularly limited, and the specific substances may be mixed in any proportion.
In the present invention, the foam stabilizer is preferably silicone oil. In the present invention, the foaming agent is preferably water, and more preferably deionized water and/or distilled water.
In the present invention, the mass ratio of the second vegetable oil polyol, polyether polyol, foam stabilizer, foaming agent and catalyst is preferably (40 to 60): (40-60): (0.5-2.0): (1.5-3.5): (1.8 to 4.0), more preferably (42 to 58): (42-58): (0.8-1.8): (1.8-3.2): (2.0 to 3.5), more preferably (45 to 55): (45-55): (1.0-1.5): (2.0-3.0): (2.2-3.3).
The process of the second mixing is not particularly limited, and may be employed as is well known to those skilled in the art.
In the present invention, the preparation of the prepolymer and the premix is not limited in order.
After the prepolymer and the premix are obtained, the invention carries out third mixing on the prepolymer and the premix, and then foams the mixture to obtain the polyurethane soft foam.
In the invention, the mass ratio of the prepolymer to the premix is preferably 4-6: 10, more preferably 4.2 to 5.8:10, more preferably 4.5 to 5.2:10.
in the present invention, the mass ratio of the first vegetable oil polyol and the second vegetable oil polyol to the polyurethane soft foam is preferably (50 to 70): (95.8 to 143.5), more preferably (52 to 68): (96 to 145), more preferably (53 to 66): (98-146).
The third mixing process is not particularly limited, and may be performed as known to those skilled in the art. In the present invention, the time of the third mixing is preferably 3 to 10 seconds, more preferably 4 to 9 seconds, and still more preferably 5 to 8 seconds.
In the present invention, the foaming time is preferably not more than 15 minutes, more preferably 10 to 14 minutes, and still more preferably 12 to 13 minutes. In the present invention, the foaming is preferably performed in a mold.
After the foaming is completed, the invention also preferably comprises demolding treatment on the polyurethane soft foam obtained by foaming. The process of the demolding treatment is not particularly limited, and may be known to those skilled in the art.
The invention also provides the polyurethane soft foam prepared by the preparation method. In the present invention, the bio-based content of the polyurethane soft foam is preferably 30% to 60%, more preferably 35% to 50%, and even more preferably 35% to 45%.
In order to further illustrate the present invention, a polyurethane soft foam and a method for preparing the same, which are provided by the present invention, are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
1000g of epoxy rapeseed oil (epoxy value is 5.85%), 0.5g of phosphoric acid with mass fraction of 85% and 40g of water are added into a high-pressure reaction kettle for mixing, then the mixture is heated to 95 ℃ for ring-opening reaction, the reaction pressure is 0.3MPa, and the reaction time is 5 hours; distilling the obtained product under reduced pressure to remove residual water and phosphoric acid, and filtering to obtain rapeseed oil-based polyol, wherein the hydroxyl value of the rapeseed oil-based polyol is 102mgKOH/g, and the functionality is about 2;
1000g of toluene diisocyanate is added into a reaction kettle filled with nitrogen, the temperature is heated to 40 ℃ at the rotating speed of 100r/min, then 350g of rapeseed oil-based polyol is added into the reaction kettle at the speed of 20g/min, the temperature is raised to 85 ℃ and the temperature is kept for 1h, and the prepolymer is obtained after cooling; wherein the molar ratio of-OH on the rapeseed oil-based polyol to-NCO on the toluene diisocyanate is 1:16.43;
60g of rapeseed oil-based polyol, 40g of polyether 330N, 0.8g of silicone oil, 1.5g of deionized water and 1.8g of triethanolamine are mixed to obtain a premix;
after 42g of prepolymer and 100g of premix are mixed for 4s, the mixture is poured into a mold for foaming, the foaming and curing time is 12 minutes, and then demolding is carried out to obtain the polyurethane soft foam.
Example 2
1000g of epoxidized soybean oil (the epoxy value is 6.25%), 2.0g of sulfuric acid with the mass fraction of 98% and 200g of water are added into a high-pressure reaction kettle for mixing, then the mixture is heated to 115 ℃ for ring-opening reaction, the reaction pressure is 0.4MPa, and the reaction time is 5 hours; distilling the obtained product under reduced pressure to remove residual water and sulfuric acid, and filtering to obtain soybean oil-based polyol, wherein the hydroxyl value of the soybean oil-based polyol is 216mgKOH/g, and the functionality is about 4;
1000g of diphenylmethane diisocyanate is added into a reaction kettle filled with nitrogen, heated to 45 ℃ at the rotating speed of 150r/min, then 300g of soybean oil-based polyol is added into the reaction kettle at the speed of 25g/min, the temperature is raised to 80 ℃ and kept for 1.5h, and the prepolymer is obtained by cooling; wherein the molar ratio of-OH on the soy oil-based polyol to-NCO on the diphenylmethane diisocyanate is 1:6.67;
mixing 55 soybean oil-based polyol, 45g polyether 3050, 1.0g silicone oil, 2.0g deionized water and 2.2g triethanolamine to obtain a premix;
45g of prepolymer and 100g of premix are mixed for 5s, then poured into a mold for foaming, the foaming and curing time is 10 minutes, and then demolding is carried out to obtain the polyurethane soft foam.
Example 3
1000g of epoxy palm oil (with an epoxy value of 4.21%), 1.5g of fluoboric acid with a mass fraction of 30% and 100g of water are added into a high-pressure reaction kettle for mixing, then heated to 100 ℃ for ring-opening reaction, the reaction pressure is 0.2MPa, and the reaction time is 4 hours; distilling the obtained product under reduced pressure to remove residual water and fluoroboric acid, and filtering to obtain palm oil-based polyol, wherein the hydroxyl value of the palm oil-based polyol is 65mgKOH/g, and the functionality is about 2;
1000g of polyphenyl polymethylene polyisocyanate is added into a reaction kettle filled with nitrogen, heated to 50 ℃ at the rotating speed of 200r/min, 550g of palm oil-based polyol is added into the reaction kettle at the speed of 30g/min, the temperature is raised to 75 ℃ and kept for 2 hours, and the prepolymer is obtained after cooling; wherein the molar ratio of-OH on the palm oil-based polyol to-NCO on the polyphenyl polymethylene polyisocyanate is 1:12.96;
a premix was obtained by mixing 50g of palm oil-based polyol, 50g of polyether 5041, 1.5g of silicone oil, 2.6g of deionized water and 2.8g of triethylenediamine;
50g of prepolymer and 100g of premix are mixed for 6s, then poured into a mold for foaming, the foaming and curing time is 14 minutes, and then demolding is carried out to obtain the polyurethane soft foam.
Example 4
1000g of epoxy cottonseed oil (the epoxy value is 6.0%), 2.0g of hydrochloric acid with the mass fraction of 36% and 250g of water are added into a high-pressure reaction kettle for mixing, then the mixture is heated to 125 ℃ for ring-opening reaction, the reaction pressure is 0.1MPa, and the reaction time is 3 hours; distilling the obtained product under reduced pressure to remove residual water and hydrochloric acid, and filtering to obtain cottonseed oil-based polyol, wherein the hydroxyl value of the cottonseed oil-based polyol is 170mgKOH/g, and the functionality is about 3;
1000g of toluene diisocyanate is added into a reaction kettle filled with nitrogen, the temperature is heated to 55 ℃ at the rotating speed of 250r/min, 450g of cottonseed oil-based polyol is added into the reaction kettle at the speed of 30g/min, the temperature is raised to 70 ℃ and the temperature is kept for 1h, and the prepolymer is obtained after cooling; wherein the molar ratio of-OH on the cottonseed oil based polyol to-NCO on the toluene diisocyanate is 1:8.52;
45g of cottonseed oil-based polyol, 55g of polyether 330N, 2.0g of silicone oil, 3.2g of deionized water and 3.5g of tetramethyl diethylenetriamine are mixed to obtain a premix;
and mixing 55g of prepolymer and 100g of premix for 8s, pouring into a mold for foaming, curing for 10 minutes, and demolding to obtain the polyurethane soft foam.
Example 5
1000g of epoxy sunflower seed oil (the epoxy value is 5.2%), 2.5g of 99% p-toluenesulfonic acid and 300g of water are added into a high-pressure reaction kettle for mixing, then the mixture is heated to 120 ℃ for ring-opening reaction, the reaction pressure is 0.2MPa, and the reaction time is 4 hours; distilling the obtained product under reduced pressure to remove residual water and p-toluenesulfonic acid, and filtering to obtain sunflower seed oil-based polyol, wherein the hydroxyl value of the sunflower seed oil-based polyol is 136mgKOH/g, and the functionality is about 2.5;
1000g of polyphenyl polymethylene polyisocyanate is added into a reaction kettle filled with nitrogen, heated to 60 ℃ at the rotating speed of 300r/min, 400g of sunflower seed oil-based polyol is added into the reaction kettle at the speed of 25g/min, the temperature is raised to 65 ℃ and the temperature is kept for 1h, and the prepolymer is obtained after cooling; wherein the molar ratio of-OH on the sunflower seed oil-based polyol to-NCO on the polyphenyl polymethylene polyisocyanate is 1:7.13;
mixing 40g of sunflower seed oil-based polyol, 60g of polyether 3050, 1.0g of silicone oil, 3.5g of deionized water and 3.2g of triethylenediamine to obtain a premix;
60g of prepolymer and 100g of premix are mixed for 10s, then poured into a mold for foaming, the foaming and curing time is 15 minutes, and then demolding is carried out to obtain the polyurethane soft foam.
Example 6
1000g of epoxidized soybean oil (the epoxy value is 6.17%), 2.0g of sulfuric acid with the mass fraction of 98% and 200g of water are added into a high-pressure reaction kettle for mixing, then the mixture is heated to 105 ℃ for ring-opening reaction, the reaction pressure is 0.2MPa, and the reaction time is 3 hours; distilling the obtained product under reduced pressure to remove residual water and sulfuric acid, and filtering to obtain soybean oil-based polyol, wherein the hydroxyl value of the soybean oil-based polyol is 125mgKOH/g, and the functionality is about 2.2;
1000g of diphenylmethane diisocyanate is added into a reaction kettle filled with nitrogen, heated to 50 ℃ at the rotating speed of 200r/min, then 500g of soybean oil-based polyol is added into the reaction kettle at the speed of 20g/min, the temperature is raised to 80 ℃ and kept for 2 hours, and the prepolymer is obtained by cooling; wherein the molar ratio of-NCO on the soybean-based polyol to-NCO on the diphenylmethane diisocyanate is 1:7.27;
60g of soybean oil-based polyol, 40g of polyether 5041, 1.0g of silicone oil, 2.0g of deionized water and 4.0g of triethanolamine are mixed to obtain a premix;
50g of prepolymer and 100g of premix are mixed for 6s, then poured into a mold for foaming, the foaming and curing time is 11 minutes, and then demolding is carried out to obtain the polyurethane soft foam.
Comparative example 1
100g of polyether 5041, 1g of silicone oil, 2g of deionized water and 1g of amine catalyst are mixed to obtain a mixture; 43g of polyphenyl polymethylene polyisocyanate and the mixture are mixed for 8 seconds, poured into a mold for foaming, the foaming and curing time is 12 minutes, and then demolding is carried out to obtain the petroleum-based polyurethane soft foam.
Comparative example 2
70g of polyether 5041, 30g of soybean oil-based polyol, 1g of silicone oil, 2g of deionized water and 1g of amine catalyst are mixed to obtain a mixture; 43g of polyphenyl polymethylene polyisocyanate and the mixture are mixed for 8 seconds, poured into a mold for foaming, the foaming and curing time is 12 minutes, and then demolding is carried out to obtain the polyurethane soft foam.
Performance testing
The bio-based content of the polyurethane soft foam obtained in examples 1 to 6 was tested according to astm d6866, and the test results are shown in table 1;
TABLE 1 Bio-based content test results of polyurethane Soft foams obtained in examples 1 to 6
Example 1 Example 2 Example 3 Example 4
Biobased content/% 30 40 35 57
Example 5 Example 6 Comparative example 1 Comparative example 2
Biobased content/% 45 50 - 20
As can be seen from Table 1, the bio-based content of the polyurethane soft foam obtained by the present invention is high.
The polyurethane flexible foams obtained in example 2, comparative example 1 and comparative example 2 were subjected to performance tests, and the test standards were carried out in accordance with GB/T24451-2020. The test results are shown in Table 2.
TABLE 2 results of Performance test of polyurethane Soft foam obtained in example 2 and comparative examples 1 and 2
As can be seen from Table 2, the polyurethane soft foam obtained by the preparation method provided by the invention is not hardened, breathable, not sultry, moderate in supporting force and degradable at low temperature, can obviously reduce dependence on petrochemical products, and is environment-friendly; and the physical properties of the polyurethane foam are similar to those of petroleum-based polyurethane foam; the polyurethane soft foam obtained by touching with hands after demolding has no phenomenon of oiling and sticking hands on the surface, and the polyurethane soft foam obtained in comparative example 2 has oiling and becomes sticky.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.

Claims (7)

1. The preparation method of the polyurethane soft foam is characterized by comprising the following steps of:
first mixing a first vegetable oil polyol and isocyanate to obtain a prepolymer; the molar ratio of-OH on the first vegetable oil polyol to-NCO on the isocyanate is 1: 6-17; the hydroxyl value of the first vegetable oil polyol and the hydroxyl value of the second vegetable oil polyol are independently 60-220 mg KOH/g, and the functionality is independently 2-5; the isocyanate comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate;
performing second mixing on the second vegetable oil polyol, the polyether polyol, the foam stabilizer, the foaming agent and the catalyst to obtain a premix; the polyether polyol comprises a slow rebound polyether polyol;
thirdly mixing the prepolymer with the premix, and foaming to obtain the polyurethane soft foam; the bio-based content of the polyurethane soft foam is 30% -60%;
the mass ratio of the mass sum of the first vegetable oil polyol and the second vegetable oil polyol to the mass ratio of the first vegetable oil polyol to the mass ratio of the second vegetable oil polyol to the mass ratio of: (95.8-143.5).
2. The method of preparation of claim 1, wherein the catalyst comprises an amine catalyst;
the foam stabilizer comprises silicone oil;
the foaming agent comprises water.
3. The preparation method according to claim 1 or 2, wherein the mass ratio of the first vegetable oil polyol to the isocyanate is (3-6): 10.
4. the preparation method of claim 1, wherein the mass ratio of the second vegetable oil polyol, the polyether polyol, the foam stabilizer, the foaming agent and the catalyst is (40-60): (40-60): (0.5 to 2.0): (1.5 to 3.5): (1.8 to 4.0).
5. The preparation method of claim 1, wherein the mass ratio of the prepolymer to the premix is (4-6): 10.
6. the preparation method according to claim 1, wherein the first mixing temperature is 65-85 ℃ for 1-3 hours;
the first mixing is performed under an inert atmosphere.
7. The polyurethane soft foam prepared by the preparation method of any one of claims 1-6, which is characterized in that the bio-based content of the polyurethane soft foam is 30% -60%.
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