CN114249873A - Polyurethane flexible foam and preparation method thereof - Google Patents
Polyurethane flexible foam and preparation method thereof Download PDFInfo
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- CN114249873A CN114249873A CN202111586139.5A CN202111586139A CN114249873A CN 114249873 A CN114249873 A CN 114249873A CN 202111586139 A CN202111586139 A CN 202111586139A CN 114249873 A CN114249873 A CN 114249873A
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- vegetable oil
- polyol
- mixing
- oil polyol
- foam
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- 239000006260 foam Substances 0.000 title claims abstract description 74
- 239000004814 polyurethane Substances 0.000 title claims abstract description 62
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229920005862 polyol Polymers 0.000 claims abstract description 113
- 150000003077 polyols Chemical class 0.000 claims abstract description 113
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 83
- 239000008158 vegetable oil Substances 0.000 claims abstract description 83
- 238000002156 mixing Methods 0.000 claims abstract description 54
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 28
- 229920000570 polyether Polymers 0.000 claims abstract description 28
- 238000005187 foaming Methods 0.000 claims abstract description 27
- 239000012948 isocyanate Substances 0.000 claims abstract description 25
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000003381 stabilizer Substances 0.000 claims abstract description 12
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 12
- 239000004088 foaming agent Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 15
- 229920002545 silicone oil Polymers 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- -1 polymethylene Polymers 0.000 claims description 10
- 229920001228 polyisocyanate Polymers 0.000 claims description 9
- 239000005056 polyisocyanate Substances 0.000 claims description 9
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 7
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 6
- 239000011496 polyurethane foam Substances 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000004604 Blowing Agent Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 33
- 238000010438 heat treatment Methods 0.000 description 21
- 239000003549 soybean oil Substances 0.000 description 15
- 235000012424 soybean oil Nutrition 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000004593 Epoxy Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 238000007142 ring opening reaction Methods 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 235000019482 Palm oil Nutrition 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 235000019484 Rapeseed oil Nutrition 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 235000012343 cottonseed oil Nutrition 0.000 description 8
- 239000002385 cottonseed oil Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- 239000002540 palm oil Substances 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 6
- 235000019486 Sunflower oil Nutrition 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002600 sunflower oil Substances 0.000 description 4
- 235000020238 sunflower seed Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 3
- 239000012445 acidic reagent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ZIKLHFPNSYDZSP-UHFFFAOYSA-N 1-n-(2-aminoethyl)-2-n,2-n,2-trimethylpropane-1,2-diamine Chemical compound CN(C)C(C)(C)CNCCN ZIKLHFPNSYDZSP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- 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. Firstly mixing a first vegetable oil polyalcohol 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; carrying 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; thirdly, mixing the prepolymer and the premix, and foaming to obtain the polyurethane soft foam; the mass sum of the first vegetable oil polyol and the second vegetable oil polyol and the mass ratio of the first vegetable oil polyol and the second vegetable oil polyol to the polyurethane soft foam are (50-70): (95.8 to 143.5). The polyurethane soft foam prepared by the preparation method provided by the invention has high content of bio-based materials, can obviously reduce the dependence on petrochemical products, and is environment-friendly.
Description
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 flexible foam is a flexible polyurethane foam plastic with certain elasticity. According to the difference of the hardness, namely the load-bearing performance, the polyurethane soft foam can be divided into common soft foam, super soft foam, high-bearing soft foam and high-resilience soft foam; according to different production processes, the soft polyurethane foam can be divided into block-shaped soft foam and molding soft foam. The polyurethane soft foam is mainly of an open pore structure, has the properties of low density, good elastic recovery, sound absorption, ventilation and heat preservation, is mainly used as cushion materials of furniture, mattresses, seats and cushions of vehicles, and is also used as a filtering material, a sound insulation material, a shockproof material, a decorative material, a packaging material, a heat insulation material and the like in industry and civil.
At present, the polyol raw material for producing the polyurethane flexible 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 oil is the only petroleum substitute which is acknowledged at present and can be regenerated, wherein the performance of the vegetable oil is the most ideal, the natural polymer which can be decomposed by microorganisms can be introduced into the polyurethane flexible foam material through the reaction between vegetable oil polyalcohol which is prepared by taking the vegetable oil as a raw material and isocyanate, the problems of petroleum resource shortage, environmental pollution and the like can be solved, and the additional value of the vegetable oil product can be improved; meanwhile, the mechanical property of the vegetable oil-based polyurethane material can be comparable to that of a polyurethane material synthesized by petrochemical-based polyol, and the vegetable oil-based polyurethane material also has excellent hydrolytic stability, thermal decomposition resistance, thermal oxidation performance and weather resistance. However, the currently obtained vegetable oil-based polyurethane flexible foam still has the defect of low content of bio-based, if a large amount of vegetable oil polyol is added in the preparation process based on the purpose of improving the content of bio-based, the reaction activity of the vegetable oil polyol is low, and the reaction of a large amount of vegetable oil polyol and isocyanate is incomplete in the foaming process, so that the surface of the obtained polyurethane flexible foam is oiled, and the practical application of the polyurethane flexible foam is influenced.
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 the preparation method provided by the invention, and the phenomenon of oil bleeding on the surface of the obtained polyurethane soft foam is avoided.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a preparation method of polyurethane flexible foam, which comprises the following steps:
carrying out first mixing on a first vegetable oil polyalcohol 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;
carrying 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;
thirdly, mixing the prepolymer and the premix, and foaming to obtain the polyurethane soft foam;
the mass sum of the first vegetable oil polyol and the second vegetable oil polyol and the mass ratio of the first vegetable oil polyol and the second vegetable oil polyol to the polyurethane soft foam are (50-70): (95.8 to 143.5).
Preferably, the hydroxyl values of the first vegetable oil polyol and the second vegetable oil polyol are 60-220 mgKOH/g independently, and the functionalities of the first vegetable oil polyol and the second vegetable oil polyol are 2-5 independently.
Preferably, the isocyanate includes 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 blowing agent includes 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 carried out under an inert atmosphere.
The invention also provides the polyurethane soft foam prepared by the preparation method of the technical scheme, and the content of the bio-based of the polyurethane soft foam is 30-60%.
The invention provides a preparation method of polyurethane flexible foam, which comprises the following steps: carrying out first mixing on a first vegetable oil polyalcohol 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; carrying 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; thirdly, mixing the prepolymer and the premix, and foaming to obtain the polyurethane soft foam; the mass sum of the first vegetable oil polyol and the second vegetable oil polyol and the mass ratio of the first vegetable oil polyol and the second vegetable oil polyol to the polyurethane soft foam are (50-70): (95.8 to 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 preferentially participate in the reaction, and the content of the vegetable oil polyol in the polyurethane flexible foam is increased by fixing the isocyanate; meanwhile, the second vegetable oil polyalcohol, the polyether glycol and other components are mixed and then mixed with the prepolymer for foaming, so that the problem of insufficient reaction caused by low activity of the vegetable oil polyalcohol at a high addition ratio can be solved, the phenomenon of oil bleeding is avoided, and the content of bio-based in the polyurethane soft foam is further improved. According to the test results of the embodiment, 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 flexible foam, which comprises the following steps:
carrying out first mixing on a first vegetable oil polyalcohol 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;
carrying 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;
thirdly, mixing the prepolymer and the premix, and foaming to obtain the polyurethane soft foam;
the mass sum of the first vegetable oil polyol and the second vegetable oil polyol and the mass ratio of the first vegetable oil polyol and the second vegetable oil polyol to the polyurethane soft foam are (50-70): (95.8 to 143.5).
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
Firstly mixing a first vegetable oil polyalcohol 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.
In the invention, the hydroxyl value of the first vegetable oil polyol is preferably 60-220 mgKOH/g, more preferably 70-210 mgKOH/g, and even more preferably 80-200 mgKOH/g; the functionality is preferably 2 to 5, more preferably 3 to 4.
In the 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 specific material may be mixed at any ratio without any specific limitation.
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 selected from the above specific choices, the specific material may be mixed at any ratio without any particular limitation in the present invention.
In the present invention, the first vegetable oil polyol is preferably prepared by a preparation method, which preferably comprises the steps of:
mixing the epoxy vegetable oil, water and an acidic reagent, and carrying out ring-opening reaction to obtain the first vegetable oil polyalcohol.
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 epoxy vegetable oil is more than two of the above specific choices, the specific material proportion is not particularly limited in the present invention, and the epoxy vegetable oil can be mixed according to any proportion. In the present invention, the epoxy value (percentage content 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 invention, the acidic reagent preferably comprises 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 specific material may be mixed at any ratio without any particular limitation in the present invention. In the present invention, the mass fraction of the concentrated hydrochloric acid is preferably 36%; the mass fraction of the concentrated sulfuric acid is 98 percent; the mass fraction of the concentrated phosphoric acid is preferably 85%; the mass fraction of the fluoroboric 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 present invention, the mass ratio of the epoxidized vegetable oil, the acidic agent and the water is preferably 1: (0.0005-0.003): (0.04 to 0.35), and more preferably 1: (0.0008-0.0028): (0.1 to 0.3), more preferably 1: (0.001-0.0025): (0.15-0.28).
The mixing process is not particularly limited in the present invention, and may be performed as is well known to those skilled in the art. In the invention, the temperature of the ring-opening reaction is preferably 90-130 ℃, more preferably 95-125 ℃, and more preferably 100-120 ℃; the time is preferably 2 to 5 hours, more preferably 2.5 to 4.5 hours, and even 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 0.3 MPa. In the present invention, the ring-opening reaction is preferably carried out in an autoclave.
After the ring-opening reaction is finished, the invention also preferably comprises the step of carrying out post-treatment on a product obtained by the reaction; the post-treatment preferably comprises a reduced pressure distillation and filtration carried out in this order.
The process of the reduced pressure distillation is not particularly limited in the present invention, and those well known to those skilled in the art can be used. The filtration process is not particularly limited in the present invention, and those skilled in the art will be familiar with the filtration process. In the present invention, the reduced pressure distillation can remove excess moisture and acidic agent.
In the invention, the mass ratio of the first vegetable oil polyol to the isocyanate is preferably 3-6: 10, and 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 and-NCO on the isocyanate is preferably 1: 6-17, and more preferably 1: 7-16, more preferably 1: 8-15.
In the present invention, the first mixing is preferably performed under stirring. In the invention, the rotation speed of the stirring is preferably 100-300 r/min, more preferably 120-280 r/min, and even more preferably 150-250 r/min. In the invention, the temperature of the first mixing is preferably 65-85 ℃, more preferably 70-80 ℃, and more preferably 72-78 ℃; 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 carried out under an inert atmosphere; the inert atmosphere is preferably nitrogen. In the present invention, the first mixing is preferably performed in a reaction tank.
In the present invention, the first mixing preferably includes the steps of: adding isocyanate into a reaction kettle filled with inert gas, and preheating while stirring; and then adding the first vegetable oil polyalcohol into a reaction kettle under stirring for heating prepolymerization, and cooling to obtain a prepolymer.
In the invention, the preheating temperature is preferably 40-60 ℃, more preferably 42-58 ℃, and more preferably 45-55 ℃. In the invention, the adding speed of the first vegetable oil polyalcohol is preferably 20-30 g/min, more preferably 22-28 g/min, and more preferably 24-27 g/min. In the present invention, the temperature of the heating is preferably the temperature of the first mixing; the time of the heating is preferably the time of the first mixing. The cooling process is not particularly limited in the present invention, and those skilled in the art can use the cooling process.
According to the invention, a second vegetable oil polyol, a polyether polyol, a foam stabilizer, a foaming agent and a catalyst are subjected to second mixing to obtain the 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 thus, the description thereof is omitted.
In the invention, the polyether polyol preferably comprises slow rebound polyether polyol, and further preferably comprises 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 specific material may be mixed at any ratio without any particular limitation in the present invention.
In the present invention, the catalyst preferably comprises an amine catalyst, and further preferably comprises one or more of triethanolamine, triethylene diamine and tetramethyl diethylene triamine; when the catalyst is two or more of the above specific choices, the specific material may be mixed at any ratio without any particular limitation.
In the present invention, the foam stabilizer is preferably a 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, the polyether polyol, the foam stabilizer, the foaming agent and the catalyst is preferably (40 to 60): (40-60): (0.5-2.0): (1.5-3.5): (1.8-4.0), more preferably (42-58): (42-58): (0.8-1.8): (1.8-3.2): (2.0-3.5), more preferably (45-55): (45-55): (1.0-1.5): (2.0-3.0): (2.2-3.3).
The process of the second mixing is not particularly limited in the present invention, and may be well known to those skilled in the art.
In the invention, the preparation of the prepolymer and the premix has no sequential limitation.
After the prepolymer and the premix are obtained, the prepolymer and the premix are subjected to third mixing and then are foamed to obtain the polyurethane soft foam.
In the invention, the mass ratio of the prepolymer to the premix is preferably 4-6: 10, and 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 sum of the mass of the first vegetable oil polyol and the second vegetable oil polyol to the mass of the polyurethane soft foam is preferably (50 to 70): (95.8 to 143.5), more preferably (52 to 68): (96-145), more preferably (53-66): (98-146).
The process of the third mixing is not particularly limited in the present invention, and may be a process known to those skilled in the art. In the present invention, the time for 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 invention, the foaming time is preferably less than or equal to 15min, more preferably 10-14 min, and even more preferably 12-13 min. In the present invention, the foaming is preferably carried out in a mold.
After the foaming is finished, the invention also preferably comprises the step of demoulding the polyurethane soft foam obtained by foaming. The process of the release treatment is not particularly limited in the present invention, and those well known to those skilled in the art may be used.
The invention also provides the polyurethane flexible foam prepared by the preparation method of the technical scheme. In the present invention, the bio-based content of the polyurethane flexible foam is preferably 30% to 60%, more preferably 35% to 50%, and still more preferably 35% to 45%.
In order to further illustrate the present invention, the following examples are provided to describe a polyurethane flexible foam and a method for preparing the same in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Adding 1000g of epoxy rapeseed oil (the epoxy value is 5.85%), 0.5g of phosphoric acid with the mass fraction of 85% and 40g of water into a high-pressure reaction kettle for mixing, and then heating to 95 ℃ for ring-opening reaction, wherein the reaction pressure is 0.3MPa, and the reaction time is 5 hours; carrying out reduced pressure distillation on the obtained product to remove residual water and phosphoric acid, and then 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;
adding 1000g of toluene diisocyanate into a reaction kettle filled with nitrogen, heating to 40 ℃ at the rotating speed of 100r/min, adding 350g of rapeseed oil-based polyol into the reaction kettle at the speed of 20g/min, heating to 85 ℃, preserving heat for 1h, and cooling to obtain a prepolymer; 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;
and mixing 42g of prepolymer and 100g of premix for 4s, pouring the mixture into a mold for foaming, wherein the foaming curing time is 12 minutes, and then demolding to obtain the polyurethane soft foam.
Example 2
Adding 1000g of epoxidized soybean oil (with the epoxy value of 6.25%), 2.0g of sulfuric acid with the mass fraction of 98% and 200g of water into a high-pressure reaction kettle for mixing, and then heating to 115 ℃ for ring-opening reaction, wherein the reaction pressure is 0.4MPa, and the reaction time is 5 hours; carrying out reduced pressure distillation on the obtained product to remove residual water and sulfuric acid, and then 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;
adding 1000g of diphenylmethane diisocyanate into a reaction kettle filled with nitrogen, heating to 45 ℃ at the rotating speed of 150r/min, adding 300g of soybean oil-based polyol into the reaction kettle at the speed of 25g/min, heating to 80 ℃, preserving heat for 1.5h, and cooling to obtain a prepolymer; wherein the molar ratio of-OH on the soybean oil-based polyol to-NCO on the diphenylmethane diisocyanate is 1: 6.67;
mixing 55 parts of soybean oil-based polyol, 45 parts of polyether 3050, 1.0 part of silicone oil, 2.0 parts of deionized water and 2.2 parts of triethanolamine to obtain a premix;
and (3) mixing 45g of prepolymer with 100g of premix for 5s, pouring the mixture into a mold for foaming, wherein the foaming curing time is 10 minutes, and then demolding to obtain the polyurethane soft foam.
Example 3
Adding 1000g of epoxy palm oil (the epoxy value is 4.21%), 1.5g of fluoboric acid with the mass fraction of 30% and 100g of water into a high-pressure reaction kettle for mixing, and then heating to 100 ℃ for ring-opening reaction, wherein 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;
adding 1000g of polyphenyl polymethylene polyisocyanate into a reaction kettle filled with nitrogen, heating to 50 ℃ at the rotating speed of 200r/min, then adding 550g of palm oil-based polyol into the reaction kettle at the speed of 30g/min, heating to 75 ℃, preserving heat for 2 hours, and cooling to obtain a prepolymer; wherein the molar ratio of-OH on the palm oil-based polyol to-NCO on the polyphenyl polymethylene polyisocyanate is 1: 12.96;
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 triethylene diamine to obtain a premix;
and mixing 50g of prepolymer and 100g of premix for 6s, pouring the mixture into a mold for foaming, wherein the foaming curing time is 14 minutes, and then demolding to obtain the polyurethane soft foam.
Example 4
Adding 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 into a high-pressure reaction kettle for mixing, and then heating to 125 ℃ for ring-opening reaction, wherein the reaction pressure is 0.1MPa, and the reaction time is 3 h; carrying out reduced pressure distillation on the obtained product to remove residual moisture and hydrochloric acid, and then 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;
adding 1000g of toluene diisocyanate into a reaction kettle filled with nitrogen, heating to 55 ℃ at the rotating speed of 250r/min, adding 450g of cottonseed oil-based polyol into the reaction kettle at the speed of 30g/min, heating to 70 ℃, preserving heat for 1h, and cooling to obtain a prepolymer; wherein the molar ratio of-OH on the cottonseed oil based polyol to-NCO on the toluene diisocyanate is 1: 8.52;
mixing 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 to obtain a premix;
and mixing 55g of prepolymer and 100g of premix for 8s, pouring the mixture into a mold for foaming, wherein the foaming curing time is 10 minutes, and then demolding to obtain the polyurethane soft foam.
Example 5
Adding 1000g of epoxy sunflower seed oil (the epoxy value is 5.2 percent), 2.5g of p-toluenesulfonic acid with the mass fraction of 99 percent and 300g of water into a high-pressure reaction kettle for mixing, and then heating to 120 ℃ for ring-opening reaction, wherein the reaction pressure is 0.2MPa, and the reaction time is 4 hours; carrying out reduced pressure distillation on the obtained product to remove residual water and p-toluenesulfonic acid, and then filtering to obtain sunflower oil-based polyol, wherein the hydroxyl value of the sunflower oil-based polyol is 136mgKOH/g, and the functionality is about 2.5;
adding 1000g of polyphenyl polymethylene polyisocyanate into a reaction kettle filled with nitrogen, heating to 60 ℃ at the rotating speed of 300r/min, then adding 400g of sunflower seed oil-based polyol into the reaction kettle at the speed of 25g/min, heating to 65 ℃, preserving heat for 1h, and cooling to obtain a prepolymer; wherein the mol 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 triethylene diamine to obtain a premix;
and mixing 60g of prepolymer and 100g of premix for 10s, pouring the mixture into a mold for foaming, wherein the foaming curing time is 15 minutes, and then demolding to obtain the polyurethane soft foam.
Example 6
Adding 1000g of epoxidized soybean oil (with the epoxy value of 6.17%), 2.0g of sulfuric acid with the mass fraction of 98% and 200g of water into a high-pressure reaction kettle for mixing, and then heating to 105 ℃ for ring-opening reaction, wherein the reaction pressure is 0.2MPa, and the reaction time is 3 hours; carrying out reduced pressure distillation on the obtained product to remove residual water and sulfuric acid, and then 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;
adding 1000g of diphenylmethane diisocyanate into a reaction kettle filled with nitrogen, heating to 50 ℃ at the rotating speed of 200r/min, adding 500g of soybean oil-based polyol into the reaction kettle at the speed of 20g/min, heating to 80 ℃, preserving heat for 2 hours, and cooling to obtain a prepolymer; wherein the molar ratio of-NCO on the soybean oil-based polyol to-NCO on the diphenylmethane diisocyanate is 1: 7.27;
mixing 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 to obtain a premix;
and mixing 50g of prepolymer and 100g of premix for 6s, pouring the mixture into a mold for foaming, wherein the foaming curing time is 11 minutes, and then demolding to obtain the polyurethane soft foam.
Comparative example 1
Mixing 100g of polyether 5041, 1g of silicone oil, 2g of deionized water and 1g of amine catalyst to obtain a mixture; mixing 43g of polyphenyl polymethylene polyisocyanate and the mixture for 8s, pouring the mixture into a mould for foaming, wherein the foaming curing time is 12 minutes, and then demoulding to obtain the petroleum-based polyurethane flexible 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; mixing 43g of polyphenyl polymethylene polyisocyanate and the mixture for 8s, pouring the mixture into a mould for foaming, wherein the foaming curing time is 12 minutes, and then demoulding to obtain the polyurethane flexible foam.
Performance testing
The bio-based content of the polyurethane soft foam obtained in the examples 1 to 6 is tested according to the ASTM D6866, and the test results are shown in Table 1;
TABLE 1 results of measurement of biobased content of polyurethane flexible 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 polyurethane flexible foam obtained by the present invention has a high biobased content.
The polyurethane flexible foams obtained in example 2, comparative example 1 and comparative example 2 were subjected to a performance test according to GB/T24451-. The test results are shown in table 2.
Table 2 results of performance test of the flexible polyurethane foams obtained in example 2 and comparative examples 1 and 2
As can be seen from the table 2, the polyurethane soft foam obtained by the preparation method provided by the invention is not hardened at low temperature, is breathable and not sultry, has moderate supporting force and is degradable, can obviously reduce the dependence on petrochemical products, and is environment-friendly; and the physical properties of the polyurethane foam are close to those of petroleum-based polyurethane flexible foam; the surface of the polyurethane soft foam obtained by the preparation method provided by the invention has no phenomenon of oil spreading and hand sticking, while the surface of the polyurethane soft foam obtained by the comparative example 2 becomes oily and hand sticking.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. The preparation method of the polyurethane flexible foam is characterized by comprising the following steps:
carrying out first mixing on a first vegetable oil polyalcohol 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;
carrying 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;
thirdly, mixing the prepolymer and the premix, and foaming to obtain the polyurethane soft foam;
the mass sum of the first vegetable oil polyol and the second vegetable oil polyol and the mass ratio of the first vegetable oil polyol and the second vegetable oil polyol to the polyurethane soft foam are (50-70): (95.8 to 143.5).
2. The method of claim 1, wherein the first vegetable oil polyol and the second vegetable oil polyol independently have hydroxyl numbers of 60 to 220mg KOH/g and functionalities of 2 to 5.
3. The method of claim 1, wherein the isocyanate comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, and polyphenyl polymethylene polyisocyanate.
4. The method of claim 1, wherein the polyether polyol comprises a slow rebound polyether polyol.
5. The method of claim 1, wherein the catalyst comprises an amine catalyst;
the foam stabilizer comprises silicone oil;
the blowing agent includes water.
6. The method according to any one of claims 1 to 3, wherein the mass ratio of the first vegetable oil polyol to the isocyanate is 3 to 6: 10.
7. the preparation method according to 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): (0.5-2.0): (1.5-3.5): (1.8-4.0).
8. The preparation method according to claim 1, wherein the mass ratio of the prepolymer to the premix is 4-6: 10.
9. the preparation method according to claim 6, wherein the temperature of the first mixing is 65-85 ℃ and the time is 1-3 h;
the first mixing is carried out under an inert atmosphere.
10. The flexible polyurethane foam prepared by the preparation method of any one of claims 1 to 9, wherein the content of the bio-based material in the flexible polyurethane foam is 30% to 60%.
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