CN115490826A - Polyurethane porous material and preparation method thereof - Google Patents
Polyurethane porous material and preparation method thereof Download PDFInfo
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- CN115490826A CN115490826A CN202211353363.4A CN202211353363A CN115490826A CN 115490826 A CN115490826 A CN 115490826A CN 202211353363 A CN202211353363 A CN 202211353363A CN 115490826 A CN115490826 A CN 115490826A
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- Prior art keywords
- polyurethane
- porous material
- chain extender
- polyurethane prepolymer
- surfactant
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- 239000011148 porous material Substances 0.000 title claims abstract description 82
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 56
- 239000004814 polyurethane Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 54
- 239000004970 Chain extender Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 30
- 239000004094 surface-active agent Substances 0.000 claims abstract description 29
- 229920005862 polyol Polymers 0.000 claims abstract description 23
- 150000003077 polyols Chemical class 0.000 claims abstract description 23
- 239000012948 isocyanate Substances 0.000 claims abstract description 16
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 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 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 150000001412 amines Chemical group 0.000 claims description 3
- 239000000539 dimer Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012454 non-polar solvent Substances 0.000 claims description 3
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 239000013638 trimer Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 abstract description 16
- 230000002209 hydrophobic effect Effects 0.000 abstract 1
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- 238000004108 freeze drying Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 229920005830 Polyurethane Foam Polymers 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 239000011496 polyurethane foam Substances 0.000 description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- -1 polytrimethylene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 229920002012 Pluronic® F 38 Polymers 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
Images
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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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/05—Open cells, i.e. more than 50% of the pores are open
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a polyurethane porous material and a preparation method thereof, belonging to the technical field of porous materials. Mixing polyol and isocyanate to carry out prepolymerization reaction to obtain a polyurethane prepolymer; and then mixing the polyurethane prepolymer with a solvent, a surfactant, a chain extender and a dispersed phase, carrying out chain extension reaction, and drying to obtain the polyurethane porous material. According to the invention, firstly, a polyurethane prepolymer is synthesized, then a solvent, a surfactant, a chain extender and a disperse phase are added to construct a high internal phase emulsion, and a chain extension reaction is carried out, so that the obtained polyurethane porous material has the advantages of low density, high aperture ratio, uniform aperture, controllable size, more regular molecular structure, elasticity, toughness and adjustable hydrophilic and hydrophobic properties. The results of the examples show that the polyurethane porous material prepared by the invention has uniform spherical pores, and through holes are arranged among the large pores, namely, the open pore structure.
Description
Technical Field
The invention relates to the technical field of porous materials, in particular to a polyurethane porous material and a preparation method thereof.
Background
Polyurethane is a kind of synthetic macromolecule, block copolymer that is synthesized by stepwise polymerization reaction of di-or poly-isocyanate and polyol, and materials with different purposes can be prepared through different molecular designs, and the polyurethane has excellent mechanical properties, processability and biocompatibility, thus the polyurethane is concerned in the field of material science. Polyurethane foam (PUF) is one of the varieties with quite wide application, and recently, the PUF also expands in the fields of filters, catalyst carriers, drug controlled release, tissue engineering scaffolds, and the like, and these fields often require that the pore size of the foam is in the range of tens of micrometers, the pore size distribution is uniform, and the foam has a high specific surface area, and the like. The current preparation method of polyurethane foam is mainly a gas foaming method, the pore size is usually from hundreds of micrometers to tens of millimeters, and the pore size distribution is difficult to control accurately. Therefore, in some application fields with special requirements on pore diameter and pore structure, the development of a novel polyurethane foam preparation technology which can be industrialized and has controllable pore diameter and structure is urgently needed. The high internal phase emulsion template method has the advantages of simple preparation, controllable pore structure, high porosity and the like, and gradually draws attention of people.
The high internal phase emulsion is a high viscosity gel-like emulsion having an internal phase volume fraction greater than 74.05%. Common HIPEs are mostly water-in-oil (W/O) or oil-in-water (O/W) types, which generate CO due to the reaction of water with isocyanate 2 The morphology of the pores is damaged, so that the pore size distribution is not uniform, therefore, the preparation of the polyurethane porous material by using an anhydrous (i.e. oil-in-oil (O/O) type) high internal phase emulsion template is a feasible method, and the polyurethane porous material prepared by the current oil-in-oil type high internal phase emulsion template method is obtained by the step-by-step polymerization reaction of small molecular monomers and has the characteristics of hydrophobicity and high modulus. These properties greatly limit their use in many applications where a certain water absorption and softness of the material is required, such as wound dressings and the like. Therefore, how to prepare a polyurethane porous material with uniform pore diameter, regular structure, open pore structure, and both elasticity and toughness is an urgent problem to be solved in the field.
Disclosure of Invention
The invention aims to provide a polyurethane porous material and a preparation method thereof. The polyurethane porous material prepared by the invention has the advantages of uniform pore size distribution, regular structure, high opening degree, elasticity and toughness.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a polyurethane porous material, which comprises the following steps:
(1) Mixing polyol and isocyanate to carry out prepolymerization reaction to obtain a polyurethane prepolymer;
(2) And (2) mixing the polyurethane prepolymer obtained in the step (1) with a solvent, a surfactant, a chain extender and a dispersed phase, carrying out chain extension reaction, and drying to obtain the polyurethane porous material.
Preferably, the polyol in the step (1) includes one or more of polyether polyol and polyester polyol.
Preferably, the isocyanate in step (1) includes one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and derived dimers and trimers thereof.
Preferably, the chain extender in the step (2) includes one or more of an alcohol chain extender and an amine chain extender.
Preferably, the ratio of the amounts of the polyol, the isocyanate and the substance of the chain extender in the step (1) is 1: (1.5-40): (0.3-41).
Preferably, the surfactant in step (2) comprises ethylene oxide-propylene oxide copolyether.
Preferably, the mass of the surfactant in the step (2) is 1-50% of the total mass of the polyurethane prepolymer, the solvent, the surfactant and the chain extender.
Preferably, the dispersed phase in step (2) is a non-polar solvent incompatible with the mixture of the polyurethane prepolymer and the solvent.
Preferably, the volume of the dispersed phase in the step (2) is 60-95% of the total volume of the polyurethane prepolymer, the solvent, the surfactant, the chain extender and the dispersed phase.
The invention provides a polyurethane porous material prepared by the preparation method in the technical scheme.
The invention provides a preparation method of a polyurethane porous material, which comprises the following steps: (1) Mixing polyol and isocyanate to carry out prepolymerization reaction to obtain a polyurethane prepolymer; (2) And (2) mixing the polyurethane prepolymer obtained in the step (1) with a solvent, a surfactant, a chain extender and a dispersed phase, carrying out chain extension reaction, and drying to obtain the polyurethane porous material. The invention firstly synthesizes polyurethane prepolymer and prepares prepolymer solution, surfactant, chain extender and disperse phase are added into the prepolymer solution to construct high internal phase emulsion and carry out chain extension reaction, the surfactant is added to ensure that the disperse phase is more uniformly and stably dispersed in the system, the uniformity of aperture is improved, the establishment of an oil-in-oil system avoids the reaction of isocyanate and water, and the polyurethane porous material which is prepared stably in the system has more uniform aperture, more regular molecular structure, open pore structure and certain strength and mechanical resilience. The results of the examples show that the polyurethane porous material prepared by the invention has uniform spherical pores, and through holes are arranged among the large pores, namely, the open pore structure.
Drawings
FIG. 1 is an SEM image of a polyurethane porous material prepared in example 1 of the present invention;
FIG. 2 is an SEM photograph of a polyurethane porous material prepared in example 2 of the present invention;
FIG. 3 is an SEM photograph of a polyurethane porous material prepared in example 3 of the present invention;
FIG. 4 is an infrared spectrum of the polyurethane porous material prepared in examples 1 to 3 of the present invention;
FIG. 5 is a water absorption capacity curve of the polyurethane porous materials prepared in examples 1 to 3 of the present invention;
FIG. 6 is a 3 cycle compressive stress-strain curve at a fixed strain of 70% for example 2 of the present invention.
Detailed Description
The invention provides a preparation method of a polyurethane porous material, which comprises the following steps:
(1) Mixing polyol and isocyanate to carry out prepolymerization reaction to obtain a polyurethane prepolymer;
(2) And (2) mixing the polyurethane prepolymer obtained in the step (1) with a solvent, a surfactant, a chain extender and a dispersed phase, carrying out chain extension reaction, and drying to obtain the polyurethane porous material.
In the present invention, the sources of the components are not particularly limited, unless otherwise specified, and commercially available products known to those skilled in the art may be used.
The invention mixes polyol and isocyanate to carry out prepolymerization reaction to obtain polyurethane prepolymer.
In the present invention, the polyol preferably includes one or more of polyether polyol and polyester polyol; more preferably one or more of polyethylene glycol, polypropylene glycol, polytetrahydrofuran glycol, polycaprolactone glycol, polytrimethylene ether glycol, and polycarbonate glycol. In the present invention, when the polyol includes a plurality of components, the ratio of the components is not particularly limited, and may be blended in any ratio.
In the present invention, the isocyanate preferably includes one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and dicyclohexylmethane diisocyanate, and a dimer and a trimer derived therefrom. In the present invention, when the isocyanate includes a plurality of components, the ratio of the components is not particularly required in the present invention, and it is sufficient if the ratio is arbitrary.
In the present invention, the ratio of the amounts of the substances of polyol and isocyanate is preferably 1: (1.5 to 40), more preferably 1: (2-20). In the present invention, the ratio of the amounts of the polyol and isocyanate is limited to the above range, and the structure of the polyurethane prepolymer can be adjusted to further improve the performance.
In the present invention, the temperature of the prepolymerization reaction is preferably 30 to 140 ℃; the time of the prepolymerization reaction is preferably 1 to 5 hours. The invention limits the temperature and time of the prepolymerization reaction within the above range, can adjust the structure of the polyurethane prepolymer, is beneficial to the subsequent chain extension reaction, and obtains the porous material with excellent performance.
After the prepolymerization reaction is finished, the product of the prepolymerization reaction is preferably cooled to obtain the polyurethane prepolymer.
After the polyurethane prepolymer is obtained, the polyurethane prepolymer is mixed with a solvent, a surfactant, a chain extender and a dispersion phase to carry out chain extension reaction, and then the mixture is dried to obtain the polyurethane porous material.
In the invention, the polyurethane prepolymer is mixed with a solvent, a surfactant, a chain extender and a dispersed phase to form an oil-in-oil type high internal phase emulsion, wherein the polyurethane prepolymer forms a continuous phase with the solvent, the surfactant and the chain extender.
In the present invention, the solvent preferably includes one or more of dimethyl sulfoxide, butanone, ethyl acetate, N-dimethylformamide, N-dimethylacetamide, formamide, toluene, and tetrahydrofuran.
In the present invention, the ratio of the total mass of the polyurethane prepolymer and the chain extender to the mass of the solvent is preferably (0.25 to 4): 1. the invention limits the ratio of the total mass of the polyurethane prepolymer and the chain extender to the mass of the solvent within the range, and can ensure that the polyurethane prepolymer is fully dissolved.
In the present invention, the surfactant preferably comprises an ethylene oxide-propylene oxide copolyether, more preferably one or more of Pluronic F-38, F88, P-85 and P-123.
In the present invention, the mass of the surfactant is preferably 1 to 50%, more preferably 5 to 40% of the total mass of the polyurethane prepolymer, the solvent, the surfactant and the chain extender. The invention limits the quality of the surfactant within the range, can reduce the interfacial tension between a dispersed phase and a continuous phase, is beneficial to forming internal phase liquid drops and preventing the liquid drops from aggregating, obtains stable high internal phase emulsion, and further improves the pore diameter uniformity of the porous material.
In the present invention, the chain extender preferably comprises one or more of an alcohol chain extender and an amine chain extender, more preferably comprises one or more of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, diaminodicyclohexylmethane, diaminodiphenylmethane, 3,3 '-dichloro-4,4' -diaminodiphenylmethane, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, glycerol and pentaerythritol. In the invention, the chain extender is used for enabling the polyurethane prepolymer to have chain extension reaction in a continuous phase, improving the regularity of a polyurethane molecular structure and endowing a porous material with better mechanical property.
In the present invention, the ratio of the amounts of the substances of the polyol and the chain extender is preferably 1: (0.3 to 41), more preferably 1: (0.5-30). According to the invention, the ratio of the amounts of the polyol and the chain extender is limited within the range, so that the polyurethane prepolymer can fully perform chain extension reaction to obtain the porous polyurethane material, and the performance of the porous polyurethane material is further improved.
In the present invention, the dispersed phase is preferably a non-polar solvent incompatible with the mixture of the polyurethane prepolymer and the solvent, and more preferably one or more of paraffin oil, octadecane, hexadecane, tetradecane, dodecane, petroleum ether, sunflower oil and soybean oil. The invention adopts the type of disperse phase incompatible with the mixture of polyurethane and solvent, aims to construct an oil-in-oil high internal phase system, and can avoid the problems that water reacts with diisocyanate to generate carbon dioxide when water is used as a disperse phase or a continuous phase in the traditional water-in-oil or oil-in-water system, so that the emulsion is unstable and large uncontrollable bubble holes appear in the subsequently obtained material.
In the invention, the volume of the dispersed phase is preferably 60-95% of the total volume of the polyurethane prepolymer, the solvent, the surfactant, the chain extender and the dispersed phase. The invention limits the volume of the dispersed phase in the range, can adjust the content of the internal phase, and improves the porosity of the porous material after removing the dispersed phase.
In the invention, the mixing of the polyurethane prepolymer, the solvent, the surfactant, the chain extender and the dispersed phase is preferably as follows: firstly, mixing a polyurethane prepolymer with a solvent to obtain a polyurethane prepolymer solution, then adding a surfactant and a chain extender, and finally adding a dispersed phase. In the present invention, the dispersed phase is preferably dropwise added. In the invention, the dropping can make the dispersed phase more easily form spherical small droplets and uniformly disperse in the continuous phase, thereby further improving the aperture uniformity and regularity of the porous polyurethane.
In the invention, the temperature of the chain extension reaction is preferably 0-120 ℃; the time of the chain extension reaction is preferably 0.5 to 24 hours. The invention limits the temperature and time of the chain extension reaction within the range, can fully carry out the chain extension reaction, and further improves the performance of polyurethane.
After the chain extension reaction is completed, the present invention preferably performs post-treatment on the product of the chain extension reaction. In the present invention, the post-treatment is for the dispersed phase, surfactant and solvent. The operation of the post-treatment in the present invention is not particularly limited, and a method of removing the dispersed phase, the surfactant and the solvent, which is well known to those skilled in the art, may be used.
In the present invention, the drying is preferably freeze-drying; the temperature of the freeze drying is preferably-40 to-100 ℃; the freeze drying time is preferably 1 to 7 days; the degree of vacuum of the freeze-drying is preferably 5 to 100Pa. In the present invention, the freeze-drying is used to remove the dispersed phase from the product, resulting in a porous structure.
According to the invention, firstly, a polyurethane prepolymer is synthesized, then a solvent, a surfactant, a chain extender and a disperse phase are added to construct a high internal phase emulsion and carry out chain extension reaction, and the composition and the dosage of each component are controlled, so that the obtained polyurethane porous material has more uniform pore diameter and more regular molecular structure.
The invention provides a polyurethane porous material prepared by the preparation method in the technical scheme.
The polyurethane porous material provided by the invention has uniform pore diameter, an open pore structure, elasticity, toughness and adjustable hydrophilicity and hydrophobicity. In the present invention, the pore diameter of the polyurethane porous material is preferably 1 to 100 μm; the density of the polyurethane porous material is preferably 100-300 mg/cm 3 。
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Adding 50g of polyethylene glycol and 16.72g of toluene diisocyanate into a 500mL round-bottom four-mouth flask with a mechanical stirrer and a vacuum device in sequence, heating to 100 ℃, carrying out prepolymerization for 3h, cooling to room temperature to obtain a polyurethane prepolymer, and adding 163.15g of tetrahydrofuran to obtain a polyurethane prepolymer solution;
(2) Adding 17g of polyurethane prepolymer solution, 0.24g of pentaerythritol (the mass ratio of the total mass of the polyurethane prepolymer and the pentaerythritol to the mass of tetrahydrofuran is 7:3) and 3242 g of P-1230.862 (the mass of P-123 is 5% of the mass of the polyurethane prepolymer solution, P-123 and pentaerythritol) into a 250mL round-bottom four-neck flask with a mechanical stirring head in sequence to form a continuous phase, then dropwise adding 23.43g of tetradecane (the volume of the tetradecane is 65% of the total volume of the polyurethane prepolymer solution, P-123 and the pentaerythritol) to obtain an oil-in-oil high internal phase emulsion, polymerizing for 24 hours at 40 ℃, removing the solvent and dispersing the phase equally, and freeze-drying for 1 day at-80 ℃ and 80Pa to obtain the polyurethane porous material PU-1.
Example 2
(1) Adding 25g of polyethylene glycol, 25g of polytrimethylene ether glycol and 18.08g of diphenylmethane diisocyanate into a 500mL round-bottom four-mouth flask with a mechanical stirrer and a vacuum device in sequence, heating to 120 ℃, carrying out prepolymerization reaction for 3h, cooling to room temperature to obtain a polyurethane prepolymer, and adding 163.92g of tetrahydrofuran to obtain a polyurethane prepolymer solution;
(2) Adding 17g of polyurethane prepolymer solution, 0.16g of diethylenetriamine (the mass ratio of the total mass of the polyurethane prepolymer and the diethylenetriamine to the mass of tetrahydrofuran is 7:3) and P-852.57g in sequence into a 250mL round-bottom four-mouth flask with a mechanical stirring head, taking the solutions as a continuous phase, then dropwise adding 41.28g of tetradecane (the volume of the tetradecane is 75 percent of the total volume of the polyurethane prepolymer solution, P-85, diethylenetriamine and the tetradecane) to obtain an oil-in-oil type high internal phase emulsion, polymerizing for 24 hours at 40 ℃, removing the solvent and dispersing the phase equally, and freeze-drying for 1 day at-80 ℃ and 80Pa to obtain the polyurethane porous material PU-2.
Example 3
(1) Adding 50g of polytetrahydrofuran glycol and 16.84g of isophorone diisocyanate into a 500mL round-bottom four-mouth flask with a mechanical stirrer and a vacuum device in sequence, heating to 60 ℃, carrying out prepolymerization for 3 hours, cooling to room temperature to obtain a polyurethane prepolymer, and adding 163.05g of tetrahydrofuran to obtain a polyurethane prepolymer solution;
(2) 17g of polyurethane prepolymer solution, 0.17g of 1, 4-butanediol (the mass ratio of the total mass of the polyurethane prepolymer and 1,4-butanediol to the mass of tetrahydrofuran is 7:3) and P884.29g are sequentially added into a 250mL round-bottom four-neck flask provided with a mechanical stirring head to serve as a continuous phase, 84.80g of tetradecane (the volume of the tetradecane is 85% of the total volume of the polyurethane prepolymer solution, P88, 1,4-butanediol and the tetradecane) is dropwise added to obtain an oil-in-oil type high internal phase emulsion, the oil-in-oil type high internal phase emulsion is polymerized for 24 hours at 40 ℃, the solvent and the dispersion phase are removed, and the oil-in-oil type high internal phase emulsion is subjected to freeze drying at 80 ℃ below zero and 80Pa for 1 day to obtain the polyurethane porous material PU-3.
The polyurethane porous materials prepared in examples 1 to 3 were tested for density, pore size and modulus, and the results are shown in Table 1.
TABLE 1 Density, pore size and modulus of polyurethane cellular materials prepared in examples 1 to 3
As can be seen from Table 1, by varying the types of polyol and diisocyanate, polyurethane cellular materials of different densities, pore sizes and mechanical properties can be obtained.
The polyurethane porous materials prepared in examples 1 to 3 were scanned, and their SEM images are shown in fig. 1 to 3, respectively. As can be seen from FIGS. 1 to 3, the polyurethane porous material prepared by the present invention has uniform spherical pores, and through holes, i.e., open pore structures, are formed between the large pores.
The infrared spectra of the polyurethane porous materials prepared in examples 1 to 3 are shown in fig. 4. As can be seen in FIG. 4, 2260cm -1 No peak was observed indicating that all isocyanate groups reacted to completion, 1702, 1622 and 1100cm -1 The absorption peaks at (a) and (b) correspond to a carbonyl group in a urethane bond (C = O), a carbonyl group in a urea bond (C = O), and an ether bond in a polyol (C-O-C), respectively, indicating successful production of a polyurethane porous material.
The water absorption capacity of the polyurethane porous materials prepared in examples 1 to 3 is shown in FIG. 5. As can be seen from FIG. 5, the polyurethane porous materials with different water absorption capacities can be obtained by changing the components and the mixture ratio of the polyol.
Fig. 6 is a stress-strain curve of 3 cycles of compression in example 2 when the constant strain is 70%, and it can be seen from fig. 6 that after the material reaches 70% strain under a certain load in the first cycle, the material can recover to 90% of the original sample after the load is removed, and the material can recover to more than 80% of the original sample and tend to be stable in the second and third cycles although the recovery degree is reduced. Indicating that the material has better flexibility and rebound resilience.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a polyurethane porous material comprises the following steps:
(1) Mixing polyol and isocyanate to carry out prepolymerization reaction to obtain a polyurethane prepolymer;
(2) And (2) mixing the polyurethane prepolymer obtained in the step (1) with a solvent, a surfactant, a chain extender and a dispersed phase, carrying out chain extension reaction, and drying to obtain the polyurethane porous material.
2. The method according to claim 1, wherein the polyol in the step (1) comprises one or more of polyether polyol and polyester polyol.
3. The method according to claim 1, wherein the isocyanate in step (1) comprises one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and derived dimers and trimers thereof.
4. The preparation method according to claim 1, wherein the chain extender in the step (2) comprises one or more of an alcohol chain extender and an amine chain extender.
5. The method according to claim 1, wherein the ratio of the amounts of the polyol, the isocyanate and the chain extender in the step (1) is 1: (1.5-40): (0.3-41).
6. The method according to claim 1, wherein the surfactant in the step (2) comprises ethylene oxide-propylene oxide copolyether.
7. The preparation method according to claim 1, wherein the mass of the surfactant in the step (2) is 1 to 50% of the total mass of the polyurethane prepolymer, the solvent, the surfactant and the chain extender.
8. The method according to claim 1, wherein the dispersed phase in the step (2) is a nonpolar solvent incompatible with the mixture of the polyurethane prepolymer and the solvent.
9. The preparation method according to claim 1 or 8, wherein the volume of the dispersed phase in the step (2) is 60 to 95% of the total volume of the polyurethane prepolymer, the solvent, the surfactant, the chain extender and the dispersed phase.
10. A polyurethane porous material produced by the production method according to any one of claims 1 to 9.
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