CN114940738A - Polyurethane composition, polyurethane foam, and preparation method and application thereof - Google Patents
Polyurethane composition, polyurethane foam, and preparation method and application thereof Download PDFInfo
- Publication number
- CN114940738A CN114940738A CN202210623817.9A CN202210623817A CN114940738A CN 114940738 A CN114940738 A CN 114940738A CN 202210623817 A CN202210623817 A CN 202210623817A CN 114940738 A CN114940738 A CN 114940738A
- Authority
- CN
- China
- Prior art keywords
- polyether polyol
- polyurethane composition
- foaming agent
- catalyst
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 51
- 239000004814 polyurethane Substances 0.000 title claims abstract description 51
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 34
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 113
- 229920000570 polyether Polymers 0.000 claims abstract description 113
- 229920005862 polyol Polymers 0.000 claims abstract description 113
- 150000003077 polyols Chemical class 0.000 claims abstract description 113
- 239000004088 foaming agent Substances 0.000 claims abstract description 70
- 239000002131 composite material Substances 0.000 claims abstract description 59
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 34
- 239000001294 propane Substances 0.000 claims abstract description 25
- 239000012948 isocyanate Substances 0.000 claims abstract description 24
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 24
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 41
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 34
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 30
- 239000003999 initiator Substances 0.000 claims description 27
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 21
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 15
- 238000005187 foaming Methods 0.000 claims description 15
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 229920002545 silicone oil Polymers 0.000 claims description 12
- 239000004604 Blowing Agent Substances 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 9
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000007259 addition reaction Methods 0.000 claims description 8
- AQZABFSNDJQNDC-UHFFFAOYSA-N 2-[2,2-bis(dimethylamino)ethoxy]-1-n,1-n,1-n',1-n'-tetramethylethane-1,1-diamine Chemical compound CN(C)C(N(C)C)COCC(N(C)C)N(C)C AQZABFSNDJQNDC-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 235000011056 potassium acetate Nutrition 0.000 claims description 7
- 235000019482 Palm oil Nutrition 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002540 palm oil Substances 0.000 claims description 6
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 6
- 238000005829 trimerization reaction Methods 0.000 claims description 6
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 claims description 5
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 5
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- WMNWJTDAUWBXFJ-UHFFFAOYSA-N 3,3,4-trimethylheptane-2,2-diamine Chemical compound CCCC(C)C(C)(C)C(C)(N)N WMNWJTDAUWBXFJ-UHFFFAOYSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 claims description 3
- NLOLSXYRJFEOTA-UPHRSURJSA-N (z)-1,1,1,4,4,4-hexafluorobut-2-ene Chemical compound FC(F)(F)\C=C/C(F)(F)F NLOLSXYRJFEOTA-UPHRSURJSA-N 0.000 claims description 3
- DPXFJZGPVUNVOT-UHFFFAOYSA-N 3-[1,3-bis[3-(dimethylamino)propyl]triazinan-5-yl]-n,n-dimethylpropan-1-amine Chemical compound CN(C)CCCC1CN(CCCN(C)C)NN(CCCN(C)C)C1 DPXFJZGPVUNVOT-UHFFFAOYSA-N 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical group [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000006260 foam Substances 0.000 description 43
- 239000000126 substance Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 5
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000006261 foam material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- LDVVMCZRFWMZSG-OLQVQODUSA-N (3ar,7as)-2-(trichloromethylsulfanyl)-3a,4,7,7a-tetrahydroisoindole-1,3-dione Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)Cl)C(=O)[C@H]21 LDVVMCZRFWMZSG-OLQVQODUSA-N 0.000 description 3
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 3
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 3
- 239000005745 Captan Substances 0.000 description 3
- 229940117949 captan Drugs 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 3
- 229960005080 warfarin Drugs 0.000 description 3
- PJVWKTKQMONHTI-UHFFFAOYSA-N warfarin Chemical compound OC=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 PJVWKTKQMONHTI-UHFFFAOYSA-N 0.000 description 3
- NLOLSXYRJFEOTA-OWOJBTEDSA-N (e)-1,1,1,4,4,4-hexafluorobut-2-ene Chemical compound FC(F)(F)\C=C\C(F)(F)F NLOLSXYRJFEOTA-OWOJBTEDSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 229940051271 1,1-difluoroethane Drugs 0.000 description 1
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 1
- -1 R600 Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000011998 white catalyst Substances 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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic 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
- C08G18/28—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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
-
- 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
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D23/00—General constructional features
- F25D23/06—Walls
- F25D23/065—Details
- F25D23/066—Liners
-
- 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
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
-
- 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
- C08G2110/0075—Foam properties prepared with an isocyanate index of 60 or lower
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/16—Unsaturated hydrocarbons
- C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
-
- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D2201/00—Insulation
- F25D2201/10—Insulation with respect to heat
- F25D2201/12—Insulation with respect to heat using an insulating packing material
Abstract
The invention discloses a polyurethane composition, polyurethane foam, and a preparation method and application thereof, wherein the polyurethane composition comprises the following components in parts by mass: 67-100 parts of polyether polyol, 0-33 parts of polyester polyol, 0.5-9 parts of surfactant, 1-15 parts of composite catalyst, 0.5-7 parts of water and 8-60 parts of composite foaming agent, wherein the isocyanate is used for leading the isocyanate index to be 1.0-1.5; the composite foaming agent comprises, by total mass, 100% of pentane 10-75%, a hydrofluoroolefin foaming agent 5-70% and propane 2-30%. The composite foaming agent provided by the invention has a synergistic effect, so that the problems caused by the independent use of each physical foaming agent can be effectively avoided, and the rigid polyurethane foam with good performance can be obtained.
Description
Technical Field
The invention relates to a polyurethane composition, in particular to a polyurethane composition, polyurethane foam, and a preparation method and application thereof.
Background
The rigid polyurethane foam is prepared by polymerization reaction of polyurethane polyol composition and isocyanate in the presence of catalyst and other assistants, has the characteristics of excellent heat insulation performance, sound insulation, light weight, high specific strength, good processability and the like, and is widely used as heat-insulating and cold-insulating materials, such as refrigerators. In order to achieve better heat insulation and heat preservation effects, a certain amount of physical foaming agent with low boiling point and low thermal conductivity is required to be added into the foam material, unfortunately, the traditional polyurethane foaming agent CFC-11 has serious damage effect on an ozone layer, the second generation foaming agent HCFC-141b is the most used hydrochlorofluorocarbon foaming agent, but the HCFC-141b is forbidden in China in 2020, and the HCFC-141b foaming agent can be replaced by the whole water, pentane, HFC-245fa, HFC-134a, HFC-152a, R600, HFO foaming agent and the like;
wherein CFC-11 is monofluorotrichloromethane, HCFC-141b is monofluorodichloroethane, HFC-245fa is 1,1,1,3, 3-pentafluoropropane, HFC-134a is 1,1,1, 2-tetrafluoroethane, HFC-152a is 1, 1-difluoroethane, R600 is n-butane, and HFO blowing agents are hydrofluoroolefin blowing agents.
In contrast to halogenated hydrocarbon blowing agents, alkane blowing agents (e.g., pentane, butane, etc.) are free of halogen atoms, have zero Ozone Depletion Potential (ODP), and have approximately zero green house effect potential (GWP). The foaming agent is environment-friendly, relatively low in price and one of ideal foaming agent alternatives, however, the boiling point of Cyclopentane (CP) is as high as 49 ℃, the boiling points of normal butane and isobutane are lower than 0 ℃, the boiling points are known to be too high or too low in the field to be suitable for being used as physical foaming agents, and the foaming agents have certain plasticity and are easy to deteriorate the dimensional stability of foams. Therefore, the pouring amount is generally required to be increased to improve the mass density of the foam so as to ensure the dimensional stability of the foam, but the production cost of the foam is greatly increased; meanwhile, the corrosion phenomenon of the liners of pentane and butane is serious, and a liner pit can be formed under the conditions of high temperature and low temperature, so that the appearance of the refrigerator is influenced.
The hydro-fluoro-olefin foaming agent has ODP (optical density distribution) of almost 0 and GWP (global warming potential) of less than 10, is a better fourth-generation foaming agent, and the refrigerator polyurethane foam using the hydro-fluoro-olefin foaming agent has low heat conductivity and better comprehensive performance. However, the foaming agent is expensive, the polyurethane foam prepared by independently adopting the foaming agent has high cost, and a large amount of the foaming agent is easy to form a complex with a milky catalyst, so that the stability of the foaming agent is reduced, and meanwhile, the foaming agent is easy to corrode a plastic liner material of a refrigerator, so that the liner is cracked, swelled and the like.
The invention aims to overcome the defects of the foaming agent and provide the polyurethane composition prepared from the environment-friendly composite foaming agent so as to meet the requirement of low manufacturing cost, and the prepared foam has the advantages of low density, good stability, low conductivity, high strength and weak corrosion to the inner container of the refrigerator.
Disclosure of Invention
In order to solve the technical problems, the invention provides a polyurethane composition, a polyurethane foam, and a preparation method and application thereof.
According to one aspect of the present invention, there is first provided a polyurethane composition comprising a polyether polyol and an isocyanate capable of reacting therewith; the foaming agent adopted by the polyurethane composition is a composite foaming agent and is a mixture consisting of pentane, a hydrofluoroolefin foaming agent and propane. The composite foaming agent has synergistic effect, so that the problems caused by the independent use of physical foaming agents can be effectively avoided, and the rigid polyurethane foam with good performance can be obtained.
According to another aspect of the present invention, there is also provided a polyurethane foam prepared from the above polyurethane composition.
According to a third aspect of the invention, a preparation method of the polyurethane foam is also provided.
According to a fourth aspect of the present invention, there is also provided a refrigerator comprising the aforementioned polyurethane foam.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a polyurethane composition comprises the following components in parts by mass:
67-100 parts of polyether polyol,
0 to 33 parts of polyester polyol,
0.5 to 9 parts of a surfactant,
1-15 parts of a composite catalyst,
0.5 to 7 parts of water,
8-60 parts of a composite foaming agent,
isocyanate with an isocyanate index of 1.0-1.5;
the composite foaming agent comprises, by total mass, 100% of pentane 10-75%, a hydrofluoroolefin foaming agent 5-70% and propane 2-30%.
Propane (R290) is poorly soluble in polyols, is less useful in rigid foam polyurethane foams, has a low boiling point (-44 ℃) and is more demanding on the process, and when propane alone is used for foaming, it easily escapes from the reactants, causing increased bubbles on the foam surface, which adversely affects the foam properties.
The invention discovers through continuous research that the pentane, the hydro-fluoroolefin foaming agent and the propane form the composite foaming agent, the performance defect caused by independently using each component as the foaming agent can be solved, the performance of the foam can be improved, the prepared polyurethane foam with fine foam holes and good heat conductivity coefficient can be prepared, the mass density of the foam can be reduced under the condition of keeping the stability of the foam, the cost of raw materials can be controlled, the corrosivity to a plastic liner is low, and the composite foaming agent is more suitable for preparing heat-insulating and cold-insulating materials.
According to the invention, the mass content of the hydro-fluoro-olefin foaming agent in the composite foaming agent is not more than 70%, so that the corrosion to a plastic liner material of a refrigerator can be reduced, the cracking and swelling risks of the liner of the refrigerator can be effectively reduced, and the complexing probability with a milky-white catalyst can be reduced; the content of pentane in the mixed foaming agent is approximately kept above 10%, and a certain amount of R290 is added, wherein the weight of R290 in the composite foaming agent is not more than 30%, so that the initial foaming capacity of the composition can be improved, the fluidity is improved, the dimensional stability of the foam is enhanced, and the problem that propane gas escapes to the surface of the foam due to too much addition can be avoided, so that the surface defects of the foam are effectively reduced, and the injection amount can be reduced to reduce the using amount of polyurethane foam and reduce the production cost due to high vapor pressure of propane; in addition, the mixed blowing agent systems used herein also allow for increased maximum allowable blowing agent loading in the composition, thereby reducing foam density.
In a preferred embodiment of the present invention, the polyether polyol is a combination of polyether polyol a, polyether polyol B, polyether polyol C, and polyether polyol D;
the polyether polyol A has a hydroxyl value of 200-550 mgKOH/g and a functionality of 6-8, and is prepared by performing addition reaction on at least one of sucrose and sorbitol serving as an initiator and olefin oxide;
the polyether polyol B is amino polyether polyol, has a hydroxyl value of 300-550 mgKOH/g and a functionality of 4-6, and is prepared by addition reaction of o-toluenediamine and alkylene oxide;
the hydroxyl value of the polyether polyol C is 250-495 mgKOH/g, the functionality is 3-6, and the polyether polyol C is prepared by performing addition reaction on at least one of palm oil and soybean oil serving as an initiator and olefin oxide;
the polyether polyol D has a hydroxyl value of 100-300 mgKOH/g and a functionality of 2-4, and is prepared by addition reaction of at least one initiator selected from diethylene glycol, glycerol and propylene glycol with an alkylene oxide.
In a preferred embodiment of the present invention, the polyether polyol comprises, based on 100% of the total mass, the following components:
5 to 85 percent of polyether polyol A, preferably 5 to 72 percent,
2-85%, preferably 10-70%,
0 to 80 percent of polyether polyol C, preferably 10 to 70 percent,
0-30% of polyether polyol D, preferably 5-20%.
The high-functionality polyether used in the polyether polyol can provide sufficient crosslinking degree and rigidity for foam, and the amine polyether with autocatalysis can improve the initial viscosity of a system at the initial reaction stage and wrap the escape of low-boiling-point propane, so that more propane can be wrapped in the foam, the flowability of the foam is improved, the density difference of the foam is reduced, the density distribution is uniform, the strength of the foam is improved, and the defect of the foam is reduced.
In a preferred embodiment of the present invention, the polyester polyol has a hydroxyl value of 150 to 400mgKOH/g, a functionality of 2 to 5, and is a phthalic anhydride polyester polyol obtained by condensing phthalic anhydride and a polyhydric alcohol.
The phthalic anhydride polyester polyol contains a benzene ring structure, so that the prepared foam has high strength, good dimensional stability and low heat conductivity coefficient, and meanwhile, the phthalic anhydride polyester has high activity, so that the initial viscosity can be improved, the foaming agent can be wrapped, the dimensional stability of the foam can be improved, the shrinkage rate of the foam can be reduced, and the foam cost can be reduced.
In a preferred embodiment of the present invention, the surfactant is a silicon-carbon surfactant, preferably at least one of silicone oil AK8830, silicone oil L6863, silicone oil B84806, and silicone oil B8492.
In a preferred embodiment of the invention, the composite catalyst comprises a foaming catalyst, a gel catalyst and a trimerization catalyst, wherein the mass ratio of the foaming catalyst to the gel catalyst to the trimerization catalyst is (0-1): 0.2-5): 0-2, preferably (0-1): 1-4): 0.5-2;
preferably, the foaming catalyst is one or a mixture of more of pentamethyldiethylenetriamine, tetramethylhexanediamine and bis-dimethylaminoethylether in any proportion;
preferably, the gel catalyst is one or a mixture of more of methylimidazole, N-dimethylcyclohexylamine, N-methylpyrrolidone and PT303 of the New chemical formula in any proportion;
preferably, the trimerization catalyst is one or a mixture of more of potassium formate, 1,3, 5-tris (dimethylaminopropyl) hexahydrotriazine, 2-hydroxy-N, N, N-trimethyl-1-propylamine formate (TMR-2) and potassium acetate in any proportion.
Preferably, the pentane is at least one of cyclopentane and isopentane, and further preferably is cyclopentane or a mixture of cyclopentane and isopentane, and the content of the cyclopentane and the isopentane in the mixture is 30-95% and 5-70% of the isopentane.
Preferably, the hydrofluoroolefin blowing agent is at least one of trans-1-chloro-3, 3, 3-trifluoropropene (LBA), cis-1, 1,1,4,4, 4-hexafluoro-2-butene (OPteon-1100), trans-1, 1,1,4,4, 4-hexafluoro-2-butene (OPteon-1150), trans-1, 1,1, 3-tetrafluoropropene (GBA), further preferably trans-1-chloro-3, 3, 3-trifluoropropene (LBA), which is the most widely used blowing agent in the industry at present.
In a preferred embodiment of the invention, the isocyanate is polymeric MDI, preferably polymeric MDI with NCO content of 29-32%, and more preferably one or more of Wanhua PM-200, Wanhua PM-2010 and Wanhua PM-400.
The present invention also provides a polyurethane foam made from the polyurethane composition described above.
The present invention also provides a process for preparing a polyurethane foam from the polyurethane composition as hereinbefore described comprising the steps of:
1) uniformly mixing polyether polyol, polyester polyol, a surfactant, a composite catalyst, water and a composite foaming agent, and cooling to below 10 ℃ to obtain a mixture;
2) mixing the mixture obtained in the step 1) with isocyanate, and foaming at high pressure to prepare hard polyurethane foam;
preferably, the high-pressure foaming condition is that the pressure of a gun head is 130-150 Kpa, and the temperature is 15-19 ℃.
The invention also provides the use of a polyurethane foam prepared from the polyurethane composition as hereinbefore described as a refrigerator material.
The polyurethane composition of the present invention has the following beneficial effects:
(1) the polyurethane foam prepared by the polyurethane composition has ODP and GWP of almost 0, is green and environment-friendly;
(2) the polyurethane foam prepared by adopting the polyurethane composition has high strength, and the pouring amount of a foaming material can be effectively reduced, so that the production cost of the foam is reduced, and the customer income is improved;
(3) the polyurethane foam prepared by adopting the polyurethane composition disclosed by the invention is fine and uniform in foam pores, low in heat conductivity coefficient and good in heat insulation performance, and can reduce the energy consumption of a refrigerator;
(4) the polyurethane foam prepared by the composition has good fluidity, uniform density distribution and small expansion rate after demoulding, can effectively wrap the low-boiling-point foaming agent, reduces surface defects and improves the appearance of products.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The following embodiments refer to the following main sources of materials and reagents:
trans-1-chloro-3, 3, 3-trifluoropropene (LBA): honeywell
Cis-1, 1,1,4,4, 4-hexafluoro-2-butene (OPteon-1100): kemu
Trans-1, 1,1,4,4, 4-hexafluoro-2-butene (OPteon-1150): kemu
Trans-1, 1,1, 3-tetrafluoropropene (GBA): honeywell
Cyclopentane (CP): chemical industry of Longshan mountain
Isopentane (IP): chemical industry of Longshan mountain
Propane: metallocene gas
Polymeric MDI: wanhua PM-200
Silicone oil B8492: mai chart
Silicone oil B84806: mai chart
Silicone oil L6863: mai chart
Silicone oil AK 8830: demeishi adhesive
Pentamethyldiethylenetriamine: chemistry of Xindian
Bis-dimethylaminoethyl ether: opening smooth enterprises
Tetramethylhexamethylenediamine: chemical industry of Demao
Methyl imidazole: merck chemistry
Potassium formate: fengtai chemical industry
1,3, 5-tris (dimethylaminopropyl) hexahydrotriazine: chemistry of Xindian
N, N-dimethylcyclohexylamine: new classic chemistry
N-methylpyrrolidone: basf et al
2-hydroxy-N, N-trimethyl-1-propylamine formate (TMR-2): chemistry of Xindian
Potassium acetate: chemical industry of Zhuo Chuang
Polyether polyol a 1: sucrose as initiator, hydroxyl value of 200mgKOH/g, functionality of 6.3, Wanhua chemical (Ningbo) Weiwei
Polyether polyol a 2: sucrose as initiator, hydroxyl value of 350mgKOH/g, functionality of 7.1, Wanhua chemical (Ningbo) Weiwei
Polyether polyol a 3: sucrose as initiator, hydroxyl value of 550mg KOH/g, functionality of 7.9, Wanhua chemical (Ningbo) Weiwei
Polyether polyol a 4: sorbitol as initiator, hydroxyl value of 278mgKOH/g, functionality of 6.5, Wanhua chemical (Ningbo) Weiwei
Polyether polyol a 5: sorbitol as initiator, hydroxyl value of 510mgKOH/g, functionality of 7.7, Wanhua chemical (Ningbo) Weiwei
Polyether polyol B1: takes o-toluenediamine as an initiator, has a hydroxyl value of 310mgKOH/g and a functionality of 4.1, and is warfarin chemical (Ningbo) captan
Polyether polyol B2: takes o-toluenediamine as an initiator, has a hydroxyl value of 450mgKOH/g and a functionality of 5.4, and is warfarin chemical (Ningbo) captan
Polyether polyol B3: o-toluenediamine is used as an initiator, the hydroxyl value is 530mgKOH/g, the functionality is 5.8, and warfarin chemical (Ningbo) captan
Polyether polyol C1: palm oil as initiator, hydroxyl value of 250mgKOH/g, functionality of 3.2, Wanhua chemical (Ningbo) Weiwei
Polyether polyol C2: palm oil as initiator, hydroxyl value of 315mgKOH/g, functionality of 4.3, Wanhua chemical (Ningbo) Weiwei
Polyether polyol C3: palm oil as initiator, hydroxyl value of 450mgKOH/g, functionality of 5.1, Wanhua chemical (Ningbo) Weiwei
Polyether polyol C4: palm oil as initiator, hydroxyl value of 480mgKOH/g, functionality of 5.8, Wanhua chemical (Ningbo) Weiwei
Polyether polyol C5: soybean oil as initiator, hydroxyl value of 470mgKOH/g, functionality of 5.5, Wanhua chemical (Ningbo) Weiwei
Polyether polyol C6: soybean oil as initiator, hydroxyl value of 270mgKOH/g, functionality of 3.4, Wanhua chemical (Ningbo) Weiwei
Polyether polyol D1: diethylene glycol as initiator, hydroxyl value of 110mgKOH/g, functionality of 2.3, Wanhua chemical (Ningbo) Weiwei
Polyether polyol D2: diethylene glycol as initiator, hydroxyl value of 240mgKOH/g, functionality of 3.1, Wanhua chemical (Ningbo) Weiwei
Polyether polyol D3: diethylene glycol as initiator, hydroxyl value of 290mgKOH/g, functionality of 3.9, Wanhua chemical (Ningbo) Weiwei
Polyether polyol D4: propylene glycol as initiator, hydroxyl value of 125mgKOH/g, functionality of 2.5, Wanhua chemical (Ningbo) Weiwei
Polyether polyol D5: propylene glycol as initiator, hydroxyl value of 280mgKOH/g, functionality of 3.7, Wanhua chemical (Ningbo) Weiwei
Polyether polyol D6: glycerin as initiator, hydroxyl value of 130mgKOH/g, functionality of 2.6, Wanhua chemical (Ningbo) Weiwei
Polyether polyol D7: glycerol as initiator, hydroxyl value of 295mgKOH/g, functionality of 4, Wanhua chemical (Ningbo) Weiwei
Phthalic anhydride polyester polyol E1: a hydroxyl value of 370mgKOH/g, a functionality of 4.7, Nanjing Spam
Phthalic anhydride polyester polyol E2: hydroxyl number 170mgKOH/g, functionality 2.5, Nanjing Spirauli
Phthalic anhydride polyester polyol E3: hydroxyl number 230mgKOH/g, functionality 3.1, Nanjing Spirauli
The following embodiments relate to a method for testing the properties of polyurethane foam as follows:
foam core density test according to standard: GB/T6343-2009
The foam thermal conductivity test was according to the standard: GB/T10295-
And (3) testing the demolding expansion rate: the size, length, width and height of the inner cavity of the die are 70cm, 35cm and 10cm, and the temperature in the die is 45 ℃; the ambient temperature was 25 ℃ and the humidity was 45%. In the evaluation test, the mold was horizontally placed (i.e., 10cm was in the upward direction), a foam material having a constant temperature (18 ℃) was injected into the mold, the foam was taken out within 10 minutes, and the expansion coefficient of the foam in the thickness direction of 10cm was measured, i.e., demold expansion.
Foam compression strength test according to the standard: GB/T8813-
Foam dimensional stability test according to the standard: GB/T8811-
Surface bubble test: adopting a testing method of a Lambda mold, wherein the size of an inner cavity of the mold is 5cm x 20cm x 200cm, and the temperature in the mold is 45 ℃; the ambient temperature was 25 ℃ and the humidity was 45%. In the evaluation test, a mold was placed vertically (i.e., 200cm in the upward direction), 650g of a foam material having a constant temperature (18 ℃ C.) was poured into the mold, and after aging, the foam was taken out to evaluate the surface bubble grade based on the size and number of bubbles. Specifically, the bubbles with the longest dimension of 3-6cm are marked as A-type bubbles, and the bubbles with the longest dimension of more than 6cm are marked as B-type bubbles; and counting the quantity of the A-type bubbles and the B-type bubbles on the surface of the foam, and recording one B-type bubble as two A-type bubbles. Classifying the surface bubbles into grades I, II and III, wherein the grade I indicates that the quantity of the A-type bubbles is 1-10; the II gear represents that the number of the A-type bubbles is 10-20; class III indicates a class A bubble count of > 20.
Flow index: adopting a testing method of a Lambda mold, wherein the size of an inner cavity of the mold is 5cm x 20cm x 200cm, and the temperature in the mold is 45 ℃; the ambient temperature was 25 ℃ and the humidity was 45%. In the evaluation experiment, a mold is vertically placed (i.e., 200cm is upward), 500g of foam raw material with constant temperature (18 ℃) is injected into the mold, and the initial height of the foam is recorded; after curing, taking out the foam, measuring the rising height of the foam, wherein the flow index is as follows: foam height/foam weight.
The overfill rate: adopting a testing method of a Lambda mold, wherein the size of an inner cavity of the mold is 5cm x 20cm x 200cm, and the temperature in the mold is 45 ℃; the ambient temperature was 25 ℃ and the humidity was 45%. In the evaluation experiment, the mold is vertically placed (i.e. 200cm is upward direction), the foam material with constant temperature (18 ℃) is injected into the mold, the foam material just filling the mold is found, the injection amount is just filling (g), the specified injection amount (g) is injected, and the overfilling rate is: specified perfusion volume/exact fill 100%.
[ example 1 ]
A polyurethane composition comprising the following components by weight:
wherein the composite foaming agent comprises 75% of cyclopentane, 23% of GBA and 2% of propane by total mass of 100%.
The polyether polyol is formed by combining 85% of polyether polyol A4, 2% of polyether polyol B1, 11% of polyether polyol C2 and 2% of polyether polyol D3;
the polyester polyol is polyester polyol E1;
the composite catalyst comprises 100 mass percent of N, N-dimethylcyclohexylamine.
The isocyanate is polymeric MDI, Wanhua PM-200.
[ example 2 ]
A polyurethane composition comprising the following components by weight:
the composite foaming agent comprises 10% of isopentane, 30% of OPteon-115060% of propane and 100% of total mass.
The polyether polyol is formed by combining 5% of polyether polyol A1, 85% of polyether polyol B3 and 10% of polyether polyol D4;
the polyester polyol is polyester polyol E2;
in the composite catalyst, the weight ratio of pentamethyl diethylenetriamine: n, N-dimethylcyclohexylamine: potassium acetate 0.2:2:0.5 by mass ratio.
The isocyanate is polymeric MDI, Wanhua PM-2010.
[ example 3 ]
A polyurethane composition comprising the following components in parts by weight:
the composite foaming agent comprises 20% of cyclopentane, 70% of LBA and 10% of propane, wherein the total mass of the composite foaming agent is 100%.
The polyether polyol is formed by combining 10% of polyether polyol A3, 10% of polyether polyol B2 and 80% of polyether polyol C6;
the polyester polyol is polyester polyol E3;
in the composite catalyst, bis-dimethylaminoethyl ether: n-methylpyrrolidone: TMR-2 ═ 0.5:2.5:1 by mass ratio.
The isocyanate is polymeric MDI, Wanhua PM-200.
[ example 4 ] A method for producing a polycarbonate
A polyurethane composition comprising the following components by weight:
wherein the composite foaming agent comprises 70% of a pentane mixture (19: 1 of cyclopentane and isopentane), 25% of OPteon-11505% and propane, wherein the total mass of the composite foaming agent is 100%.
The polyether polyol is formed by combining 25% of polyether polyol A2, 20% of polyether polyol B2, 25% of polyether polyol C1 and 30% of polyether polyol D5;
the polyester polyol is polyester polyol E1;
in the composite catalyst, pentamethyldiethylenetriamine: n-methylpyrrolidone: and (3) potassium formate is 0.7:3:1.5 in mass ratio.
The isocyanate is polymeric MDI, Wanhua PM-400.
[ example 5 ]
A polyurethane composition comprising the following components by weight:
wherein the composite foaming agent comprises 30% of a pentane mixture (3: 7 of cyclopentane and isopentane), 5% of OPteon-110065 and 100% of propane.
The polyether polyol is formed by combining 55% of polyether polyol A5, 30% of polyether polyol B3, 10% of polyether polyol C3 and 5% of polyether polyol D2;
the polyester polyol is polyester polyol E3;
in the composite catalyst, bis-dimethylaminoethyl ether: n-methylpyrrolidone: and potassium acetate is 0.8:4:1.8 in mass ratio.
The isocyanate is polymeric MDI, Wanhua PM-200.
[ example 6 ]
A polyurethane composition comprising the following components by weight:
wherein the composite foaming agent comprises 41 percent of pentane mixture (5: 5 of cyclopentane and isopentane), 51 percent of GBA and 8 percent of propane by taking the total mass as 100 percent.
The polyether polyol is formed by combining 20% of polyether polyol A5, 40% of polyether polyol B1, 20% of polyether polyol C5 and 20% of polyether polyol D6;
the polyester polyol is polyester polyol E2;
in the composite catalyst, bis-dimethylaminoethyl ether: n, N-dimethylcyclohexylamine: and TMR-2 is 1:5:2 in mass ratio.
The isocyanate is polymeric MDI, Wanhua PM-2010.
[ example 7 ]
A polyurethane composition comprising the following components in parts by weight:
wherein the composite foaming agent comprises 57% of isopentane, 57% of OPteon-115030% of OPteon and 13% of propane by total mass of 100%.
The polyether polyol is formed by combining 75% of polyether polyol A4, 5% of polyether polyol B3, 5% of polyether polyol C4 and 15% of polyether polyol D7;
the polyester polyol is polyester polyol E1;
the composite catalyst comprises 100% of methylimidazole by mass.
The isocyanate is polymeric MDI, Wanhua PM-200.
[ example 8 ]
A polyurethane composition comprising the following components by weight:
wherein the composite foaming agent comprises 47% of cyclopentane, 37% of LBA and 16% of propane by total mass of 100%.
The polyether polyol is formed by combining 35% of polyether polyol A2, 50% of polyether polyol B1, 9% of polyether polyol C1 and 6% of polyether polyol D3;
the polyester polyol is polyester polyol E2;
in the composite catalyst, the weight ratio of tetramethyl hexanediamine: n, N-dimethylcyclohexylamine: and potassium acetate is 0.2:2:0.5 in mass ratio.
The isocyanate is polymeric MDI, Wanhua PM-2010.
[ example 9 ]
A polyurethane composition comprising the following components by weight:
wherein the composite foaming agent comprises 20% of pentane (cyclopentane: isopentane 4: 6), 110044% of OPteon and 19% of propane by total mass of 100%.
The polyether polyol is formed by combining 15% of polyether polyol A1, 8% of polyether polyol B2, 65% of polyether polyol C2 and 12% of polyether polyol D2;
the polyester polyol is polyester polyol E3;
in the composite catalyst, bis-dimethylaminoethyl ether: n-methylpyrrolidone: TMR-2 ═ 0.5:2.5:1 by mass ratio.
The isocyanate is polymeric MDI, Wanhua PM-200.
[ example 10 ]
A polyurethane composition comprising the following components by weight:
the composite foaming agent comprises 60% of a pentane mixture (cyclopentane and isopentane 6:4), 23% of OPteon-110017 and 23% of propane, wherein the total mass of the composite foaming agent is 100%.
The polyether polyol is formed by combining 8% of polyether polyol A3, 70% of polyether polyol B2, 14% of polyether polyol C3 and 8% of polyether polyol D1;
the polyester polyol is polyester polyol E1;
in the composite catalyst, pentamethyldiethylenetriamine: methyl imidazole: potassium acetate 0.7:3:1.5 by mass ratio.
The isocyanate is polymeric MDI, Wanhua PM-400.
[ example 11 ]
A polyurethane composition comprising the following components in parts by weight:
the composite foaming agent comprises 61% of a pentane mixture (7: 3 of cyclopentane and isopentane), 11% of LBA and 28% of propane, wherein the total mass of the composite foaming agent is 100%.
The polyether polyol is formed by combining 27% of polyether polyol A3, 18% of polyether polyol B1, 40% of polyether polyol C4 and 15% of polyether polyol D4;
in the composite catalyst, the weight ratio of tetramethyl hexanediamine: n-methylpyrrolidone: and (3) potassium formate is 0.8:4:1.8 in mass ratio.
The isocyanate is polymeric MDI, Wanhua PM-200.
Comparative example 1
A polyurethane composition is provided with reference to substantially the same process as in example 1, except that: the composite blowing agent was replaced with LBA of the same mass.
Comparative example 2
A polyurethane composition is provided with reference to essentially the same process as in example 1, except that: the composite foaming agent is replaced by cyclopentane with the same mass.
Comparative example 3
A polyurethane composition is provided with reference to substantially the same process as in example 1, except that: the composite blowing agent was replaced with the same mass of propane.
Comparative example 4
A polyurethane composition is provided with reference to essentially the same process as in example 1, except that: replacing the composite foaming agent with a mixture of cyclopentane and LBA with the same mass ratio of 14: 60.
comparative example 5
A polyurethane composition is provided with reference to essentially the same process as in example 1, except that: replacing the composite foaming agent with a mixture of LBA and propane with the same mass ratio of 60: 26.
comparative example 6
A polyurethane composition is provided with reference to essentially the same process as in example 1, except that: the material proportion of the composite foaming agent is modified to be that the composite foaming agent comprises 7% of cyclopentane, 58% of LBA and 35% of propane, wherein the total mass of the composite foaming agent is 100%.
[ application example ]
Using the polyurethane compositions prepared in examples 1 to 11 and comparative examples 1 to 6, respectively, polyurethane foams were prepared according to the following methods:
1) uniformly mixing polyether polyol, polyester polyol, a surfactant, a composite catalyst, water and a composite foaming agent, and cooling to below 10 ℃ to obtain a mixture;
2) mixing the mixture obtained in the step 1) with isocyanate, and foaming at high pressure to prepare hard polyurethane foam;
the high-pressure foaming conditions comprise the gun head pressure of 140Kpa and the temperature of 18 ℃.
The polyurethane foams prepared from the polyurethane compositions of the examples and comparative examples were subjected to the performance tests in Table 1, and the test results are shown in Table 1. As can be seen from Table 1, the polyurethane foam prepared by the scheme of the invention has the advantages of heat conductivity coefficient, demolding expansion coefficient, lower bubbles, good strength and better performance than that of a comparative example under the condition of the same overfilling rate, so that the technical scheme of the invention can effectively reduce the raw material pouring amount and the foam density under the condition of the same process parameters, thereby reducing the production cost.
TABLE 1 polyurethane foam Property parameter Table
Claims (11)
1. The polyurethane composition is characterized by comprising the following components in parts by mass:
67-100 parts of polyether polyol,
0 to 33 parts of polyester polyol,
0.5 to 9 parts of a surfactant,
1-15 parts of a composite catalyst,
0.5 to 7 parts of water,
8-60 parts of a composite foaming agent,
isocyanate with an isocyanate index of 1.0-1.5;
the composite foaming agent comprises, by total mass, 100% of pentane 10-75%, a hydrofluoroolefin foaming agent 5-70% and propane 2-30%.
2. The polyurethane composition of claim 1, wherein the polyether polyol is a combination of polyether polyol a, polyether polyol B, polyether polyol C, and polyether polyol D;
the polyether polyol A has a hydroxyl value of 200-550 mgKOH/g and a functionality of 6-8, and is prepared by performing addition reaction on at least one of sucrose and sorbitol serving as an initiator and olefin oxide;
the polyether polyol B is amino polyether polyol, has a hydroxyl value of 300-550 mgKOH/g and a functionality of 4-6, and is prepared by addition reaction of o-toluenediamine and alkylene oxide;
the polyether polyol C has a hydroxyl value of 250-495 mgKOH/g and a functionality of 3-6, and is prepared by performing addition reaction on at least one of palm oil and soybean oil serving as an initiator and alkylene oxide;
the polyether polyol D has a hydroxyl value of 100-300 mgKOH/g and a functionality of 2-4, and is prepared by addition reaction of at least one initiator selected from diethylene glycol, glycerol and propylene glycol with an alkylene oxide.
3. The polyurethane composition according to claim 2, wherein the polyether polyol comprises the following components in percentage by mass based on 100% of the total mass:
5 to 85 percent of polyether polyol A, preferably 5 to 72 percent,
2-85%, preferably 10-70%,
0 to 80%, preferably 10 to 70%, of polyether polyol C,
0-30% of polyether polyol D, preferably 5-20%.
4. The polyurethane composition according to claim 3, wherein the polyester polyol has a hydroxyl value of 150 to 400mgKOH/g and a functionality of 2 to 5, and is a phthalic anhydride polyester polyol obtained by condensing phthalic anhydride and a polyhydric alcohol.
5. The polyurethane composition according to any one of claims 1 to 4, wherein the surfactant is a silicon-carbon surfactant, preferably at least one of silicone oil AK8830, silicone oil L6863, silicone oil B84806, and silicone oil B8492.
6. The polyurethane composition as claimed in any one of claims 1 to 4, wherein the composite catalyst comprises a foaming catalyst, a gel catalyst and a trimerization catalyst, wherein the mass ratio of the foaming catalyst to the gel catalyst to the trimerization catalyst is (0-1): 0.2-5): 0-2, preferably (0-1): 1-4): 0.5-2;
preferably, the foaming catalyst is one or a mixture of more of pentamethyldiethylenetriamine, tetramethylhexanediamine and bis-dimethylaminoethylether in any proportion;
preferably, the gel catalyst is one or a mixture of more of methylimidazole, N-dimethylcyclohexylamine, N-methylpyrrolidone and PT303 in any proportion;
preferably, the trimerization catalyst is one or a mixture of more of potassium formate, 1,3, 5-tris (dimethylaminopropyl) hexahydrotriazine, 2-hydroxy-N, N, N-trimethyl-1-propylamine formate and potassium acetate in any proportion.
7. The polyurethane composition as claimed in any one of claims 1 to 4, wherein the pentane is at least one of cyclopentane and isopentane;
preferably, the hydrofluoroolefin blowing agent is at least one of trans-1-chloro-3, 3, 3-trifluoropropene, cis-1, 1,1,4,4, 4-hexafluoro-2-butene, trans-1, 1,1, 3-tetrafluoropropene.
8. A polyurethane composition according to any one of claims 1 to 4, wherein the isocyanate is polymeric MDI, preferably polymeric MDI having an NCO content of 29 to 32%, more preferably one or more of Wanhua PM-200, Wanhua PM-2010 and Wanhua PM-400.
9. A polyurethane foam made from the polyurethane composition of any one of claims 1 to 8.
10. A method for preparing a polyurethane foam from the polyurethane composition of any one of claims 1 to 8, comprising the steps of:
1) uniformly mixing polyether polyol, polyester polyol, a surfactant, a composite catalyst, water and a composite foaming agent, and cooling to below 10 ℃ to obtain a mixture;
2) mixing the mixture obtained in the step 1) with isocyanate, and foaming at high pressure to prepare rigid polyurethane foam;
preferably, the high-pressure foaming condition is that the pressure of a gun head is 130-150 Kpa, and the temperature is 15-19 ℃.
11. Use of a polyurethane foam prepared from the polyurethane composition of any one of claims 1 to 8 as a refrigerator material.
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| CN117467113A (en) * | 2023-12-28 | 2024-01-30 | 山东一诺威新材料有限公司 | Polyurethane material for foam filled insulating tube and preparation method thereof |
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