CN109642004A - 聚氨酯泡沫和包含其的聚氨酯复合材料 - Google Patents
聚氨酯泡沫和包含其的聚氨酯复合材料 Download PDFInfo
- Publication number
- CN109642004A CN109642004A CN201780031253.7A CN201780031253A CN109642004A CN 109642004 A CN109642004 A CN 109642004A CN 201780031253 A CN201780031253 A CN 201780031253A CN 109642004 A CN109642004 A CN 109642004A
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- isocyanate
- polyether polyol
- reactive
- polyurethane foam
- 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
- 239000004814 polyurethane Substances 0.000 title claims abstract description 47
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 46
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 33
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 26
- 150000001875 compounds Chemical class 0.000 title claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 57
- 239000012948 isocyanate Substances 0.000 claims abstract description 20
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 229920000570 polyether Polymers 0.000 claims description 61
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 57
- 150000003077 polyols Chemical class 0.000 claims description 44
- 229920005862 polyol Polymers 0.000 claims description 43
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 40
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 20
- 239000006260 foam Substances 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 239000004088 foaming agent Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000004364 calculation method Methods 0.000 claims description 10
- -1 3-pentafluorobutane Chemical compound 0.000 claims description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 8
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 7
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- YACLCMMBHTUQON-UHFFFAOYSA-N 1-chloro-1-fluoroethane Chemical compound CC(F)Cl YACLCMMBHTUQON-UHFFFAOYSA-N 0.000 claims description 2
- LDTMPQQAWUMPKS-UHFFFAOYSA-N 1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=CCl LDTMPQQAWUMPKS-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- SXKNYNUXUHCUHX-UHFFFAOYSA-N 1,1,2,3,3,4-hexafluorobut-1-ene Chemical compound FCC(F)(F)C(F)=C(F)F SXKNYNUXUHCUHX-UHFFFAOYSA-N 0.000 claims 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 5
- 229920005903 polyol mixture Polymers 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005187 foaming Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- ZMBQZWCDYKGVLW-UHFFFAOYSA-N 1-methylcyclohexa-3,5-diene-1,2-diamine Chemical compound CC1(N)C=CC=CC1N ZMBQZWCDYKGVLW-UHFFFAOYSA-N 0.000 description 1
- RWEISEYGJSRYKT-UHFFFAOYSA-N 2-[3,4-dihydroxy-2,5-bis(hydroxymethyl)oxolan-2-yl]oxy-6-(hydroxymethyl)oxane-2,3,4,5-tetrol Chemical compound OC1C(O)C(CO)OC1(CO)OC1(O)C(O)C(O)C(O)C(CO)O1 RWEISEYGJSRYKT-UHFFFAOYSA-N 0.000 description 1
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- PBONCSGLBNLRPG-UHFFFAOYSA-N isocyanoazaniumylidynemethane Chemical compound [C-]#[N+][N+]#[C-] PBONCSGLBNLRPG-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229960004624 perflexane Drugs 0.000 description 1
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000008961 swelling Effects 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
- C08G18/48—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
- B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
- B29C44/18—Filling preformed cavities
-
- 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
- C08G18/14—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
- 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
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols 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
- C08G18/28—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
- C08G18/4825—Polyethers containing two 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- 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
- C08G18/487—Polyethers containing cyclic groups
- C08G18/4883—Polyethers containing cyclic groups containing cyclic groups having at least one oxygen atom in the ring
-
- 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
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
-
- 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
- C08J9/125—Water, e.g. hydrated salts
-
- 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
- C08J9/141—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
- 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
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0041—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
- C08G2110/0041—Foam properties having specified density
- C08G2110/0058—≥50 and <150kg/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
- C08G2120/00—Compositions for reaction injection moulding processes
-
- 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
- C08J2203/10—Water or water-releasing compounds
-
- 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
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
- C08J2203/144—Perhalogenated saturated hydrocarbons, e.g. F3C-CF3
-
- 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
- C08J2203/164—Perhalogenated unsaturated hydrocarbons, e.g. F2C=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
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
-
- 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
-
- 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
Landscapes
- 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)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明涉及可用于制备均匀反应性聚氨酯组合物的包含特定多元醇混合物的异氰酸酯反应性组分。本发明还涉及包含这样的异氰酸酯反应性组分和异氰酸酯组分的反应性聚氨酯组合物。其还涉及由这样的反应性聚氨酯组合物制成的具有良好脱模性质和表面质量的均匀聚氨酯泡沫。在另一方面中，其涉及包含这样的均匀聚氨酯泡沫并在加工后具有良好和平整的表面外观的聚氨酯复合材料。
Description
本发明涉及可用于制备均匀反应性聚氨酯组合物的包含特定多元醇混合物的异氰酸酯反应性组分。本发明还涉及包含这样的异氰酸酯反应性组分和异氰酸酯组分的反应性聚氨酯组合物。其还涉及由这样的反应性聚氨酯组合物制成的具有良好脱模性质和表面质量的均匀聚氨酯泡沫。在另一方面中，其涉及包含这样的均匀聚氨酯泡沫并在加工后具有良好和平整的表面外观的聚氨酯复合材料。
如本申请中提到的聚氨酯复合材料通常包含壳和填充在其中的聚氨酯泡沫。
用于生产隔热系统，如集装箱、冷藏库、预制住宅、管线和空调隔热板等的非常灵活和广泛应用的方法是不连续方法，其中在板形外壳中以板部件的形式制备聚氨酯复合材料，然后将这些板部件组装成各自的隔热系统。或者，可以使用例如由各种板组装的任何几何的预制中空壳。
用于生产聚氨酯复合材料的不连续方法包括下列步骤：将预制壳安置在模具中、将反应性聚氨酯组合物注入模具中和关闭模具。然后使聚氨酯树脂发泡。最后，通过从模具中脱出而获得聚氨酯复合材料。
现有技术已公开了各种反应性聚氨酯组合物，它们通常通过混合异氰酸酯组分和多元醇组分来制备。但是，在现有技术的组合物中，常出现可溶性问题，其最常由多元醇和发泡剂的混溶性不足造成。因此，由这样的组合物制成的聚氨酯泡沫通常较不均匀，这在含有由其制成的聚氨酯材料，即聚氨酯复合材料的产品中也造成质量问题。
此外，由现有反应性聚氨酯组合物制成的聚氨酯泡沫的已知问题是该复合材料的不良脱模性质，即可观察到在脱模后的一定程度膨胀，这造成制成的聚氨酯复合材料的粗糙和不平整表面。此外，由已知反应性聚氨酯组合物制成的聚氨酯泡沫也可能表现出表面气泡问题，这随后导致在由其制成的聚氨酯复合材料中出现凸起或甚至严重的质量问题。
因此，在本领域中仍然需要包含均匀聚氨酯泡沫并具有良好和平整的表面外观的聚氨酯复合材料，其通过包括将反应性聚氨酯组合物注入模具中提供的壳中和使这样的反应性组合物发泡的步骤的不连续方法来制备。
现在已经令人惊讶地发现，可以通过使用包含聚醚多元醇组合物的异氰酸酯反应性组分B)克服现有技术的问题，所述聚醚多元醇组合物包含：
b1) 第一聚醚多元醇，其具有1.6-2.4的官能度、60-140 mg KOH/g的羟基值、基于所述聚醚多元醇组合物的理论计算总摩尔数计30-40摩尔%的量，
b2) 第二聚醚多元醇，其具有7.6-8.4的官能度、480-560 mg KOH/g的羟基值，基于所述聚醚多元醇组合物的理论计算总摩尔数计35-55摩尔%的量，和
b3) 第三聚醚多元醇，其选自衍生自二苯基甲烷二胺和/或甲苯二胺的聚醚多元醇、具有3.6-4.4的官能度和290-370 mg KOH/g的羟基值、基于所述聚醚多元醇组合物的理论计算总摩尔数计13-27摩尔%的量。
本发明还提供可用于生产具有良好和平整的表面外观的聚氨酯泡沫的反应性聚氨酯组合物，其包含：
A) 异氰酸酯组分，所述异氰酸酯组分包含一种或多种多异氰酸酯；
B) 包含聚醚多元醇组合物的异氰酸酯反应性组分，所述聚醚多元醇组合物包含：
b1) 第一聚醚多元醇，其具有1.6-2.4的官能度、60-140 mg KOH/g的羟基值、基于所述聚醚多元醇组合物的理论计算总摩尔数计30-40摩尔%的量，
b2) 第二聚醚多元醇，其具有7.6-8.4的官能度、480-560 mg KOH/g的羟基值、基于所述聚醚多元醇组合物的理论计算总摩尔数计35-55摩尔%的量，和
b3) 第三聚醚多元醇，其选自衍生自二苯基甲烷二胺和/或甲苯二胺的聚醚多元醇、具有3.6-4.4的官能度和290-370 mg KOH/g的羟基值、基于所述聚醚多元醇组合物的理论计算总摩尔数计13-27摩尔%的量；和
C) 发泡剂。
可用于制备聚氨酯泡沫的组分A)的有机多异氰酸酯包括有机二异氰酸酯，其可以是已知可用于制备聚氨酯的任何脂族、脂环族或芳族异氰酸酯。其实例包括但不限于2,2’-、2,4-和4,4’-二苯基甲烷二异氰酸酯（单体MDI）；单体二苯基甲烷二异氰酸酯和具有更多环的二苯基甲烷二异氰酸酯同系物（聚合MDI）的混合物；异佛尔酮二异氰酸酯（IPDI）或其低聚物；甲苯二异氰酸酯（TDI），例如甲苯二异氰酸酯异构体，如甲苯-2,4-或2,6-二异氰酸酯或其混合物；四亚甲基二异氰酸酯或其低聚物；六亚甲基二异氰酸酯（HDI）或其低聚物；萘二异氰酸酯（NDI）或其混合物。
在本发明的优选实施方案中，有机多异氰酸酯包括基于二苯基甲烷二异氰酸酯的异氰酸酯，尤其是包含聚合MDI的那些。该有机多异氰酸酯优选具有1.9-3.5，特别优选2.0-2.8的官能度。该有机多异氰酸酯优选具有根据GB/T 12008.8-1992在25℃下测得的100-600 mPas，特别优选150-300 mPas的粘度。基于所述聚氨酯组合物的总重量为100重量%计，该异氰酸酯组分可以20-60重量%的量存在。
有机多异氰酸酯也可以以多异氰酸酯预聚物的形式使用。这些多异氰酸酯预聚物可通过过量的上述有机多异氰酸酯与具有至少两个异氰酸酯反应性基团的化合物在例如30-100℃，优选大约80℃的温度下的反应获得。本发明的多异氰酸酯预聚物的NCO含量优选为20-33重量%（GB 12009.4-1989），特别优选25-32重量%。具有至少两个异氰酸酯反应性基团的化合物是本领域技术人员公知的，例如如“Plastics Handbook”(“Kunststoffhandbuch, 7, Polyurethanes”, Carl Hanser-Verlag, 第3版, 1993)的章节3.1中所述。
可用于制备本发明提供的聚氨酯泡沫的异氰酸酯反应性组分包含聚醚多元醇组合物。本文所用的“聚醚多元醇”具有本领域技术人员公知的定义。其可通过已知方法，例如通过环氧烷与起始剂在催化剂存在下的反应制备。与根据本发明的组分，例如某些多元醇结合使用词语“一”在本申请的意义内不应被理解为数值。术语“多元醇”因此也可定义多元醇的混合物，在这种情况下各多元醇所需的参数（如官能度、羟基值等）对应于对各自多元醇混合物测量或计算的平均值。
例如，术语“官能度”在本发明的上下文中是指由多元醇混合物中使用的已知组分及其比例计算的理论官能度。
用于本发明的第一聚醚多元醇b1)具有1.6-2.4，优选1.8-2.2的官能度、60-140mg KOH/g，优选80-120 mg KOH/g的羟基值（根据GB/T12008.3-2009测得），并以基于该聚醚多元醇组合物的理论计算总摩尔数计30-40摩尔%的量，优选32-38摩尔%的量使用。
在本发明的优选实施方案中，第一聚醚多元醇选自衍生自1,2-丙二醇和/或1,3-丙二醇的聚醚多元醇。更优选地，第一聚醚多元醇选自衍生自1,2-丙二醇的基于环氧丙烷的聚醚多元醇。
用于本发明的第二聚醚多元醇b2)具有7.6-8.4，优选7.8-8.2的官能度、480-560mg KOH/g，优选490-530 mg KOH/g的羟基值，并以基于所述聚醚多元醇组合物的理论计算总摩尔数计35-55摩尔%的量，在优选实施方案中分别35-50摩尔%或35-45摩尔%的量，再更优选分别40-50摩尔%或38-48摩尔%的量使用。
在本发明的一个优选实施方案中，第一聚醚多元醇选自衍生自蔗糖的聚醚多元醇。更优选地，第一聚醚多元醇选自衍生自蔗糖的基于环氧丙烷的聚醚多元醇。
用于本发明的第三聚醚多元醇b3)选自衍生自二苯基甲烷二胺和/或甲苯二胺的聚醚多元醇，并具有3.6-4.4，优选3.8-4.2的官能度和290-370 mg KOH/g，优选320 mgKOH/g-360 mg KOH/g的羟基值，并以基于所述聚醚多元醇组合物的理论计算总摩尔数计13-27摩尔%的量，在优选实施方案中分别15-25摩尔%，特别优选17-23摩尔%的量使用。邻甲苯二胺或二苯基甲烷二胺（所有异构体）优选用作起始剂。邻甲苯二胺（o-TDA）可以为2,3-和3,4-异构体的混合物的形式。衍生自o-TDA的基于环氧丙烷的聚醚多元醇特别优选用于第三聚醚。在本发明的另一特别优选的实施方案中，第三聚醚多元醇选自衍生自二苯基甲烷二胺的基于环氧丙烷的聚醚多元醇。
包含上述聚醚多元醇b1) – b3)的聚醚多元醇组合物表现出3.5-6，优选4.5-5.5的平均官能度和280-450 mg KOH/g，优选300-350 mg KOH/g的平均羟基值。
用于制备本发明提供的聚氨酯泡沫的异氰酸酯反应性组合物进一步包括发泡剂C)。所述发泡剂可选自各种物理发泡剂或化学发泡剂，优选但不限于水、卤代烃、烃化合物，和气体，优选正戊烷、异戊烷、环戊烷、丁烷、异丁烷、醚（例如甲缩醛）、卤代醚、具有1至8个碳原子的全氟化烃（例如全氟己烷）、氢烯烃和它们的相互混合物。在本发明的一个优选实施方案中，所述发泡剂选自水、二氯氟乙烷、环戊烷、五氟丁烷、五氟丙烷、三氟氯丙烯、六氟丁烯或其组合。在本发明的另一优选实施方案中，基于该异氰酸酯反应性组分的重量为100重量%计，所述发泡剂以2-30重量%，优选5-25重量%的量存在。环戊烷异常特别优选用作发泡剂。
也优选添加水或其它化学发泡剂作为助发泡剂。如果使用，其通常以0-6重量%的量添加，基于包括发泡剂的总异氰酸酯反应性组分重量为100重量%计。
可用于制备根据本发明的聚氨酯泡沫的组分可进一步包含本领域中常用的其它助剂或添加剂，包括但不限于催化剂、阻燃剂和泡沫稳定剂等。
在本发明的一个实施方案中，所述聚氨酯泡沫的芯密度为35-70 kg/m3（GB/T6343-1995）。
在本发明的另一实施方案中，所述聚氨酯泡沫的闭孔比例为85-98%（GB/T 10799-2008）。
在可用于制备根据本发明的聚氨酯泡沫的组分中，异氰酸酯反应性组分B)与发泡剂组分C)具有良好相容性，因此能够制备具有均匀分布的泡沫。同时，由其制备的聚氨酯泡沫和用该泡沫制成的聚氨酯复合材料具有良好脱模性质以及良好的表面质量。
本发明还提供通过包括下列步骤的不连续方法制成的聚氨酯复合材料：
i) 在模具中提供壳
ii) 关闭模具
iii) 将本发明的反应性聚氨酯组合物注入模具中的所述壳中
iv) 使所述反应性聚氨酯组合物发泡
v) 从模具中脱出包含壳和聚氨酯泡沫的所得聚氨酯复合材料。
在一个备选方案中，壳可由覆盖板构成，该覆盖板在关闭模具前放置和任选接合在模具内壁。
在该方法的另一备选实施方案中，首先使用板材，如金属、塑料和复合板等预制中空壳件；然后对中空壳件的接缝部分施以密封处理，其中保留注入孔和排气孔；和最后将中空壳件安置到泡沫成型模具中；经由模具和中空壳件的注入孔将本发明的反应性聚氨酯组合物引入中空壳件的空腔中；和在反应性聚氨酯组合物的发泡反应完成后从模具中取出包含泡沫和壳的聚氨酯复合材料。
在本发明的一些实施方案中，所述预制壳具有板状或空心圆柱形状。
本发明还提供通过本发明的不连续方法制成的聚氨酯复合材料。
通过这种不连续方法制成的聚氨酯复合材料可有利地用于制造集装箱的顶板、侧板、底板或门板；预制住宅的顶板、侧板或底板或门板；冷藏室的顶板、侧板或底板或门板；空调机的隔热板和隔热管线。
实施例
下面联系具体实施例进一步描述本发明。但是，本领域技术人员会理解，这些实施例仅例示本发明并且不应被解释为限制本发明的范围。
下面显示实施例中所用的市售原材料：
Polyol 1：用丙二醇作为引发剂的基于环氧丙烷的聚醚多元醇，具有2的官能度和100mg KOH/g的羟基值；
Polyol 2：用蔗糖作为引发剂的基于环氧丙烷的聚醚多元醇，具有8的官能度和525 mgKOH/g的羟基值；
Polyol 3：用o-TDA作为引发剂的基于环氧丙烷的聚醚多元醇，具有4的官能度和345mg KOH/g的羟基值；
Yoke TCPP：磷酸三(2-氯异丙基)酯，阻燃剂，购自Jiangsu Yoke Technology Co.,Ltd.；
Niax L6920：泡沫稳定剂，购自Momentive Performance Materials (China) Co.,Ltd.；
Dabco Polycat 41：聚氨酯合成催化剂，购自Air Products and Chemicals (China)Co., Ltd.；
Dabco Polycat PC8：聚氨酯合成催化剂，购自Air Products and Chemicals (China)Co., Ltd.；
Desmodur® 44V20L：聚合MDI，具有31.5重量%的NCO含量，购自Covestro Polymers(China) Co., Ltd.。
聚氨酯复合材料的制备
将预制中空壳件（板形）置于模具中并关闭模具。该中空壳件在模具中预热直至其表面材料的表面温度达到30-45℃。
除异氰酸酯和物理发泡剂组分外的表1中的组分（总量：80 kg）在搅拌下混合以获得异氰酸酯反应性混合物。
此后，在高压发泡机的混合头中引入和混合异氰酸酯反应性混合物和异氰酸酯组分（该混合头在100至160巴的压力下）。
然后将聚氨酯反应性混合物经混合头注入模具中的预制中空壳件中，在中空壳中发泡和膨胀直至完全填满中空壳。在发泡反应完成后，从模具中取出发泡制品并获得聚氨酯复合材料。
相容性测试方法
将环戊烷和合并聚醚储料（stock）（即除异氰酸酯和环戊烷外的表1中所列的所有组分）充分混合，其中环戊烷与合并聚醚的混合重量比为12 : 100、15 : 100、18 : 100和21 :100。在充分混合后，用透明管密封该溶液并在室温（20℃）下静置72小时以供观察。如果管内的溶液表现出清澈性，其表明优异的相容性；如果管内的溶液表现出轻微浑浊，其表明良好的相容性；但如果管内的溶液表现出严重浑浊、两相或多相分离，其表明差的相容性。表1中的测试结果显示配方1、2和3的相容性分别为差、良好和优异。
表1: 聚氨酯泡沫的配方及其相容性
1mol-%，基于聚醚多元醇组合物的理论计算总摩尔数计(多元醇1-3)
2wt.-%，相对于聚氨酯反应性组合物计。
脱模性能的测试方法
使用300 × 300 × 100mm的模具，将模具温度控制在40℃且模具的总泡沫密度为55kg/m3。混合表2中的组分（总量 = 495g），然后置于放在模具中的硬纸盒中。紧密关闭模具。在模具中发生发泡反应。在从混合组分开始20分钟后，打开模具并取出发泡的模制品。测量发泡的模制品中心的最大膨胀高度。膨胀高度越大，脱模性能越差。通常，1.0-3.5 mm的膨胀高度表明良好的脱模性能。测试结果显示在下表2中。
表2: 脱模性质的试验
| 对比例1 | 实施例5 | 对比例9 | |
| 膨胀高度(mm) | 4.5 | 2.6 | 1.8 |
表面气泡试验
使用L形模具，将模具温度控制在40℃并用脱模剂均匀涂覆模具的内表面。模具的总泡沫密度为55 kg/m3。混合表1中的配方，然后置于模具中。关闭模具并在模具中发生发泡反应。在从混合组分开始30分钟后，打开模具并取出发泡的模制品。
如下分析L形泡沫表面上的气泡：
i. 气泡深度，
ii. 气泡体积和
iii. 气泡总数。
这三个值越小，整体表面气泡性能（表面质量）越好。对比例1和9和实施例5的所得聚氨酯泡沫的表面质量显示在图1中。表3显示聚氨酯泡沫的表面质量的分析结果。图1显示泡沫照片：左侧是对比例9的泡沫，中间是实施例5的泡沫且右侧是对比例1的泡沫。
表3: 聚氨酯泡沫的表面气泡试验
| 对比例1 | 实施例5 | 对比例9 | |
| 表面气泡等级 | 优异 | 良好 | 差 |
通过比较上述配方的相容性、脱模性质和表面性质，发现只有本发明的配方2实现各性质之间的有利平衡。
Claims (13)
1.包含聚醚多元醇组合物的异氰酸酯反应性组分B)，所述聚醚多元醇组合物包含：
b1) 第一聚醚多元醇，其具有1.6-2.4的官能度、60-140 mg KOH/g的羟基值、基于所述聚醚多元醇组合物的理论计算总摩尔数计30-40摩尔%的量，
b2) 第二聚醚多元醇，其具有7.6-8.4的官能度、480-560 mg KOH/g的羟基值、基于所述聚醚多元醇组合物的理论计算总摩尔数计35-55摩尔%的量，和
b3) 第三聚醚多元醇，其选自衍生自二苯基甲烷二胺和/或甲苯二胺的聚醚多元醇、具有3.6-4.4的官能度和290-370 mg KOH/g的羟基值、基于所述聚醚多元醇组合物的理论计算总摩尔数计13-27摩尔%的量。
2.根据权利要求1的异氰酸酯反应性组分，其中所述第二聚醚多元醇选自衍生自蔗糖的聚醚多元醇。
3.根据权利要求1或2的异氰酸酯反应性组分，其中所述第一聚醚多元醇、第二聚醚多元醇和第三聚醚多元醇都选自基于环氧丙烷的聚醚多元醇。
4.根据权利要求1-3任一项的异氰酸酯反应性组分，其中所述发泡剂包括二氯氟乙烷、环戊烷、五氟丁烷、五氟丙烷、三氟氯丙烯、六氟丁烯或其组合。
5.根据权利要求4任一项的异氰酸酯反应性组分，其中所述发泡剂另外包括水。
6.可用于生产具有良好和平整的表面外观的聚氨酯泡沫的反应性聚氨酯组合物，其包含：
异氰酸酯组分A)，所述异氰酸酯组分包含一种或多种多异氰酸酯；
根据权利要求1-5的至少一项的异氰酸酯反应性组分B)，和
发泡剂C)。
7.通过根据权利要求6的反应性聚氨酯组合物的反应而获得的聚氨酯泡沫。
8.根据权利要求7的聚氨酯泡沫，其中所述聚氨酯泡沫的芯密度为35-70 kg/m3。
9.根据权利要求7的聚氨酯泡沫，其中所述聚氨酯泡沫的闭孔比例为85-98%。
10.用于生产包含壳和在其中的聚氨酯泡沫的聚氨酯复合材料的不连续方法，其包括步骤：
i) 在模具中提供壳
ii) 关闭模具
iii) 将根据权利要求6的反应性聚氨酯组合物注入模具中的所述壳中
iv) 使所述反应性聚氨酯组合物发泡
v) 从模具中脱出包含壳和聚氨酯泡沫的所得聚氨酯复合材料。
11.通过根据权利要求10的不连续方法制成的聚氨酯复合材料。
12.通过根据权利要求10的不连续方法制成的聚氨酯复合材料，其中所述壳具有板状或空心圆柱形状。
13.通过根据权利要求10的不连续方法制成的聚氨酯复合材料的用途，其中所述聚氨酯复合材料选自集装箱的顶板、侧板、底板或门板；预制住宅的顶板、侧板或底板或门板；冷藏室的顶板、侧板或底板或门板；空调机的隔热板；和隔热管线。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610370868 | 2016-05-20 | ||
| CN201610370868X | 2016-05-20 | ||
| PCT/CN2017/084139 WO2017198115A1 (en) | 2016-05-20 | 2017-05-12 | A polyurethane foam and a polyurethane composite comprising the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109642004A true CN109642004A (zh) | 2019-04-16 |
| CN109642004B CN109642004B (zh) | 2021-08-17 |
Family
ID=60324831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780031253.7A Expired - Fee Related CN109642004B (zh) | 2016-05-20 | 2017-05-12 | 聚氨酯泡沫和包含其的聚氨酯复合材料 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US10793663B2 (zh) |
| EP (1) | EP3458492A4 (zh) |
| JP (1) | JP6893522B2 (zh) |
| KR (1) | KR20190009748A (zh) |
| CN (1) | CN109642004B (zh) |
| WO (1) | WO2017198115A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111349206A (zh) * | 2020-04-14 | 2020-06-30 | 万华节能科技(烟台)有限公司 | 一种冷库用高强度聚氨酯保温垫块双组分原料及制备方法 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243304A (zh) * | 2015-06-11 | 2016-12-21 | 科思创聚合物（中国）有限公司 | 粘弹性网状聚氨酯泡沫及其制备方法 |
| CN113929852B (zh) * | 2021-09-18 | 2023-05-30 | 红宝丽集团股份有限公司 | 聚氨酯组合物、组合聚醚、聚氨酯硬泡及其制备方法 |
Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3509077A (en) * | 1966-07-07 | 1970-04-28 | Allied Chem | Rigid polyurethane foams from certain polyether mixtures |
| JPH06239956A (ja) * | 1993-02-12 | 1994-08-30 | Sumitomo Bayer Urethane Kk | 硬質ポリウレタンフォームの製造法 |
| CN1214058A (zh) * | 1996-03-22 | 1999-04-14 | 拜尔公司 | 烃化合物发泡的聚氨酯－硬泡沫塑料的制造方法 |
| JPH11140155A (ja) * | 1997-11-07 | 1999-05-25 | Sumitomo Bayer Urethane Kk | 硬質ポリウレタンフォームの製造方法及び硬質ポリウレタンフォーム用組成物 |
| US6005016A (en) * | 1998-10-06 | 1999-12-21 | Bayer Corporation | Rigid polyurethane foam based on polyethers of TDA |
| WO2000005289A1 (en) * | 1998-07-23 | 2000-02-03 | Huntsman Ici Chemicals, Llc | Blends of sucrose- and aromatic amine initiated polyether polyols and their use in rigid polyurethane foam manufacture |
| JP2001329036A (ja) * | 2000-05-19 | 2001-11-27 | Toho Chem Ind Co Ltd | 硬質ポリウレタンフォームの製造方法 |
| CN1908028A (zh) * | 2006-08-18 | 2007-02-07 | 南京红宝丽股份有限公司 | 低密度低热导率聚氨酯硬质泡沫 |
| CN1986593A (zh) * | 2006-08-18 | 2007-06-27 | 南京红宝丽股份有限公司 | 一种具有快速脱模性能的硬质聚氨酯泡沫组成物 |
| CN101035826A (zh) * | 2004-10-05 | 2007-09-12 | 巴斯福股份公司 | 生产硬聚氨酯泡沫材料的方法 |
| CN101044180A (zh) * | 2004-10-19 | 2007-09-26 | 巴斯福股份公司 | 生产硬质聚氨酯泡沫的方法 |
| CN101289530A (zh) * | 2008-06-04 | 2008-10-22 | 常熟一统聚氨酯制品有限公司 | 聚氨酯硬质泡沫组合料 |
| CN102391466A (zh) * | 2011-09-14 | 2012-03-28 | 可利亚多元醇（南京）有限公司 | 低粘度快速脱模的硬质聚氨酯组合物及其制备方法 |
| CN102432794A (zh) * | 2011-09-14 | 2012-05-02 | 可利亚多元醇（南京）有限公司 | 低导热系数快速脱模的硬质聚氨酯组合物及其制备方法 |
| CN102666627A (zh) * | 2009-09-29 | 2012-09-12 | 陶氏环球技术有限责任公司 | 包含1,3-和/或1,4-二(氨基甲基)环己烷-引发的多元醇以及亚甲基二(环己胺)-引发的多元醇和环己烷二胺-引发的至少一种多元醇的多元醇混合物、以及由其制得的聚氨酯 |
| CN103415544A (zh) * | 2011-03-08 | 2013-11-27 | 巴斯夫欧洲公司 | 聚氨酯硬质泡沫的制备方法 |
| CN103642026A (zh) * | 2013-11-28 | 2014-03-19 | 山东蓝星东大化工有限责任公司 | 喷涂用硬泡聚醚多元醇的制备方法 |
| CN105199071A (zh) * | 2015-09-16 | 2015-12-30 | 万华化学（北京）有限公司 | 一种聚氨酯组合料、其制备聚氨酯复合材料的方法及制得产品的用途 |
| CN105367742A (zh) * | 2015-12-10 | 2016-03-02 | 上海东大聚氨酯有限公司 | 组合聚醚、聚氨酯泡沫及其制备方法和应用 |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4742089A (en) * | 1987-08-12 | 1988-05-03 | Hitachi, Ltd. | Rigid polyurethane foam and process for producing the same |
| JPH02284912A (ja) * | 1989-04-27 | 1990-11-22 | Hitachi Ltd | 硬質ポリウレタンフォーム及びその製造方法と断熱材並びにそれを用いた冷蔵庫 |
| JP3618791B2 (ja) * | 1994-09-06 | 2005-02-09 | 住化バイエルウレタン株式会社 | 硬質ポリウレタンフォーム用のポリオール組成物およびその用途 |
| DE19723193A1 (de) * | 1997-06-03 | 1998-12-10 | Bayer Ag | Verfahren zur Herstellung von geschlossenzelligen Polyurethan-Hartschaumstoffen mit geringer Wärmeleitfähigkeit |
| CN1097071C (zh) * | 1997-09-25 | 2002-12-25 | 亨茨曼Ici化学品有限公司 | 硬质聚氨酯泡沫塑料的制法 |
| EP1167414A1 (en) * | 2000-06-29 | 2002-01-02 | Huntsman International Llc | Process for making rigid polyurethane foams having high adhesion |
| KR100850995B1 (ko) | 2002-01-04 | 2008-08-12 | 주식회사 엘지이아이 | 경질 폴리우레탄 발포체 제조용 조성물 및 그로부터제조된 경질 폴리우레탄 발포체 |
| KR100935517B1 (ko) | 2003-03-07 | 2010-01-06 | 엘지전자 주식회사 | 접착력과 탈형성이 개선된 폴리우레탄 발포체 제조를 위한원액 조성물, 이로부터 제조된 폴리우레탄 발포체 및 그제조방법 |
| CN103709367B (zh) | 2012-09-29 | 2018-09-04 | 科思创聚合物（中国）有限公司 | 聚氨酯组合物以及聚氨酯道碴道床的维修方法 |
| US9296856B2 (en) | 2013-03-25 | 2016-03-29 | Covestro Deutschland Ag | Rigid polyurethane foams with uniform cell size distribution and homogeneous open-cell content |
-
2017
- 2017-05-12 KR KR1020187033077A patent/KR20190009748A/ko not_active Application Discontinuation
- 2017-05-12 WO PCT/CN2017/084139 patent/WO2017198115A1/en unknown
- 2017-05-12 JP JP2018560842A patent/JP6893522B2/ja active Active
- 2017-05-12 EP EP17798678.3A patent/EP3458492A4/en not_active Withdrawn
- 2017-05-12 CN CN201780031253.7A patent/CN109642004B/zh not_active Expired - Fee Related
- 2017-05-12 US US16/094,524 patent/US10793663B2/en active Active
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3509077A (en) * | 1966-07-07 | 1970-04-28 | Allied Chem | Rigid polyurethane foams from certain polyether mixtures |
| JPH06239956A (ja) * | 1993-02-12 | 1994-08-30 | Sumitomo Bayer Urethane Kk | 硬質ポリウレタンフォームの製造法 |
| CN1214058A (zh) * | 1996-03-22 | 1999-04-14 | 拜尔公司 | 烃化合物发泡的聚氨酯－硬泡沫塑料的制造方法 |
| JPH11140155A (ja) * | 1997-11-07 | 1999-05-25 | Sumitomo Bayer Urethane Kk | 硬質ポリウレタンフォームの製造方法及び硬質ポリウレタンフォーム用組成物 |
| WO2000005289A1 (en) * | 1998-07-23 | 2000-02-03 | Huntsman Ici Chemicals, Llc | Blends of sucrose- and aromatic amine initiated polyether polyols and their use in rigid polyurethane foam manufacture |
| US6005016A (en) * | 1998-10-06 | 1999-12-21 | Bayer Corporation | Rigid polyurethane foam based on polyethers of TDA |
| JP2001329036A (ja) * | 2000-05-19 | 2001-11-27 | Toho Chem Ind Co Ltd | 硬質ポリウレタンフォームの製造方法 |
| CN101035826A (zh) * | 2004-10-05 | 2007-09-12 | 巴斯福股份公司 | 生产硬聚氨酯泡沫材料的方法 |
| CN101044180A (zh) * | 2004-10-19 | 2007-09-26 | 巴斯福股份公司 | 生产硬质聚氨酯泡沫的方法 |
| CN1986593A (zh) * | 2006-08-18 | 2007-06-27 | 南京红宝丽股份有限公司 | 一种具有快速脱模性能的硬质聚氨酯泡沫组成物 |
| CN1908028A (zh) * | 2006-08-18 | 2007-02-07 | 南京红宝丽股份有限公司 | 低密度低热导率聚氨酯硬质泡沫 |
| CN101289530A (zh) * | 2008-06-04 | 2008-10-22 | 常熟一统聚氨酯制品有限公司 | 聚氨酯硬质泡沫组合料 |
| CN102666627A (zh) * | 2009-09-29 | 2012-09-12 | 陶氏环球技术有限责任公司 | 包含1,3-和/或1,4-二(氨基甲基)环己烷-引发的多元醇以及亚甲基二(环己胺)-引发的多元醇和环己烷二胺-引发的至少一种多元醇的多元醇混合物、以及由其制得的聚氨酯 |
| CN103415544A (zh) * | 2011-03-08 | 2013-11-27 | 巴斯夫欧洲公司 | 聚氨酯硬质泡沫的制备方法 |
| CN102391466A (zh) * | 2011-09-14 | 2012-03-28 | 可利亚多元醇（南京）有限公司 | 低粘度快速脱模的硬质聚氨酯组合物及其制备方法 |
| CN102432794A (zh) * | 2011-09-14 | 2012-05-02 | 可利亚多元醇（南京）有限公司 | 低导热系数快速脱模的硬质聚氨酯组合物及其制备方法 |
| CN103642026A (zh) * | 2013-11-28 | 2014-03-19 | 山东蓝星东大化工有限责任公司 | 喷涂用硬泡聚醚多元醇的制备方法 |
| CN105199071A (zh) * | 2015-09-16 | 2015-12-30 | 万华化学（北京）有限公司 | 一种聚氨酯组合料、其制备聚氨酯复合材料的方法及制得产品的用途 |
| CN105367742A (zh) * | 2015-12-10 | 2016-03-02 | 上海东大聚氨酯有限公司 | 组合聚醚、聚氨酯泡沫及其制备方法和应用 |
Non-Patent Citations (4)
| Title |
|---|
| IOLANDA ROTARU，等: "Synthesis of a New Mannich Polyether Polyol with Isocyanuric Structure", 《MATERIALE PLASTICE》 * |
| 俞丽珍，等: "环戊烷发泡剂/组合聚醚体系的研究", 《塑料科技》 * |
| 南京塑料厂: "《环氧化物合成聚醚》", 30 April 1976, 石油化学工业出版社 * |
| 杨鸣波，等: "《塑料成型工艺学》", 30 June 2014, 中国轻工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111349206A (zh) * | 2020-04-14 | 2020-06-30 | 万华节能科技(烟台)有限公司 | 一种冷库用高强度聚氨酯保温垫块双组分原料及制备方法 |
| CN111349206B (zh) * | 2020-04-14 | 2022-02-08 | 万华节能科技(烟台)有限公司 | 一种冷库用高强度聚氨酯保温垫块双组分原料及制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20190009748A (ko) | 2019-01-29 |
| CN109642004B (zh) | 2021-08-17 |
| WO2017198115A1 (en) | 2017-11-23 |
| JP2019516843A (ja) | 2019-06-20 |
| EP3458492A4 (en) | 2020-02-19 |
| EP3458492A1 (en) | 2019-03-27 |
| US10793663B2 (en) | 2020-10-06 |
| JP6893522B2 (ja) | 2021-06-23 |
| US20190119430A1 (en) | 2019-04-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11505670B2 (en) | Polyurethane foams co-blown with a mixture of a hydrocarbon and a halogenated olefin | |
| CN101878253B (zh) | 包含顺式-1,1,1,4,4,4-六氟-2-丁烯泡沫形成组合物的组合物以及所述组合物制备基于多异氰酸酯的泡沫的用途 | |
| US8318826B2 (en) | Ortho-cyclohexanediamine-initiated polyols and rigid polyurethane foam made therefrom | |
| CN109983050B (zh) | 聚氨酯硬质泡沫材料、其制备方法及其用途 | |
| US11161931B2 (en) | Polyol blends and their use in producing PUR-PIR foam-forming compositions | |
| CN102325818A (zh) | 包含2-氯-3，3，3-三氟丙烯和至少一种氢氟烯烃的混合物的泡沫形成组合物以及它们在基于多异氰酸酯的泡沫制备中的用途 | |
| JP5172861B2 (ja) | アミン開始ポリオール及びアミン開始ポリオールから作製される硬質ポリウレタンフォーム | |
| WO2020185443A1 (en) | Hcfo-containing isocyanate-reactive compositions, related foam-forming compositions and pur-pir foams | |
| ES2301811T3 (es) | Espumas de poliuretano o de poliisocianurato sopladas con hidrocarburos fluorados y dioxido de carbono. | |
| CN100523041C (zh) | 以甲苯二胺-引发的多元醇为基础的硬质聚氨酯泡沫体 | |
| CN109642004A (zh) | 聚氨酯泡沫和包含其的聚氨酯复合材料 | |
| US20220403096A1 (en) | Hcfo-containing isocyanate-reactive compositions, related foam-forming compositions and polyurethane foams | |
| MXPA04002807A (es) | Espuma rigida de poliuretano, dimensionalmente estables, y un proceso para producir dichas espumas en el que se reduce la presion de la espuma. | |
| JP3948014B2 (ja) | 硬質ポリイソシアヌレートフォームの製造方法 | |
| US11767407B1 (en) | HCFO-containing polyurethane foam-forming compositions, related foams and methods for their production | |
| US11767394B2 (en) | HCFO-containing polyurethane foam-forming compositions, related foams and methods for their production | |
| JP2002322232A (ja) | 硬質ポリウレタンフォーム用組成物、及びこれを用いた硬質ポリウレタンフォームの製造方法 | |
| US11753516B2 (en) | HFO-containing compositions and methods of producing foams | |
| WO2018025836A1 (ja) | 軟質ポリウレタンフォーム成型用ポリオール組成物及び軟質ポリウレタンフォーム | |
| JP2018141118A (ja) | 軟質ポリウレタンフォーム成型用ポリオール組成物 | |
| EP4306562A1 (en) | Polyurethane foaming system and rigid foam prepared therefrom | |
| CN117209706A (zh) | 聚氨酯发泡体系及由其制备的硬质泡沫 | |
| EP4306563A1 (en) | Polyurethane foaming system and rigid foam prepared therefrom | |
| US20240002575A1 (en) | Polyol blends that include an isopropylidenediphenol-based polyether polyol, related compositions and foams | |
| JP2023541370A (ja) | 硬質ポリウレタンフォーム及びフォームを含む多層断熱アセンブリ |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210817 |