CN110172173B - Composition for reaction with isocyanate - Google Patents
Composition for reaction with isocyanate Download PDFInfo
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- CN110172173B CN110172173B CN201910479963.7A CN201910479963A CN110172173B CN 110172173 B CN110172173 B CN 110172173B CN 201910479963 A CN201910479963 A CN 201910479963A CN 110172173 B CN110172173 B CN 110172173B
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- polyol
- hydroxyl value
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- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 239000012948 isocyanate Substances 0.000 title claims abstract description 17
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 title description 10
- 229920005862 polyol Polymers 0.000 claims abstract description 115
- 150000003077 polyols Chemical class 0.000 claims abstract description 114
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 68
- 229920000570 polyether Polymers 0.000 claims abstract description 68
- 239000004088 foaming agent Substances 0.000 claims abstract description 44
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 36
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004094 surface-active agent Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000010703 silicon Substances 0.000 claims abstract description 21
- 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 abstract description 20
- 150000001412 amines Chemical class 0.000 claims abstract description 20
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 19
- 239000004417 polycarbonate Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims abstract description 18
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001273 butane Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 76
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 20
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 16
- 239000001282 iso-butane Substances 0.000 claims description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical group [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 239000006260 foam Substances 0.000 abstract description 35
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 229920005830 Polyurethane Foam Polymers 0.000 description 21
- 239000011496 polyurethane foam Substances 0.000 description 21
- -1 carbonate polyol Chemical class 0.000 description 14
- 238000005187 foaming Methods 0.000 description 14
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 11
- 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 description 11
- 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 description 11
- 239000000600 sorbitol Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 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 description 7
- 229930006000 Sucrose Natural products 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 7
- 239000005720 sucrose Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 5
- 229960002887 deanol Drugs 0.000 description 5
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 5
- 239000012972 dimethylethanolamine Substances 0.000 description 5
- PGYPOBZJRVSMDS-UHFFFAOYSA-N loperamide hydrochloride Chemical compound Cl.C=1C=CC=CC=1C(C=1C=CC=CC=1)(C(=O)N(C)C)CCN(CC1)CCC1(O)C1=CC=C(Cl)C=C1 PGYPOBZJRVSMDS-UHFFFAOYSA-N 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 3
- YTLUDYJZQJMFKO-UHFFFAOYSA-M 2-hydroxypropyl(trimethyl)azanium;acetate Chemical compound CC([O-])=O.CC(O)C[N+](C)(C)C YTLUDYJZQJMFKO-UHFFFAOYSA-M 0.000 description 2
- OTOLFQXGRCJFQN-UHFFFAOYSA-M 2-hydroxypropyl(trimethyl)azanium;formate Chemical compound [O-]C=O.CC(O)C[N+](C)(C)C OTOLFQXGRCJFQN-UHFFFAOYSA-M 0.000 description 2
- 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 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 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 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000218378 Magnolia Species 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000013012 foaming technology Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
- C08G18/5027—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups directly linked to carbocyclic 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
- C08J9/14—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
-
- 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
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Abstract
The invention discloses a composition for reacting with isocyanate, which comprises the following components in parts by weight: complex polyol: 100 parts of composite polyol, wherein the composite polyol comprises 70-95 parts of polyether polyol, 0-15 parts of polyester polyol and 0-15 parts of polycarbonate polyol; amine catalyst: 2.0-5.1 parts; silicon surface active agent: 1.5-4.5 parts; water: 1.1-2.8 parts; mixing foaming agent: 12-22 parts of a mixed foaming agent, wherein the mixed foaming agent comprises 7-15 parts of cyclopentane, 2-10 parts of trans-1-chloro-3, 3, 3-trifluoropropene and 1-5 parts of butane. The composition is environment-friendly, has good fluidity, and the prepared foam has excellent comprehensive performance and low heat conductivity coefficient, and can effectively reduce the filling amount of raw materials and reduce the production cost of the foam.
Description
Technical Field
The present invention relates to a composition for reacting with isocyanates to produce rigid polyurethane foams.
Background
Rigid polyurethane foam is prepared by the polymerization reaction of isocyanate reactant and isocyanate in the presence of catalyst and other auxiliary agent, 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 material. 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 coefficient is added into the foam material. Unfortunately, the ozone layer is severely damaged by the conventional polyurethane blowing agent, fluorotrichloromethane (CFC-11). After the sign of Montreal protocol (1987), many countries developed the research of CFC-11 to replace foaming agent. After the release of the Kyoto protocol in 1997, people began to pay attention to both the protection of the ozone layer and the reduction of the greenhouse effect. Currently, countries around the world are working on developing new green energy-saving zero Ozone Depletion Potential (ODP) and zero Global Warming Potential (GWP) foaming systems to alleviate the increasingly serious environmental problems worldwide.
Compared with halogenated hydrocarbon foaming agents, the alkane foaming agent (such as pentane, butane and the like) has no halogen atoms, has zero ODP and approximately zero GWP, is environment-friendly and relatively low in price, and is one of ideal foaming agent alternatives. However, cyclopentane has a boiling point as high as 49 ℃ and a certain plasticity, which tends to deteriorate the dimensional stability of the foam. It is common practice to increase the foam density to ensure dimensional stability of the foam, which increases the cost of producing the foam.
Butane is poor in solubility in polyhydric alcohol, is less used for rigid polyurethane foam, and has a low boiling point, wherein the boiling point of n-butane is-0.5 ℃, the boiling point of isobutane is-11.73 ℃, the requirements on the operation process are stricter, and when butane is used for foaming alone, the butane easily escapes from a reaction material, so that the pores on the surface of the foam are increased, and the foam performance is adversely affected.
Trans-1-chloro-3, 3, 3-trifluoropropene with the molecular formula of ClCH ═ CHCF3The polyurethane foam has a boiling point of 19 ℃, an ozone layer depletion potential value (ODP) of almost 0 and a GWP value of less than 7, is a better fourth-generation foaming agent, and is foamed to prepare the hard polyurethane foam for the refrigerator, wherein the hard polyurethane foam has low heat conductivity coefficient and better comprehensive performance. However, the foaming agent is expensive, and rigid polyurethane foam prepared by using the foaming agent alone is high in cost and difficult to popularize. Moreover, if the foaming material contains a large amount of trans-1-chloro-3, 3, 3-trifluoropropene, the foaming material 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 respective defects of the foaming agent and provide a composition which is used for reacting with isocyanate and adopts an environment-friendly ternary compound foaming system to prepare rigid polyurethane foam with excellent performance.
Disclosure of Invention
The invention aims to overcome the defects of the prior foaming technology and provides an isocyanate reactant of an environment-friendly ternary compound foaming system to prepare rigid polyurethane foam with excellent performance.
The specific technical scheme is as follows:
1. a composition for reacting with isocyanate comprises the following components in parts by weight:
complex polyol: 100 parts of composite polyol, wherein the composite polyol comprises 70-95 parts of polyether polyol, 0-15 parts of polyester polyol and 0-15 parts of polycarbonate polyol;
amine catalyst: 2.0-5.1 parts;
silicon surface active agent: 1.5-4.5 parts;
water: 1.1-2.8 parts;
mixing foaming agent: 12-22 parts of a mixed foaming agent, wherein the mixed foaming agent comprises 7-15 parts of cyclopentane, 2-10 parts of trans-1-chloro-3, 3, 3-trifluoropropene and 1-5 parts of butane.
In the invention, the mixed foaming agent with the proportion can cause various foaming agents to exert synergistic action, effectively avoids the problems caused by the single use of each foaming agent and obtains the rigid polyurethane foam with good performance. The mixed foaming system of the invention takes alkane foaming agent as the main component and is matched with proper amount of trans-1-chloro-3, 3, 3-trifluoropropene, which is not only beneficial to improving the foam performance and preparing the hard polyurethane foam with fine and uniform foam holes and good heat insulation performance, but also can effectively control the raw material cost of the foam.
In the invention, the weight content of trans-1-chloro-3, 3, 3-trifluoropropene in the mixed foaming agent is not more than 56%, so that the corrosion to the liner material can be reduced, and the risks of cracking, swelling and the like of the refrigerator liner can be effectively reduced; the weight content of cyclopentane in the mixed foaming agent is kept to be more than 32 percent approximately, and a certain amount of butane is added, wherein the weight content of butane in the mixed foaming agent is not more than 36 percent, so that the initial foaming capability of the composition can be improved, the low-temperature dimensional stability of the foam can be enhanced, and the phenomenon that butane escapes from the surface of the foam due to too large addition amount can be avoided, thereby effectively reducing the defects on the surface of the foam. In addition, the mixed foaming system used in the application can increase the maximum allowable addition amount of the foaming agent in the composition, thereby reducing the foam density and reducing the production cost.
The components of the composition have good compatibility and can mutually act in a synergistic manner, and the prepared foam has uniform density distribution, good heat insulation performance, improved compression strength and high and low temperature dimensional stability and good comprehensive performance.
In the composition, the polyether polyol is prepared by reacting one or more of sucrose, sorbitol, pentaerythritol, glycerol, trimethylolpropane, toluenediamine, ethylenediamine and the like serving as an initiator with an alkylene oxide, and has the viscosity of 10000-35000 mPa & s and the hydroxyl value of 350-480 mgKOH/g.
Polyether polyols are the largest amount of polyol starting material used in polyurethane foam industry. The polyether polyol with high functionality can provide enough crosslinking degree and rigidity for the foam, and the heat resistance of the foam is good. In addition, the tolylenediamine polyether polyol having an autocatalytic effect rapidly increases the viscosity of the system at the initial stage of the reaction, and can reduce the escape of low-boiling butane. And the butane expands rapidly, so that the flowing property of the reaction liquid is improved, and the prepared foam has good fluidity and uniform density distribution.
In the composition, the polyester polyol is modified phthalic anhydride polyester polyol, the average functionality is 2.2-2.5, the viscosity is 800-5000 mPa & s, and the hydroxyl value is 360-450 mgKOH/g.
The modified phthalic anhydride polyester polyol contains rigid benzene ring structure in the molecule, and the prepared foam has high strength, good dimensional stability and reduced heat conductivity coefficient.
In the composition, the polycarbonate polyol is prepared by reacting carbon dioxide and alkylene oxide, the viscosity of the polycarbonate polyol is 500-3500 mPa.s, and the hydroxyl value is 110-250 mgKOH/g.
The carbonate polyol contains a large amount of carbonyl in a molecular structure, has large intermolecular cohesive energy, can bring excellent mechanical properties to a foam material, and can improve the foam strength so as to reduce the stable density of the foam, but the excessive use amount can cause the viscosity of a reaction material to be obviously increased and the operability to be reduced.
In the above composition, the amine catalyst is selected from two or more of pentamethyldiethylenetriamine, bis- (dimethylamino) ethyl ether, triethylenediamine, tetramethylethylenediamine, tetramethylhexamethylenediamine, N-dimethylcyclohexylamine, N-dimethylbenzylamine, dimethylethanolamine, triethanolamine, 2-hydroxypropyltrimethyl ammonium formate, 2-hydroxypropyltrimethyl ammonium acetate, 2-hydroxypropyltrimethyl octylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 1,3, 5-tris (dimethylaminopropyl) -hexahydrotriazine.
In specific production, the catalyst can be compounded according to actual needs, so that the reaction is carried out stably and balancedly.
In the composition, the silicon surfactant is a silicon-carbon surfactant and is prepared by reacting hydrogen-containing silicone oil and unsaturated polyether polyol. The choice of silicon-carbon based surfactants is well known to those skilled in the art. Specifically, the compounds can be selected from commercially available Niax L-6863, Niax L-6989, Niax L-6861 and Niax L-6866 of the Michelia; maillard AK-8805, AK 8832 and AK 8860.
The silicon-carbon surfactant has good stability and excellent hydrolysis resistance, can be stored for a long time without deterioration, has strong foam emulsifying capacity, can effectively reduce the escape tendency of alkane foaming agents, plays a role of a nucleating agent at the initial stage of foaming reaction, is beneficial to forming a large number of fine bubble nuclei, improves the nucleation speed and the fine degree of foam pores, can improve the viscoelasticity of the pore walls at the middle stage of the reaction, effectively inhibits the breakage of the foam pores, reduces surface pores and improves the foam performance.
In the composition, the butane is normal butane or isobutane, or a mixture of normal butane and isobutane in any proportion.
In the production of rigid polyurethane foams by using the composition of the present invention and isocyanate, the isocyanate is usually polymethylene polyphenyl polyisocyanate selected from commercially available ones such as 44V-10L, 44V-20L and 44V-40L from Bayer, SUPRASEC 5005, SUPRASEC2085 and SUPRASEC 5000 from Huntsman, M20S from BASF, MR200 and MR100 from Mitsui, PM2010 and PM200 from Nitidow, PAPI27 and PAPI135 from Dow, etc.
The weight ratio of the composition to the isocyanate is controlled to be 1 (0.95-1.35), during production, the composition and the isocyanate are mixed on a foaming gun head in a one-step mode according to the weight ratio of 1 (0.95-1.35), the mixture is injected into a closed mold, and the mixture is cured and formed to obtain the polyurethane foam material, wherein the set process parameters are well known to those skilled in the art, generally, the material temperature is controlled to be 15-30 ℃, the mold temperature is controlled to be 35-55 ℃, and the overfilling coefficient is 105-130%. Or a manual foaming method can be adopted, after the composition is prepared, isocyanate is quickly poured into the composition, and the mixture is immediately and quickly stirred for 3 to 6 seconds and then poured into a mould to be cured to prepare the hard polyurethane foam.
Overall, the compositions of the invention have the following advantages:
1) the rigid polyurethane foam prepared by the composition has high specific strength, and can reduce the injection amount of foaming materials, thereby reducing the production cost of the foam.
2) The hard polyurethane foam prepared by the composition has fine and uniform foam holes, low heat conductivity coefficient and good heat insulation performance.
3) The rigid polyurethane foam prepared by the composition has good high-low temperature dimensional stability, small expansion rate after demoulding and less surface defects.
4) The mixed foaming agent used in the invention has extremely low ODP and GWP, is green and environment-friendly and is environment-friendly.
Detailed Description
The examples, which are not subject to specific techniques or conditions, may be performed according to techniques known in the art.
The density, the thermal conductivity coefficient, the compression strength, the expansion rate and the high-low temperature dimensional change rate of the foam are respectively measured according to national standards GB/T6343-.
In the following examples, the isocyanate is referred to as the second component and the composition for reaction with isocyanate is referred to as the first component, and low density rigid polyurethane foams are produced according to the following steps:
(1) preparing a first component: adding the composite polyol, the amine catalyst, the silicon surfactant, the water and the mixed foaming agent into a mixing kettle according to a set proportion, and uniformly stirring to obtain a first component. And is conveyed to a first storage tank, and the temperature of the first component is controlled to be 20 ℃ for standby.
(2) Preparing a second component: and conveying the second component to a second storage tank, and controlling the temperature of the second component to be 20 ℃ for standby.
(3) Mixing and injecting: the first component and the second component are mixed and injected into a closed mould (1100 multiplied by 300 multiplied by 50mm) through a high-pressure machine gun head according to the weight ratio of 1 (1.0-1.25), the reaction is fully carried out, the mould temperature is controlled to be 40 ℃, the over-filling coefficient of a foaming material in the mould is 110-118%, and the rigid polyurethane foam can be obtained after 6min demoulding.
The parameters involved in the examples and comparative examples are shown in tables 1 and 2.
The parts in the following examples and comparative examples are parts by weight, and in each example, 100 parts of the complex polyol is used as a reference.
Example 1
A first component:
complex polyol: the hydroxyl value is 370mgKOH/g, 100 portions, comprising:
(1) polyether polyol A: 60 parts of sorbitol polyether polyol with a hydroxyl value of 380-440 mgKOH/g and viscosity of 15000-30000 mPa & s;
(2) polyether polyol B: 25 parts of toluene diamine polyether polyol with the hydroxyl value of 340-400 mgKOH/g and the viscosity of 10000-28000 mPa & s;
(3) polycarbonate polyol: 15 parts of hydroxyl value of 220-250 mgKOH/g, viscosity of 500-3500 mPa.s;
amine catalyst: 2.8 parts including pentamethyldiethylenetriamine 0.5 part, N, N-dimethylcyclohexylamine 1.5 parts, 2-hydroxypropyl trimethyl octylamine 0.8 part;
silicon surface active agent: 2.5 parts of Niax L-6863 and 1.0 part of Niax L-6989;
water: 2.0 parts of (B);
mixing foaming agent: 14 parts of cyclopentane 7 parts, trans-1-chloro-3, 3, 3-trifluoropropene 2 parts, n-butane 2 parts and isobutane 3 parts;
a second component: 44V-20L, 125 parts.
Example 2
A first component:
complex polyol: the hydroxyl value is 430mgKOH/g, 100 parts, and comprises the following components:
(1) polyether polyol A: 60 parts of sucrose polyether polyol with the hydroxyl value of 440-480 mgKOH/g and the viscosity of 20000-35000 mPa & s;
(2) polyether polyol B: 30 parts of toluene diamine polyether polyol with the hydroxyl value of 340-400 mgKOH/g and the viscosity of 10000-28000 mPa & s;
(3) modified phthalic anhydride polyester polyol: 10 parts of hydroxyl value of 360-450 mgKOH/g and viscosity of 800-5000 mPa & s;
amine catalyst: 2.0 parts of bis- (dimethylamino) ethyl ether and 1.6 parts of N, N-dimethylbenzylamine;
silicon surface active agent: AK-8860, 1.5 shares;
water: 1.1 parts;
mixing foaming agent: 19 parts of cyclopentane 15 parts, trans-1-chloro-3, 3, 3-trifluoropropene 3 parts and isobutane 1 part; a second component: SUPRASEC 5005, 126 parts.
Example 3
A first component:
complex polyol: the hydroxyl value is 410mgKOH/g, 100 parts, and comprises the following components:
(1) polyether polyol: 85 parts of sucrose polyether polyol with a hydroxyl value of 400-450 mgKOH/g and viscosity of 18000-32000 mPa & s;
(2) modified phthalic anhydride polyester polyol: 15 parts of hydroxyl value of 360-450 mgKOH/g and viscosity of 800-5000 mPa & s;
amine catalyst: 2.5 parts including 0.5 part of pentamethyldiethylenetriamine, 0.2 part of triethylenediamine, 1.0 part of N, N-dimethylcyclohexylamine and 0.8 part of 2-hydroxypropyl trimethyl ammonium acetate;
silicon surface active agent: 3.0 parts of Niax L-6989, 0.5 part of Niax L-6861 and 1.0 part of AK-8832;
water: 2.5 parts;
mixing foaming agent: 16 parts of cyclopentane 7 parts, trans-1-chloro-3, 3, 3-trifluoropropene 8 parts and n-butane 1 part; a second component: 44V-10L, 144 parts.
Example 4
A first component:
complex polyol: the hydroxyl value is 390mgKOH/g, 100 portions, comprising:
(1) polyether polyol A: 50 parts of sucrose polyether polyol with the hydroxyl value of 400-460 mgKOH/g and the viscosity of 18000-32000 mPa & s;
(2) polyether polyol A: 20 parts of glycerol polyether polyol, wherein the hydroxyl value is 350-400 mgKOH/g, and the viscosity is 10000-20000 mPa & s;
(3) modified phthalic anhydride polyester polyol: 15 parts of hydroxyl value of 360-450 mgKOH/g and viscosity of 800-5000 mPa & s;
(4) polycarbonate polyol: 15 parts of hydroxyl value of 110-220 mgKOH/g, viscosity of 500-3200 mPa & s;
amine catalyst: 3.5 parts of pentamethyldiethylenetriamine (0.6 part), N, N-dimethylbenzylamine (1.7 parts), 2,4, 6-tris (dimethylaminomethyl) phenol (1.2 parts),
silicon surface active agent: 4.0 parts, 2 parts comprise Niax L-6866 parts, 1 part of Niax L-6989 parts and 1 part of Niax L-6861 parts;
water: 2.8 parts;
mixing foaming agent: 12 parts of cyclopentane 7 parts, trans-1-chloro-3, 3, 3-trifluoropropene 2 parts, n-butane 2 parts and isobutane 1 part;
a second component: and 30, 2085 parts of Suprasec.
Example 5
A first component:
complex polyol: hydroxyl value is 380mgKOH/g, 100 portions, comprising:
(1) polyether polyol A: 60 parts of sorbitol polyether polyol with the hydroxyl value of 350-400 mgKOH/g and the viscosity of 15000-25000 mPa & s;
(2) polyether polyol B: 25 parts of toluene diamine polyether polyol with the hydroxyl value of 340-400 mgKOH/g and the viscosity of 10000-28000 mPa & s;
(3) modified phthalic anhydride polyester polyol: 10 parts of hydroxyl value of 360-450 mgKOH/g and viscosity of 800-5000 mPa & s;
(4) polycarbonate polyol: 5 parts of hydroxyl value of 220-250 mgKOH/g and viscosity of 1500-3500 mPa & s;
amine catalyst: 5.1 parts of bis- (dimethylamino) ethyl ether, 0.5 part of tetramethylethylenediamine, 1.0 part of N, N-dimethylcyclohexylamine, 2.0 parts of dimethylethanolamine, 1.2 parts of 2,4, 6-tris (dimethylaminomethyl) phenol,
silicon surface active agent: 3.5 parts and 2.0 parts of AK-8832 and 1.5 parts of AK-8860;
water: 1.4 parts;
mixing foaming agent: 22 parts of cyclopentane 10 parts, trans-1-chloro-3, 3, 3-trifluoropropene 10 parts and n-butane 2 parts; a second component: suprasec 5000, 120 parts.
Example 6
A first component:
complex polyol: the hydroxyl value is 390mgKOH/g, 100 portions, comprising:
(1) polyether polyol A: 65 parts of sucrose polyether polyol with a hydroxyl value of 400-480 mgKOH/g and a viscosity of 18000-35000 mPa & s;
(2) polyether polyol B: 15 parts of glycerol polyether polyol, wherein the hydroxyl value is 350-380 mgKOH/g, and the viscosity is 10000-18000 mPa & s;
(3) modified phthalic anhydride polyester polyol: 8 parts of hydroxyl value of 360-450 mgKOH/g and viscosity of 800-5000 mPa & s;
(4) polycarbonate polyol: 12 parts of hydroxyl value of 220-250 mgKOH/g and viscosity of 500-3500 mPa & s;
amine catalyst: 4.2 parts of pentamethyldiethylenetriamine 0.6 part, tetramethylhexamethylenediamine 0.8 part, N, N-dimethylbenzylamine 0.8 part, triethanolamine 1.5 parts, and 1,3, 5-tris (dimethylaminopropyl) -hexahydrotriazine 0.5 part;
silicon surface active agent: 4.5 parts including 1.5 parts of Niax L-6863, 1.0 part of Niax L-6861 and 2.0 parts of AK-8805;
water: 1.6 parts;
mixing foaming agent: 19 parts of cyclopentane 10 parts, trans-1-chloro-3, 3, 3-trifluoropropene 7 parts, n-butane 1 part and isobutane 1 part;
a second component: and PM2010, 127 parts.
Example 7
A first component:
complex polyol: the hydroxyl value is 370mgKOH/g, 100 portions, comprising:
(1) polyether polyol A: 80 parts of sorbitol polyether polyol with the hydroxyl value of 350-400 mgKOH/g and the viscosity of 15000-25000 mPa & s;
(2) polyether polyol B: 10 parts of glycerol polyether polyol, wherein the hydroxyl value is 350-380 mgKOH/g, and the viscosity is 10000-18000 mPa & s;
(3) modified phthalic anhydride polyester polyol: 5 parts of hydroxyl value of 360-450 mgKOH/g and viscosity of 800-5000 mPa & s;
(4) polycarbonate polyol: 5 parts of hydroxyl value of 220-250 mgKOH/g and viscosity of 500-3500 mPa & s;
amine catalyst: 3.0 parts including bis- (dimethylamino) ethyl ether 0.3 parts, N, N-dimethylcyclohexylamine 0.8 parts, dimethylethanolamine 0.7 parts, 2,4, 6-tris (dimethylaminomethyl) phenol 1.2 parts;
silicon surface active agent: 3.8 parts including 2.5 parts of Niax L-6866 and 1.3 parts of Niax L-6861;
water: 1.8 parts;
mixing foaming agent: 17 parts of cyclopentane 11 parts, trans-1-chloro-3, 3, 3-trifluoropropene 4 parts and n-butane 2 parts; a second component: PAPI27, 122 parts.
Example 8
A first component:
complex polyol: the hydroxyl value is 420mgKOH/g, 100 parts, and comprises the following components:
(1) polyether polyol: 80 parts of sucrose polyether polyol with the hydroxyl value of 400-480 mgKOH/g and the viscosity of 18000-35000 mPa & s;
(2) modified phthalic anhydride polyester polyol: 10 parts of hydroxyl value of 360-450 mgKOH/g and viscosity of 800-5000 mPa & s;
(3) polycarbonate polyol: 10 parts of hydroxyl value of 220-250 mgKOH/g and viscosity of 500-3500 mPa & s;
amine catalyst: 4.5 parts including pentamethyldiethylenetriamine 0.5 parts, N, N-dimethylbenzylamine 1.8 parts, dimethylethanolamine 1.0 parts, 2,4, 6-tris (dimethylaminomethyl) phenol 1.2 parts;
silicon surface active agent: 4.2 parts including 1.5 parts of AK-8832, 1.5 parts of AK-8860 and 1.2 parts of AK-8805;
water: 1.5 parts;
mixing foaming agent: 18 parts of cyclopentane 9 parts, trans-1-chloro-3, 3, 3-trifluoropropene 5 parts and isobutane 4 parts; a second component: and 130 parts of PM.
Example 9
A first component:
complex polyol: the hydroxyl value is 410mgKOH/g, 100 parts, and comprises the following components:
(1) polyether polyol A: 45 parts of sucrose polyether polyol with a hydroxyl value of 400-480 mgKOH/g and a viscosity of 18000-35000 mPa & s;
(2) polyether polyol B: 40 parts of sorbitol polyether polyol with a hydroxyl value of 380-440 mgKOH/g and viscosity of 15000-30000 mPa & s;
(3) polyether polyol C: 10 parts of toluene diamine polyether polyol, wherein the hydroxyl value is 340-400 mgKOH/g, and the viscosity is 10000-28000 mPa & s;
(4) polycarbonate polyol: 5 parts of hydroxyl value of 220-250 mgKOH/g and viscosity of 500-3500 mPa & s;
amine catalyst: 3.8 parts of pentamethyldiethylenetriamine 0.6 part, triethylenediamine 0.4 part, tetramethylhexanediamine 1.2 parts, dimethylethanolamine 0.8 part and 2-hydroxypropyl trimethyl ammonium formate 0.8 part;
silicon surface active agent: 2.2 parts, 1.2 parts comprise Niax L-6861 and 1.0 part of AK-8860;
water: 1.2 parts;
mixing foaming agent: 20 parts of cyclopentane 12 parts, trans-1-chloro-3, 3, 3-trifluoropropene 6 parts and n-butane 2 parts; a second component: PAPI135, 123 parts.
Example 10
A first component:
complex polyol: the hydroxyl value is 390mgKOH/g, 100 portions, comprising:
(1) polyether polyol A: 70 parts of sorbitol polyether polyol with a hydroxyl value of 380-440 mgKOH/g and viscosity of 15000-30000 mPa & s;
(2) polyether polyol B: 15 parts of toluene diamine polyether polyol, wherein the hydroxyl value is 340-400 mgKOH/g, the viscosity is 10000-28000 mPa & s;
(3) modified phthalic anhydride polyester polyol: 7 parts of hydroxyl value of 360-450 mgKOH/g and viscosity of 800-5000 mPa & s;
(4) polycarbonate polyol: 8 parts of hydroxyl value of 220-250 mgKOH/g and viscosity of 500-3500 mPa & s;
amine catalyst: 3.2 parts including bis- (dimethylamino) ethyl ether 0.4 part, N, N-dimethylcyclohexylamine 1.3 parts, 2,4, 6-tris (dimethylaminomethyl) phenol 1.5 parts;
silicon surface active agent: 2.8 parts of AK-8832 and 0.8 part of AK-8860;
water: 2.0 parts of (B);
mixing foaming agent: 15 parts of cyclopentane 8 parts, trans-1-chloro-3, 3, 3-trifluoropropene 3 parts and n-butane 4 parts; a second component: M20S, 132 parts.
Example 11
A first component:
complex polyol: the hydroxyl value is 390mgKOH/g, 100 portions, comprising:
(1) polyether polyol A: 70 parts of sorbitol polyether polyol with a hydroxyl value of 380-440 mgKOH/g and viscosity of 15000-30000 mPa & s;
(2) polyether polyol B: 15 parts of toluene diamine polyether polyol, wherein the hydroxyl value is 340-400 mgKOH/g, the viscosity is 10000-28000 mPa & s;
(3) modified phthalic anhydride polyester polyol: 7 parts of hydroxyl value of 360-450 mgKOH/g and viscosity of 800-5000 mPa & s;
(4) polycarbonate polyol: 8 parts of hydroxyl value of 220-250 mgKOH/g and viscosity of 500-3500 mPa & s;
amine catalyst: 3.2 parts including bis- (dimethylamino) ethyl ether 0.4 part, N, N-dimethylcyclohexylamine 1.3 parts, 2,4, 6-tris (dimethylaminomethyl) phenol 1.5 parts;
silicon surface active agent: 2.8 parts of AK-8832 and 0.8 part of AK-8860;
water: 2.0 parts of (B);
mixing foaming agent: 15 parts of cyclopentane 8 parts, trans-1-chloro-3, 3, 3-trifluoropropene 3 parts and n-butane 4 parts; a second component: M20S, 132 parts.
Comparative example 1
A first component:
complex polyol: the hydroxyl value is 390mgKOH/g, 100 portions, comprising:
(1) polyether polyol A: 70 parts of sorbitol polyether polyol with a hydroxyl value of 380-440 mgKOH/g and viscosity of 15000-30000 mPa & s;
(2) polyether polyol B: 15 parts of toluene diamine polyether polyol, wherein the hydroxyl value is 340-400 mgKOH/g, the viscosity is 10000-28000 mPa & s;
(3) modified phthalic anhydride polyester polyol: 7 parts of hydroxyl value of 360-450 mgKOH/g and viscosity of 800-5000 mPa & s;
(4) polycarbonate polyol: 8 parts of hydroxyl value of 220-250 mgKOH/g and viscosity of 500-3500 mPa & s;
amine catalyst: 3.2 parts including bis- (dimethylamino) ethyl ether 0.4 part, N, N-dimethylcyclohexylamine 1.3 parts, 2,4, 6-tris (dimethylaminomethyl) phenol 1.5 parts;
silicon surface active agent: 2.8 parts of AK-8832 and 0.8 part of AK-8860;
water: 2.0 parts of (B);
foaming agent: 14 parts of cyclopentane;
a second component: M20S, 132 parts.
Comparative example 2
A first component:
complex polyol: the hydroxyl value is 390mgKOH/g, 100 portions, comprising:
(1) polyether polyol A: 70 parts of sorbitol polyether polyol with a hydroxyl value of 380-440 mgKOH/g and viscosity of 15000-30000 mPa & s;
(2) polyether polyol B: 15 parts of toluene diamine polyether polyol with the hydroxyl value of 340-400 mgKOH/g and the viscosity of 10000-28000 mPa & s;
(3) modified phthalic anhydride polyester polyol: 7 parts of hydroxyl value of 360-450 mgKOH/g and viscosity of 800-5000 mPa & s;
(4) polycarbonate polyol: 8 parts of hydroxyl value of 220-250 mgKOH/g and viscosity of 500-3500 mPa & s;
amine catalyst: 3.2 parts including bis- (dimethylamino) ethyl ether 0.4 part, N, N-dimethylcyclohexylamine 1.3 parts, 2,4, 6-tris (dimethylaminomethyl) phenol 1.5 parts;
silicon surface active agent: 2.8 parts of AK-8832 and 0.8 part of AK-8860;
water: 2.0 parts of (B);
foaming agent: 12 parts of n-butane;
a second component: M20S, 132 parts.
Comparative example 3
A first component:
complex polyol: the hydroxyl value is 390mgKOH/g, 100 portions, comprising:
(1) polyether polyol A: 70 parts of sorbitol polyether polyol with a hydroxyl value of 380-440 mgKOH/g and viscosity of 15000-30000 mPa & s;
(2) polyether polyol B: 15 parts of toluene diamine polyether polyol with the hydroxyl value of 340-400 mgKOH/g and the viscosity of 10000-28000 mPa & s;
(3) modified phthalic anhydride polyester polyol: 7 parts of hydroxyl value of 360-450 mgKOH/g and viscosity of 800-5000 mPa & s;
(4) polycarbonate polyol: 8 parts of hydroxyl value of 220-250 mgKOH/g and viscosity of 500-3500 mPa & s;
amine catalyst: 3.2 parts including bis- (dimethylamino) ethyl ether 0.4 part, N, N-dimethylcyclohexylamine 1.3 parts, 2,4, 6-tris (dimethylaminomethyl) phenol 1.5 parts;
silicon surface active agent: 2.8 parts of AK-8832 and 0.8 part of AK-8860;
water: 2.0 parts of (B);
mixing foaming agent: 28 parts of trans-1-chloro-3, 3, 3-trifluoropropene;
a second component: M20S, 132 parts.
Comparative example 4
A first component:
complex polyol: the hydroxyl value is 390mgKOH/g, 100 portions, comprising:
(1) polyether polyol A: 70 parts of sorbitol polyether polyol with a hydroxyl value of 380-440 mgKOH/g and viscosity of 15000-30000 mPa & s;
(2) polyether polyol B: 15 parts of toluene diamine polyether polyol with the hydroxyl value of 340-400 mgKOH/g and the viscosity of 10000-28000 mPa & s;
(3) modified phthalic anhydride polyester polyol: 7 parts of hydroxyl value of 360-450 mgKOH/g and viscosity of 800-5000 mPa & s;
(4) polycarbonate polyol: 8 parts of hydroxyl value of 220-250 mgKOH/g and viscosity of 500-3500 mPa & s;
amine catalyst: 3.2 parts including bis- (dimethylamino) ethyl ether 0.4 part, N, N-dimethylcyclohexylamine 1.3 parts, 2,4, 6-tris (dimethylaminomethyl) phenol 1.5 parts;
silicon surface active agent: 2.8 parts of AK-8832 and 0.8 part of AK-8860;
water: 2.0 parts of (B);
mixing foaming agent: 15 parts of cyclopentane, 5 parts of trans-1-chloro-3, 3, 3-trifluoropropene and 8 parts of butane;
a second component: M20S, 132 parts.
Table 1 examples 1-7 raw material ratios and foam properties
TABLE 2 raw material ratios and foam properties for examples 8-11 and comparative examples 1-4
As can be seen from tables 1 and 2, the rigid polyurethane foams prepared by using the composition of the present invention have the same over-filling coefficient, the raw material pouring amount and the foam core density of examples 1 to 10 are obviously less than those of comparative examples 1 to 4, but the thermal conductivity is lower, the thermal insulation performance is better, the dimensional stability is better, and the linear expansion rate is low after 5min of demolding. In contrast, in example 11, compared with comparative examples 1 to 4, the injection amount and the foam density are similar, but the performances are obviously superior to those of the comparative examples. The composition of the invention can obviously improve the application performance of the foam. Therefore, under the same process parameters, the technical scheme of the invention can effectively reduce the raw material pouring amount and the foam density, thereby reducing the production cost.
Claims (6)
1. A composition for reacting with isocyanate, characterized by consisting of, in parts by weight:
complex polyol: 100 parts of composite polyol, wherein the composite polyol comprises 70-95 parts of polyether polyol, 0-15 parts of polyester polyol and 0-15 parts of polycarbonate polyol;
amine catalyst: 2.0-5.1 parts;
silicon surface active agent: 1.5-4.5 parts;
water: 1.1-2.8 parts;
mixing foaming agent: 12-22 parts of a mixed foaming agent, wherein the mixed foaming agent comprises 7-15 parts of cyclopentane, 2-10 parts of trans-1-chloro-3, 3, 3-trifluoropropene and 1-5 parts of butane.
2. The composition according to claim 1, wherein the polyether polyol has a viscosity of 10000 to 35000 mPa-s and a hydroxyl value of 350 to 480 mgKOH/g.
3. The composition according to claim 1, wherein the polyester polyol is a modified phthalic anhydride polyester polyol, has an average functionality of 2.2 to 2.5, a viscosity of 800 to 5000 mPa-s, and a hydroxyl value of 360 to 450 mgKOH/g.
4. The composition according to claim 1, wherein the polycarbonate polyol is obtained by reacting carbon dioxide with an alkylene oxide, and has a viscosity of 500 to 3500mPa · s and a hydroxyl value of 110 to 250 mgKOH/g.
5. The composition of claim 1, wherein the silicon surfactant is a silicon-carbon based surfactant and is prepared by reacting a hydrogen-containing silicone oil with an unsaturated polyether polyol.
6. The composition according to claim 1, wherein the butane is n-butane or isobutane, or a mixture of n-butane and isobutane in any ratio.
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| CN201910479963.7A CN110172173B (en) | 2019-06-04 | 2019-06-04 | Composition for reaction with isocyanate |
| PCT/CN2020/090670 WO2020244371A1 (en) | 2019-06-04 | 2020-05-15 | Composition used for reacting with isocyanate |
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| CN114716722A (en) * | 2021-01-04 | 2022-07-08 | 海信容声(广东)冰箱有限公司 | Refrigerator, hard polyurethane foam and preparation method of hard polyurethane foam |
| CN114940738B (en) * | 2022-06-02 | 2024-02-27 | 万华化学（宁波）容威聚氨酯有限公司 | Polyurethane composition, polyurethane foam, and preparation method and application thereof |
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| CN101952336A (en) * | 2007-10-12 | 2011-01-19 | 霍尼韦尔国际公司 | Amine catalysts for polyurethane foams |
| CN104271650A (en) * | 2011-12-09 | 2015-01-07 | 霍尼韦尔国际公司 | Foams and articles made from foams containing HCFO or HFO blowing agents |
| CN104356335A (en) * | 2014-11-14 | 2015-02-18 | 南京红宝丽聚氯酯有限公司 | Open-pore polyurethane rigid foam prepared from polyurethane rigid foam degradation liquid |
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| US9000061B2 (en) * | 2006-03-21 | 2015-04-07 | Honeywell International Inc. | Foams and articles made from foams containing 1-chloro-3,3,3-trifluoropropene (HFCO-1233zd) |
| CN105601978B (en) * | 2015-11-10 | 2018-05-11 | 南京红宝丽聚氨酯有限公司 | A kind of hard polyurethane foams |
| CN107177028B (en) * | 2017-06-13 | 2020-08-04 | 合肥华凌股份有限公司 | Combined polyether, polyurethane foam and preparation method and application thereof |
| CN108976463B (en) * | 2018-06-13 | 2021-01-26 | 合肥华凌股份有限公司 | Composition set for preparing polyurethane foam, preparation method and application thereof |
| CN109762136B (en) * | 2019-01-25 | 2021-05-25 | 海信容声(广东)冰箱有限公司 | Polyurethane foaming composition, polyurethane foam, and preparation method and application thereof |
| CN110172173B (en) * | 2019-06-04 | 2021-07-09 | 红宝丽集团股份有限公司 | Composition for reaction with isocyanate |
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|---|---|---|---|---|
| CN101952336A (en) * | 2007-10-12 | 2011-01-19 | 霍尼韦尔国际公司 | Amine catalysts for polyurethane foams |
| CN104271650A (en) * | 2011-12-09 | 2015-01-07 | 霍尼韦尔国际公司 | Foams and articles made from foams containing HCFO or HFO blowing agents |
| CN104356335A (en) * | 2014-11-14 | 2015-02-18 | 南京红宝丽聚氯酯有限公司 | Open-pore polyurethane rigid foam prepared from polyurethane rigid foam degradation liquid |
| CN109021207A (en) * | 2018-05-22 | 2018-12-18 | 南京红宝丽聚氨酯有限公司 | A kind of hard polyurethane foam for refrigerator |
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Application publication date: 20190827 Assignee: NANJING HONGBAOLI POLYURETHANE Co.,Ltd. Assignor: HONGBAOLI GROUP Co.,Ltd. Contract record no.: X2022980017547 Denomination of invention: Composition for reaction with isocyanate Granted publication date: 20210709 License type: Common License Record date: 20221009 |
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Denomination of invention: A composition for reacting with isocyanates Effective date of registration: 20231215 Granted publication date: 20210709 Pledgee: Bank of China Limited by Share Ltd. Gaochun branch Pledgor: HONGBAOLI GROUP Co.,Ltd. Registration number: Y2023980071636 |