DE19701074A1 - Flexible to semi-rigid integral polyurethane foam production - Google Patents
Flexible to semi-rigid integral polyurethane foam productionInfo
- Publication number
- DE19701074A1 DE19701074A1 DE19701074A DE19701074A DE19701074A1 DE 19701074 A1 DE19701074 A1 DE 19701074A1 DE 19701074 A DE19701074 A DE 19701074A DE 19701074 A DE19701074 A DE 19701074A DE 19701074 A1 DE19701074 A1 DE 19701074A1
- Authority
- DE
- Germany
- Prior art keywords
- butane
- semi
- functionality
- polyol
- flexible
- 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.)
- Withdrawn
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 229920005830 Polyurethane Foam Polymers 0.000 title description 2
- 239000011496 polyurethane foam Substances 0.000 title description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920005862 polyol Polymers 0.000 claims abstract description 26
- 150000003077 polyols Chemical class 0.000 claims abstract description 26
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001273 butane Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 9
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 9
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000001413 cellular effect Effects 0.000 claims abstract description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 4
- 239000003381 stabilizer Substances 0.000 claims abstract description 4
- 239000012190 activator Substances 0.000 claims abstract description 3
- 239000000654 additive Substances 0.000 claims abstract description 3
- FJWZMLSQLCKKGV-UHFFFAOYSA-N 1-(2-ethylphenyl)propane-1,1-diamine Chemical class CCC1=CC=CC=C1C(N)(N)CC FJWZMLSQLCKKGV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 abstract description 9
- 238000000465 moulding Methods 0.000 abstract description 5
- 239000004970 Chain extender Substances 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 235000019589 hardness Nutrition 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- -1 n- and iso-pentane Chemical class 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 239000003380 propellant Substances 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000013016 damping Methods 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 4
- WGECXQBGLLYSFP-UHFFFAOYSA-N 2,3-dimethylpentane Chemical compound CCC(C)C(C)C WGECXQBGLLYSFP-UHFFFAOYSA-N 0.000 description 3
- BZHMBWZPUJHVEE-UHFFFAOYSA-N 2,3-dimethylpentane Natural products CC(C)CC(C)C BZHMBWZPUJHVEE-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- CXOWYJMDMMMMJO-UHFFFAOYSA-N 2,2-dimethylpentane Chemical compound CCCC(C)(C)C CXOWYJMDMMMMJO-UHFFFAOYSA-N 0.000 description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Chemical compound CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- AEXMKKGTQYQZCS-UHFFFAOYSA-N 3,3-dimethylpentane Chemical compound CCC(C)(C)CC AEXMKKGTQYQZCS-UHFFFAOYSA-N 0.000 description 2
- VLJXXKKOSFGPHI-UHFFFAOYSA-N 3-methylhexane Chemical compound CCCC(C)CC VLJXXKKOSFGPHI-UHFFFAOYSA-N 0.000 description 2
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000000779 depleting effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 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
- 239000000463 material Substances 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical group O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- ZRWNRAJCPNLYAK-UHFFFAOYSA-N 4-bromobenzamide Chemical compound NC(=O)C1=CC=C(Br)C=C1 ZRWNRAJCPNLYAK-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241001425800 Pipa Species 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- NLUNLVTVUDIHFE-UHFFFAOYSA-N cyclooctylcyclooctane Chemical compound C1CCCCCCC1C1CCCCCCC1 NLUNLVTVUDIHFE-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000019000 fluorine Nutrition 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
- C08J9/34—Chemical features in the manufacture of articles consisting of a foamed macromolecular core and a macromolecular surface layer having a higher density than the core
-
- 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
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
-
- 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
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols
- C08G18/8019—Masked aromatic polyisocyanates
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0008—Foam properties flexible
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0016—Foam properties semi-rigid
-
- 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
- C08G2110/0033—Foam properties having integral skins
-
- 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
- C08G2110/0066—≥ 150kg/m3
-
- 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
- C08J2205/06—Flexible foams
-
- 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
- C08J2205/08—Semi-flexible foams
-
- 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
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)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
Gegenstand der Erfindung ist ein Verfahren zur Herstellung von weichen bis halbhar ten Polyurethanformkörpern mit einer verdichteten Randzone mit gegebener Härte und einem deutlich weicheren Zellkern von hoher Biegefestigkeit, sogenannten Inte gralschaumstoffen, bei denen als Treibmittel Butan und/oder Butan/C5-C7-Kohlen wasserstoffgemische verwendet werden.The invention relates to a process for the production of soft to semi-rigid polyurethane moldings with a densified edge zone with a given hardness and a significantly softer cell core with high flexural strength, so-called integral foams, in which butane and / or butane / C 5 -C 7 - are used as blowing agents. Coals hydrogen mixtures are used.
Zum Aufbau einer verdichteten Randzone mit zelliger Innenstruktur von weichen bis halbharten Polyurethanformteilen wurde bis zur Kenntnis des ozonschädigenden Verhaltens nahezu ausschließlich Monofluortrichlormethan (R 11) als Treibmittel verwendet. Einhergehend mit diesen Befunden wurde eine Vielzahl neuer Fluor enthaltender Treibgase vom Typ der Hydrogenfluorkohlenwasserstoffe (HFCKW) und Fluorkohlenwasserstoffe (FKW) entwickelt und untersucht. In diese Untersuchungen wurden schon früher Kohlenwasserstoffe einbezogen, wie aus einigen Patentveröffentlichungen hervorgeht (DE-A 34 30 285, US 3 178 490, US 3 182 104 , US 4 065 410, DE-A 26 22 957, US 3 931106 und DE-A 25 44 560).To build a densified edge zone with a cellular inner structure of soft to semi-hard molded polyurethane parts was known until the ozone depleting Behavior almost exclusively monofluorotrichloromethane (R 11) as a blowing agent used. Along with these findings, a large number of new fluorines were created Containing propellants of the hydrogen fluorocarbon (HCFC) type and fluorocarbons (PFC) developed and investigated. In these Studies have previously included hydrocarbons, such as from some patent publications (DE-A 34 30 285, US 3 178 490, US 3 182 104 , US 4 065 410, DE-A 26 22 957, US 3 931106 and DE-A 25 44 560).
Nach Bekanntwerden des ozonschädlichen Verhaltens der Fluorkohlenwasserstoffe hat es nicht an Versuchen gefehlt, andere Arten von Treibmitteln zur Herstellung von zellhaltigen Polyurethanen einzusetzen. So wird in EP-A 364 854 ein Verfah ren zur Herstellung von Formkörpern mit einer verdichteten Randzone und einem zelligen Kern, vorzugsweise Schuhsohlen, beschrieben aus an sich bekannten Aus gangsstoffen, jedoch unter Verwendung von niedrig siedenden aliphatischen und/oder cycloaliphatischen Kohlenwasserstoffen mit 4 bis 8 Kohlenstoffatomen im Molekül.After the ozone depleting behavior of the fluorocarbons became known there has been no shortage of attempts to manufacture other types of propellants use of cell-containing polyurethanes. A method is thus described in EP-A 364 854 ren for the production of moldings with a compressed edge zone and cellular core, preferably shoe soles, described from known per se materials, but using low-boiling aliphatic and / or cycloaliphatic hydrocarbons with 4 to 8 carbon atoms in the Molecule.
Wie sich beim Nacharbeiten des in EP 364 854 beschriebenen Verfahrens gezeigt hat, sind die mechanischen Eigenschaften mit Hilfe von aliphatischen Kohlenwasserstoffen, wie n- und iso-Pentan, hergestellten weichen bis halbharten Polyurethanformkörper noch verbesserungsfähig, insbesondere was z. B. die Anwendung solcher Schaum stoffe im Bereich von Schuhsohlen betrifft. Ideal im Aufbau von Schuhsohlen wäre eine relativ harte, in ihrer Größe begrenzte Außenzone in Kombination mit einem weicheren Kernbereich. Ein solcher Aufbau ist dann besonders für eine gute Schwingungsdämpfung sowie zur Erzielung eines guten mechanischen Werteniveaus, insbesondere guter Dauerbiegefestigkeit, geeignet.As has been shown when reworking the method described in EP 364 854, are the mechanical properties with the help of aliphatic hydrocarbons, such as n- and iso-pentane, produced soft to semi-hard molded polyurethane bodies still room for improvement, especially what z. B. the application of such foam fabrics in the area of shoe soles. Would be ideal in the construction of shoe soles a relatively hard, limited size outer zone in combination with one softer core area. Such a structure is then particularly good Vibration damping and to achieve a good mechanical value level, especially good fatigue strength.
Es wurde nun gefunden, daß durch Einsatz von Butan oder auch Abmischungen von Butan mit C5-C7-Kohlenwasserstoffen als Treibmittel eine günstigere Relation zwischen dem Integralaußen- und Innenbereich bei den PU-Formkörpern resultiert, was mit einer vorteilhaften Schwingungsdämpfung einhergeht.It has now been found that the use of butane or mixtures of butane with C 5 -C 7 hydrocarbons as blowing agents results in a more favorable relationship between the integral outer and inner areas in the PU molded articles, which is associated with advantageous vibration damping.
Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zur Herstellung von
weichen bis halbharten Polyurethanformkörpern mit einer verdichteten Randzone und
einem weichen, zelligen Kern, das dadurch gekennzeichnet ist, daß man
The present invention therefore relates to a process for the production of soft to semi-hard molded polyurethane articles with a compressed edge zone and a soft, cellular core, which is characterized in that
- a) organische und/oder modifizierte organische Polyisocyanate und/oder Polyiso cyanatprepolymere mita) organic and / or modified organic polyisocyanates and / or polyiso cyanate prepolymers with
- b) mindestens einer Polyolkomponente der OH-Zahl 20 bis 200 und einer Funk tionalität von 2 bis 6, bevorzugt 2 bis 3,b) at least one polyol component with an OH number of 20 to 200 and one radio tionality from 2 to 6, preferably 2 to 3,
- c) gegebenenfalls in Kombination mit einer Polyolkomponente der OH-Zahl 201 bis 899 und einer Funktionalität von 2 bis 3, sowie mitc) optionally in combination with a polyol component with OH number 201 up to 899 and a functionality of 2 to 3, as well as with
- d) mindestens einer Kettenverlängerungskomponente der OH- oder Amin-Zahl von 900 bis 1850 und der Funktionalität von 2 bis 4 und mitd) at least one chain extension component of the OH or amine number from 900 to 1850 and the functionality from 2 to 4 and with
-
e) gegebenenfalls an sich bekannten Zusatzstoffen, Aktivatoren und/oder Stabili
satoren
e) optionally known additives, activators and / or stabilizers
in Gegenwart von Wasser und in Gegenwart von Butan und/oder Gemischen von Butan mit C5 in the presence of water and in the presence of butane and / or mixtures of butane with C 5
-C7 -C 7
-Kohlenwasserstoffen als Treibmittel umsetzt. -Carbohydrates are used as blowing agents.
Die nach dem erfindungsgemäßen Verfahren hergestellten weichen bis halbharten Po lyurethanschaumstoffe mit Integralstruktur besitzen Shore A-Härten von 40 bis 80 im Bereich der Randzone, die dann im Kernbereich sehr schnell auf Härten von 20 bis 40, bevorzugt 25 bis 35 abfällt. Die Rohdichte beträgt 250 bis 900, bevorzugt 350 bis 700 kg/m3.The soft to semi-hard polyurethane foams with an integral structure produced by the process according to the invention have Shore A hardnesses of 40 to 80 in the region of the edge zone, which then drops very quickly to hardnesses of 20 to 40, preferably 25 to 35, in the core region. The bulk density is 250 to 900, preferably 350 to 700 kg / m 3 .
Besonders geeignet zur Einstellung dieser gewünschten Härteabstufung ist eine Kombination aus Butan und Wasser, obwohl man wegen des ausgesprochen niedrigen Siedepunktes von Butan erfahrungsgemäß annehmen kann, daß dieses Treibmittel nicht oder zumindest mäßig zur Ausbildung einer Integralschicht befähigt ist. Das Fließverhalten ist trotz des niedrigen Siedepunktes sehr gut, es lassen sich niedrige Freischaumdichten problemlos auch in Kombination mit Wasser auf das 2- bis 4-fache verdichten, wobei eine einwandfreie Formfüllung erreicht wird und der Schaumstoff den gewünschten Härteaufbau bei gutem Abrieb, Dämpfungsverhalten und guter Bie gefestigkeit hat.One is particularly suitable for setting this desired hardness gradation Combination of butane and water, although due to the extremely low Experience has shown that the boiling point of butane is that this blowing agent is not or at least moderately capable of forming an integral layer. The Flow behavior is very good despite the low boiling point, it can be low Free-foam sealing easily in combination with water 2 to 4 times compress, whereby a perfect mold filling is achieved and the foam the desired hardness build-up with good abrasion, damping behavior and good flex has strength.
Gleichermaßen geeignet sind Abmischungen von Butan und C5-C7-Kohlenwasserstof fen.Mixtures of butane and C 5 -C 7 hydrocarbons are equally suitable.
Als Kohlenwasserstofftreibmittel sind verwendbar:
The following can be used as hydrocarbon propellants:
- a) n-Butan, iso-Butan sowie deren Gemische mita) n-butane, isobutane and their mixtures with
- b) n-Pentan, Cyclopentan, Methylcyclopentan, 2-Methylpentan, 3-Methylpentan, 2,2-Dimethylbutan, 2,3-Dimethylbutan, Cyclohexan, n-Hexan, n-Heptan, 3- Methylhexan, 2-Methylhexan, 2,2-Dimethylpentan, 2,3-Dimethylpentan, 3,3- Dimethylpentan und/oder 2,4-Dimethylpentan.b) n-pentane, cyclopentane, methylcyclopentane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, n-hexane, n-heptane, 3- Methylhexane, 2-methylhexane, 2,2-dimethylpentane, 2,3-dimethylpentane, 3,3- Dimethylpentane and / or 2,4-dimethylpentane.
Wie zuvor erwähnt, wird bei dem erfindungsgemäßen Verfahren zusätzlich als Treibmittel noch Wasser verwendet. Die Menge an Wasser, die der Polyurethan-For mulierung zusätzlich einverleibt wird, beträgt üblicherweise 0,05 bis 0,6 Gew.-Teile, vorzugsweise 0,1 bis 0,4 Gew.-Teile, bezogen auf 100 Gew.-Teile der Komponente b) bzw. c) (Polyolkomponenten). Die Menge an Kohlenwasserstofftreibmittel beträgt 0,2 bis 10 Gew.-Teile, bevorzugt 0,5 bis 5 Gew.-Teile, bezogen auf 100 Gew.-Teile der Komponenten b, c und d.As mentioned above, in the method according to the invention is additionally used as Propellant still uses water. The amount of water that the Polyurethane For is additionally incorporated, is usually 0.05 to 0.6 part by weight, preferably 0.1 to 0.4 parts by weight, based on 100 parts by weight of the component b) or c) (polyol components). The amount of hydrocarbon blowing agent is 0.2 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of components b, c and d.
Als organische Polyisocyanate (a) kommen die an sich bekannten aliphatischen, cy cloaliphatischen, araliphatischen und vorzugsweise aromatischen mehrwertigen Isocyanate in Frage, wie sie beispielsweise in EP-A 364 854 genannt sind. Besonders geeignet sind die Toluylendiisocyanate und die Diphenylmethandiisocyanate, deren Modifizierungsprodukte oder ihre entsprechenden Prepolymere, die durch Urethan-, Harnstoff-, Biuret-, Allophanat-, Carbodiimid- oder Uretdion-Gruppen modifiziert sein können. Insbesondere werden als aromatische Polyisocyanate genannt: 4,4- Diphenylmethandiisocyanat, Mischungen aus 2,4'- und/oder 4,4'-Diphenylmethan diisocyanat oder Roh-MDI-Typen und/oder 2,4- und/oder 2,6-Toluylendiisocyanat sowie deren Mischungen untereinander.As organic polyisocyanates (a) come the known aliphatic, cy cloaliphatic, araliphatic and preferably aromatic polyvalent Isocyanates in question, such as those mentioned for example in EP-A 364 854. Especially suitable are the tolylene diisocyanates and the diphenylmethane diisocyanates, the Modification products or their corresponding prepolymers, which are replaced by urethane, Modified urea, biuret, allophanate, carbodiimide or uretdione groups could be. The following are mentioned in particular as aromatic polyisocyanates: Diphenylmethane diisocyanate, mixtures of 2,4'- and / or 4,4'-diphenylmethane diisocyanate or crude MDI types and / or 2,4- and / or 2,6-tolylene diisocyanate and their mixtures with one another.
Als Polyolkomponente (b) eignen sich insbesondere solche mit einer OH-Zahl von bevorzugt 20 bis 200, besonders bevorzugt 20 bis 50, und einer Funktionalität von bevorzugt 2 bis 3, wobei die Polyetherpolyole eine Molmasse von 2 000 bis 8 000 und die Polyesterpolyole eine Molmasse von 2 000 bis 4 000 aufweisen. Weniger bevorzugt sind Polyole der OH-Zahl 201 bis 899 und einer Funktionalität von 2 bis 3, jedoch können sie als Anteil der Polyolkomponente b) mitverwendet werden. Insbesondere bewährt haben sich Polyole ausgewählt aus der Gruppe Polyether- Polyole und Polyester-Polyole, wie sie durch Addition von Alkylenoxiden, wie Ethylenoxid und Propylenoxid, an mehrfunktionellen Starter, wie Ethylenglykol, Propylenglykol, Glycerin, Trimethylolpropan, Sorbit und/oder Ethylendiamin, oder durch Kondensation von Dicarbonsäuren, wie Adipinsäure, Bernsteinsäure, Glutarsäure, Korksäure, Sebacinsäure, Maleinsäure, Phthalsäure, mit überwiegend bifunktionellen Hydroxykomponenten, wie Ethylenglykol, Propylenglykol, Diethylen glykol, erhalten werden. Insbesondere genannt werden Polyetherpolyole, aufgebaut aus Ethylenoxid und Propylenoxid sowie Glycerin, Trimethylolpropan, Ethylendiamin, Propylenglykol, Ethylenglykol, Sorbit und deren Gemische als Starter. Als Polyolkomponente (b) können auch modifizierte Polyole verwendet werden, wie sie durch Pfropfung von Polyole mit Styrol und/oder Arylnitril, als Polyharnstoffdis persionen oder als PIPA-Polyole erhalten werden.Particularly suitable polyol components (b) are those with an OH number of preferably 20 to 200, particularly preferably 20 to 50, and a functionality of preferably 2 to 3, the polyether polyols having a molecular weight of 2,000 to 8,000 and the polyester polyols have a molecular weight of 2,000 to 4,000. Fewer polyols with an OH number of from 201 to 899 and a functionality of from 2 to 3 are preferred, however, they can be used as part of the polyol component b). Polyols selected from the group of polyether Polyols and polyester-polyols, such as those obtained by adding alkylene oxides, such as Ethylene oxide and propylene oxide, on multifunctional starters, such as ethylene glycol, Propylene glycol, glycerin, trimethylolpropane, sorbitol and / or ethylenediamine, or by condensation of dicarboxylic acids, such as adipic acid, succinic acid, Glutaric acid, suberic acid, sebacic acid, maleic acid, phthalic acid, with predominantly bifunctional hydroxy components, such as ethylene glycol, propylene glycol, diethylene glycol. Polyether polyols are particularly mentioned from ethylene oxide and propylene oxide and glycerol, trimethylolpropane, ethylenediamine, Propylene glycol, ethylene glycol, sorbitol and their mixtures as starters. As Polyol component (b) can also be used as modified polyols by grafting polyols with styrene and / or aryl nitrile, as polyurea dis persions or as PIPA polyols.
Die Polyether- und Polyesterpolyole können sowohl einzeln als auch im Gemisch un tereinander eingesetzt werden.The polyether and polyester polyols can be used both individually and in a mixture can be used together.
Als Komponente (d) eignen sich besonders solche, deren OH- oder Aminzahl 900 bis 1850 und deren Funktionalität zwischen 2 und 4, insbesondere 2 und 3, liegt. Beispielhaft zu nennen sind hier Ethylenglykol, 1,4-Butandiol, Glycerin, Trimethylol propan und deren kurzkettige Alkoxylierungsprodukte sowie Diethyltoluylendiamin- Isomere. Die Vernetzerkomponente d) wird in Mengen von 3 bis 20 Gew.-%, bezogen auf die Polyolkomponente b) und c), verwendet, wobei Ethylenglycol und 1,4-Butandiol sowie als Diamine Diethyltoluylendiamin-Isomere bevorzugt werden.Particularly suitable as component (d) are those whose OH or amine number is 900 to 1850 and their functionality is between 2 and 4, especially 2 and 3. Examples include ethylene glycol, 1,4-butanediol, glycerin, trimethylol propane and its short-chain alkoxylation products and diethyltoluenediamine Isomers. Crosslinker component d) is used in amounts of 3 to 20% by weight, based on the polyol component b) and c) used, wherein ethylene glycol and 1,4-Butanediol and as diamines diethyltoluenediamine isomers are preferred.
Als unter d) aufgeführte Komponenten sind zu verstehen:
Tertiäre Aminogruppen enthaltende Verbindungen, wie 1,4-Diester-(2.2.2)-bicyclo
octan und Bis-(2-dimethylaminoethyl)-ether, sowie Organometallverbindungen, wie
Dimethylzinndilaurat oder Dibutylzinndilaurat, weiter Farbpasten, Vergilbungsschutz
mittel, Füllstoffe, Flammschutzmittel, bei Polyester-Mikrobenschutzmittel, interne
Trennmittel und Stabilisatoren, wie sie aus der EP 0 364 854 bekannt sind.The components listed under d) are to be understood:
Compounds containing tertiary amino groups, such as 1,4-diester (2.2.2) bicyclo octane and bis (2-dimethylaminoethyl) ether, and organometallic compounds, such as dimethyltin dilaurate or dibutyltin dilaurate, further color pastes, anti-yellowing agents, fillers, and flame retardants Polyester microbial protection agents, internal release agents and stabilizers, as are known from EP 0 364 854.
Die Mengen sind abhängig vom jeweiligen Einsatzgebiet und können durch Vorversuche ermittelt werden.The quantities depend on the respective area of application and can be determined by Preliminary tests can be determined.
Die Herstellung der erfindungsgemäßen Formkörper ist dem Fachmann ebenfalls be kannt und braucht im Detail nicht mehr näher beschrieben zu werden. Verwiesen wird in diesem Zusammenhang wiederum auf EP-A 364 854.The preparation of the moldings according to the invention is also known to those skilled in the art knows and need not be described in detail anymore. Is referred in this connection again to EP-A 364 854.
Die nach dem erfindungsgemäßen Verfahren hergestellten Polyurethanformkörper mit Integralstruktur weisen eine Randzonenhärte von 40 bis 80 Shore A, die dann im Kernbereich sehr schnell auf Härten von 20 bis 40 Shore A abfällt. Sie eignen sich besonders als Schuhsohlenmaterial mit gutem Dämpfungsverhalten sowie verbesserter Biegefestigkeit als auch zur Ummantelung von Lenkrad- und Nackenstützeneinlagen, als Türgriff und als Türverkleidung im Automobilbereich sowie im Bereich der Körperschutzkleidung.The polyurethane moldings produced by the process according to the invention with Integral structure have an edge zone hardness of 40 to 80 Shore A, which is then in Core area drops very quickly to hardnesses of 20 to 40 Shore A. They are suitable especially as a shoe sole material with good cushioning behavior and improved Flexural strength as well as for covering steering wheel and neck support inserts, as a door handle and as door trim in the automotive sector and in the area of Body protection clothing.
Polyol 1 Polyetherpolyol der OH-Zahl 28, hergestellt durch Addition von 70 Gew.-% Propylenoxid und 30 Gew.-% Ethylenoxid an Propylen glykol als Starter mit überwiegend primären OH-Gruppen.Polyol 1 polyether polyol of OH number 28, prepared by adding 70% by weight of propylene oxide and 30% by weight of ethylene oxide on propylene glycol as a starter with predominantly primary OH groups.
Polyol 2 Polyetherpolyol der OH-Zahl 27, hergestellt durch Addition von 77 Gew.-% Propylenoxid und 23 Gew.-% Ethylenoxid an Trimethylol propan als Starter mit überwiegend primären OH-Gruppen.Polyol 2 polyether polyol of OH number 27, prepared by adding 77% by weight of propylene oxide and 23% by weight of ethylene oxide of trimethylol propane as a starter with predominantly primary OH groups.
Polyol 3 Polyetherpolyol der OH-Zahl 35, hergestellt durch Addition von 87 Gew.-% Propylenoxid und 13 Gew.-% Ethylenoxid an Glycerin als Starter mit überwiegend primären OH-Gruppen.Polyol 3 polyether polyol of OH number 35, produced by addition of 87% by weight of propylene oxide and 13% by weight of ethylene oxide as glycerol Starter with predominantly primary OH groups.
Polyisocyanat 1 Mit Tripropylenglykol umgesetztes 4,4'-Diphenylmethandiiso cyanat von 23 Gew.-% NCO-Gehalt.Polyisocyanate 1 4,4'-diphenylmethane diiso reacted with tripropylene glycol cyanate of 23 wt .-% NCO content.
Über eine für die Herstellung von Schuhsohlen üblichen Niederdruckdosieranlage mit Rührwerk der Fa. Elastogran Maschinenbau wird in eine Plattform der Größe 200 × 200 × 10 mm ein schaumfähiges Gemisch der nachstehenden Zusammensetzung in einer solchen Menge eingetragen, daß die jeweils angegebene Form-Rohdichte resul tiert. Werkzeugtemperatur: 45°C, Rohstofftemperatur: 25°C, Formstandzeit: 4 min.Via a low-pressure metering system that is customary for the production of shoe soles Agitator from Elastogran Maschinenbau is placed on a platform of size 200 × 200 × 10 mm a foamable mixture of the composition below such an amount entered that the given shape bulk density results animals. Tool temperature: 45 ° C, raw material temperature: 25 ° C, tool life: 4 min.
Die Innenwände der Form wurden mit einem handelsüblichen Formtrennmittel be sprüht (Keck-Öko 65A der Fa. J. Keck, Pirmasens). The inside walls of the mold were coated with a commercially available mold release agent sprays (Keck-Öko 65A from J. Keck, Pirmasens).
Tabelle 1Table 1
Tabelle 2Table 2
Aus Beispiel 1 geht hervor, daß Butan als Treibmittel bezüglich des Sempoflex- Dauerbiegetests als Maß für die Dauerbiegebeanspruchung einer Sohle R 11 übertrifft (Beispiel 2) und Pentan sowie Hexan (Beispiele 3, 4) deutlich überlegen ist. Die beigebrachte Einschnittstelle wird im Rahmen der Dauerbelastung nicht nennenswert vergrößert. Vorteilhaft für eine bessere Dämpfung ist zudem die Härteverteilung zwischen Rand- und Innenbereich.Example 1 shows that butane as a blowing agent with regard to the Sempoflex Permanent bending tests as a measure of the permanent bending stress of an R 11 sole exceeds (Example 2) and pentane and hexane (Examples 3, 4) is clearly superior. The The incision point provided is not significant in the context of permanent exposure enlarged. The hardness distribution is also advantageous for better damping between edge and interior.
Dieser vorteilhafte Einfluß des Butans ist auch in den Abmischungen mit höheren Kohlenwasserstoffen gegeben, wie in Tabelle 2 mit den Beispielen 6 bis 8 gezeigt. Auch hier werden Verbesserungen in der Dauerbiegefestigkeit zusammen mit einer geringen Aufweitung des Einschnitts bewirkt.This advantageous influence of the butane is also in the blends with higher ones Given hydrocarbons, as shown in Table 2 with Examples 6 to 8. Again, improvements in fatigue strength along with one causes slight widening of the incision.
Überraschend ist die Ausbildung einer sehr kompakten Randzone durch Butan, da der niedrige Siedepunkt im Vergleich zu üblichen Treibmitteln wegen der geringeren Kondensationsneigung zumindest gegenteiliges erwarten läßt.The formation of a very compact edge zone by butane is surprising since the low boiling point compared to conventional blowing agents because of the lower Condensation tendency can be expected at least to the contrary.
Weiterhin vorteilhaft ist das Schwindungsverhalten der erfindungsgemäßen Integral schaumstoffe, wie es aus nachstehender Tabelle hervorgeht. The shrinkage behavior of the integral according to the invention is also advantageous foams as shown in the table below.
Tabelle 3Table 3
Butan zeigt bei unterschiedlichen Treibgasmengen in den Beispielen 9 bis 11 nahezu eine konstante Schwindung von ca. 1,5%, während die höheren C5- und C6- Kohlenwasserstoffe eine wesentlich höhere Schwindung ergeben (12, 13). Bei Butan/C5 - und Butan/C6-Gemischen resultieren wieder deutlich niedrigere Schwin dungsreste (14, 15).With different amounts of propellant in examples 9 to 11, butane shows almost a constant shrinkage of approx. 1.5%, while the higher C 5 and C 6 hydrocarbons result in a significantly higher shrinkage (12, 13). With butane / C 5 - and butane / C 6 mixtures again significantly lower shrinkage residues result (14, 15).
Durch Butan oder Butan-Gemische werden somit Schwindungswerte erreicht, die beim Treibmittel R11 üblich waren. Demnach ist eine Weiterverwendung dieser Formen gegeben.The butane or butane mixtures thus achieve shrinkage values which were customary for blowing agent R 11 . Accordingly, these forms can be used further.
Claims (5)
- a) organische und/oder modifizierte organische Polyisocyanate und/oder Polyisocyanatprepolymere mit
- b) mindestens einer Polyolkomponente der OH-Zahl 20 bis 200 und einer Funktionalität von 2 bis 6
- c) gegebenenfalls in Kombination mit einer Polyolkomponente der OH-Zahl 201 bis 899 sowie mit
- d) mindestens einer Kettenverlängerungskomponente der OH- oder Amin-Zahl von 900 bis 1850 und Funktionalität von 2 bis 3 und mit
- e) gegebenenfalls an sich bekannten Zusatzstoffen, Aktivatoren und/oder Stabilisatoren
- a) organic and / or modified organic polyisocyanates and / or polyisocyanate prepolymers
- b) at least one polyol component with an OH number of 20 to 200 and a functionality of 2 to 6
- c) optionally in combination with a polyol component of OH number 201 to 899 and with
- d) at least one chain extension component of OH or amine number from 900 to 1850 and functionality of 2 to 3 and with
- e) optionally known additives, activators and / or stabilizers
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| DE19701074A DE19701074A1 (en) | 1997-01-15 | 1997-01-15 | Flexible to semi-rigid integral polyurethane foam production |
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| DE19701074A DE19701074A1 (en) | 1997-01-15 | 1997-01-15 | Flexible to semi-rigid integral polyurethane foam production |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10208952A1 (en) * | 2002-02-28 | 2003-09-18 | Bayer Ag | Screening process for the production and characterization of polyurethane foams |
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| US5100925A (en) * | 1991-03-07 | 1992-03-31 | E. R. Carpenter Company, Inc. | Flexible polyurethane foam having reduced discoloration due to scorch during manufacture |
| DE4115456A1 (en) * | 1991-05-11 | 1992-11-12 | Basf Ag | METHOD FOR PRODUCING FLUOROCHLOROCHOES OXYGEN FREE FORM BODIES CONTAINING URETHANO GROUPS, WITH A CELL CORE AND A COMPRESSED EDGE ZONE |
| US5240965A (en) * | 1991-04-03 | 1993-08-31 | Imperial Chemical Industries Plc | Manufacture of cellular polymers and compositions therefor |
| US5254597A (en) * | 1991-11-30 | 1993-10-19 | Basf A.G. | Production of chlorofluorocarbon-free, urethane-containing moldings having a cellular core and a compacted peripheral zone |
| US5260343A (en) * | 1993-01-04 | 1993-11-09 | Basf Corporation | Low density flexible integral skin polyurethane systems using thermoplastic hydrocarbon microspheres and water as co-blowing agents |
| US5264461A (en) * | 1992-07-15 | 1993-11-23 | Basf Corporation | Integral skin rigid polyurethane structural foam |
| GB2270918A (en) * | 1992-06-22 | 1994-03-30 | Basf Corp | Water blown polyurethane intergral skin foam |
| DE4328383A1 (en) * | 1993-02-10 | 1994-08-11 | Bayer Ag | Process for the production of isocyanate-based foams |
| DE4332771A1 (en) * | 1993-09-25 | 1995-03-30 | Hoechst Ag | Chlorofluorocarbons-free, flame-retardant rigid polyurethane foam |
| DE4434604A1 (en) * | 1994-09-28 | 1996-04-04 | Basf Ag | A process for the preparation of fluorochlorohydrocarbon-free, urethane-containing moldings having a cellular core and a compacted edge zone |
| DE19506671A1 (en) * | 1995-02-25 | 1996-08-29 | Basf Ag | Urethane] foam prodn. useful in prod. of block, moulded and integral foam with little fogging |
| DE19519335A1 (en) * | 1995-05-26 | 1996-11-28 | Basf Ag | Process for the production of molded articles containing ester and urethane groups, isocyanate semiprepolymers therefor containing them and their use |
| DE19526979A1 (en) * | 1995-07-25 | 1997-01-30 | Basf Ag | Process for the production of rigid foams based on isocyanate |
-
1997
- 1997-01-15 DE DE19701074A patent/DE19701074A1/en not_active Withdrawn
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| EP0364854A2 (en) * | 1988-10-15 | 1990-04-25 | BASF Aktiengesellschaft | Process for the production of mouldings - preferably shoe soles - having a compact outer layer and a cellular core |
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| US5240965A (en) * | 1991-04-03 | 1993-08-31 | Imperial Chemical Industries Plc | Manufacture of cellular polymers and compositions therefor |
| DE4115456A1 (en) * | 1991-05-11 | 1992-11-12 | Basf Ag | METHOD FOR PRODUCING FLUOROCHLOROCHOES OXYGEN FREE FORM BODIES CONTAINING URETHANO GROUPS, WITH A CELL CORE AND A COMPRESSED EDGE ZONE |
| US5254597A (en) * | 1991-11-30 | 1993-10-19 | Basf A.G. | Production of chlorofluorocarbon-free, urethane-containing moldings having a cellular core and a compacted peripheral zone |
| GB2270918A (en) * | 1992-06-22 | 1994-03-30 | Basf Corp | Water blown polyurethane intergral skin foam |
| US5264461A (en) * | 1992-07-15 | 1993-11-23 | Basf Corporation | Integral skin rigid polyurethane structural foam |
| US5260343A (en) * | 1993-01-04 | 1993-11-09 | Basf Corporation | Low density flexible integral skin polyurethane systems using thermoplastic hydrocarbon microspheres and water as co-blowing agents |
| DE4328383A1 (en) * | 1993-02-10 | 1994-08-11 | Bayer Ag | Process for the production of isocyanate-based foams |
| DE4332771A1 (en) * | 1993-09-25 | 1995-03-30 | Hoechst Ag | Chlorofluorocarbons-free, flame-retardant rigid polyurethane foam |
| DE4434604A1 (en) * | 1994-09-28 | 1996-04-04 | Basf Ag | A process for the preparation of fluorochlorohydrocarbon-free, urethane-containing moldings having a cellular core and a compacted edge zone |
| DE19506671A1 (en) * | 1995-02-25 | 1996-08-29 | Basf Ag | Urethane] foam prodn. useful in prod. of block, moulded and integral foam with little fogging |
| DE19519335A1 (en) * | 1995-05-26 | 1996-11-28 | Basf Ag | Process for the production of molded articles containing ester and urethane groups, isocyanate semiprepolymers therefor containing them and their use |
| DE19526979A1 (en) * | 1995-07-25 | 1997-01-30 | Basf Ag | Process for the production of rigid foams based on isocyanate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10208952A1 (en) * | 2002-02-28 | 2003-09-18 | Bayer Ag | Screening process for the production and characterization of polyurethane foams |
| DE10208952B4 (en) * | 2002-02-28 | 2004-04-08 | Bayer Ag | Screening process for the production and characterization of polyurethane foams |
| US6840124B2 (en) | 2002-02-28 | 2005-01-11 | Bayer Aktiengesellschaft | Screening process for the production and characterization of polyurethane foam materials |
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| OP8 | Request for examination as to paragraph 44 patent law | ||
| 8130 | Withdrawal |