CA2069651A1 - Stabilization of dichlorotrifluoroethane-containing mixtures - Google Patents
Stabilization of dichlorotrifluoroethane-containing mixturesInfo
- Publication number
- CA2069651A1 CA2069651A1 CA 2069651 CA2069651A CA2069651A1 CA 2069651 A1 CA2069651 A1 CA 2069651A1 CA 2069651 CA2069651 CA 2069651 CA 2069651 A CA2069651 A CA 2069651A CA 2069651 A1 CA2069651 A1 CA 2069651A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- chcl2
- tert
- mixture
- dmp
- 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.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 64
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 230000006641 stabilisation Effects 0.000 title claims abstract description 7
- 238000011105 stabilization Methods 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 36
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 11
- 229920001228 polyisocyanate Polymers 0.000 claims description 11
- 229920005862 polyol Polymers 0.000 claims description 7
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011496 polyurethane foam Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 230000008030 elimination Effects 0.000 description 9
- 238000003379 elimination reaction Methods 0.000 description 9
- 238000003860 storage Methods 0.000 description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 4
- 238000006298 dechlorination reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- VOOVDZMAQQVAEW-PFONDFGASA-N [(z)-2-methyl-4-phenylpent-3-en-2-yl]benzene Chemical compound C=1C=CC=CC=1C(/C)=C\C(C)(C)C1=CC=CC=C1 VOOVDZMAQQVAEW-PFONDFGASA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229940029284 trichlorofluoromethane Drugs 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- ICLPNZMYHDVKKI-UHFFFAOYSA-N 1,1,3-trimethyl-3-phenyl-2h-indene Chemical compound C12=CC=CC=C2C(C)(C)CC1(C)C1=CC=CC=C1 ICLPNZMYHDVKKI-UHFFFAOYSA-N 0.000 description 1
- BOUGCJDAQLKBQH-UHFFFAOYSA-N 1-chloro-1,2,2,2-tetrafluoroethane Chemical compound FC(Cl)C(F)(F)F BOUGCJDAQLKBQH-UHFFFAOYSA-N 0.000 description 1
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical compound CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- QPAXMPYBNSHKAK-UHFFFAOYSA-N chloro(difluoro)methane Chemical compound F[C](F)Cl QPAXMPYBNSHKAK-UHFFFAOYSA-N 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 description 1
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- ZJULYDCRWUEPTK-UHFFFAOYSA-N dichloromethyl Chemical compound Cl[CH]Cl ZJULYDCRWUEPTK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- -1 for example Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- GWUSZQUVEVMBPI-UHFFFAOYSA-N nimetazepam Chemical compound N=1CC(=O)N(C)C2=CC=C([N+]([O-])=O)C=C2C=1C1=CC=CC=C1 GWUSZQUVEVMBPI-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000011495 polyisocyanurate Substances 0.000 description 1
- 229920000582 polyisocyanurate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000029305 taxis Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical class CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
- C07C19/10—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine
- C07C19/12—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine having two carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/42—Use of additives, e.g. for stabilisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Abstract of the disclosure:
Stabilization of dichlorotrifluoxoethane containing mixtures The invention relates to a mixture which essentially comprises 2,4-diphenyl-4-methylpentene, 4-tert.-butyl-pyrocatechol and at least one of the two dichlorotri-fluoroethanes CF3-CHCl2 and CClF2-CHClF, and to a process for the stabilization of mixtures containing at least one of the dichlorotrifluoroethanes CF3-CHCl2 and CClF2-CHClF
and at least one aminopolyol and/or amine, which com-prises adding an effective amount of 2,4-diphenyl-4-methylpentene and 4-tert.-butylpyrocatechol to the mixtures.
Stabilization of dichlorotrifluoxoethane containing mixtures The invention relates to a mixture which essentially comprises 2,4-diphenyl-4-methylpentene, 4-tert.-butyl-pyrocatechol and at least one of the two dichlorotri-fluoroethanes CF3-CHCl2 and CClF2-CHClF, and to a process for the stabilization of mixtures containing at least one of the dichlorotrifluoroethanes CF3-CHCl2 and CClF2-CHClF
and at least one aminopolyol and/or amine, which com-prises adding an effective amount of 2,4-diphenyl-4-methylpentene and 4-tert.-butylpyrocatechol to the mixtures.
Description
2 ~
HOECHST AKTIENGESELLSCHAFT HOE 91/F 163 Dr.MA/rh Description Stabilization of dichlorotrifluoroethane-containing mixtures The invention relates to the stabilization of dichloro-trifluoroethane-containing mixtures which are used for the preparation of polyurethane foam.
Dichlorotrifluoroethane (CF3-CHCl2 and CClF2-CHClF) is intended as a replacement for trichlorofluoromethane (CFC
11), which will soon b~ unavailable due to presumed damage to the ozone layer in the atmosphere and which i8 used as a blowing agent in the production of foams based on polyisocyanates, in particular polyurethane and polyisocyanurate foams (US Patent 3,183,19~). The produc-tion of such foams is known and is described, forexample, in ~uns~stoff-Handbuch, Volume YII, Polyure-thane, Carl Hanser Verlag, Munich, Vienna (1983), pages 246 to 331, and in EP-A-0 077 964, EP-A-0 334 059, and DE-B 1 694 138 t= ~ritish Patent 1,209,243).
Ullmanns Enzyklopadie der technischen Chemie (1980), Volume 19, pages 301 ~o 341, gives a review of the raw materials which can be used and the possible processes for the production of rigid polyurethane foams.
In addition, corresponding information can be found in Kirk-Othmer, Encycl. of Chem. Technology, 3rd edition, Vol. 11 (1980), pages 87 - 89, and Yol. 23 (1983), pages 576 - 607.
Por the production of polyurethane foams, a mixture of polyols, catalysts, foam stabilizers, dichlorotrifluoro-ethane as blowing agent, water and, if desired, flame-proofing agents and other additives ~this mixture is referred to below as component A), is in many cases supplied in ready-mixed form to the user. In this case, the dichlorotrifluoroethane is in contact with th~ other constituents of component A for some time before the reaction with polyisocyanate (refexred to below as component B) taXes place to give the polyurethane foam.
An alternative is the preparation of component A from the abovementioned individual co]mponents or from partial mixtures of these directly by the foam maker. Again, component A must in this case be stored before foaming.
Polyisocyanates which are suitable for foaming are alipha~ic, cycloaliphatic and aromatic diisocyanates or polyisocyanates. Preference is given to 2,4- and 2,6-tolylene diisocyanates, diphenylmethane diisocyanate, polymethylene-polyphenyl isocyanate and mixtures thereof.
It is also possible to use polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups, which ar~ known as ~modified polyisocyanates~ or "isocyana~e prepolymers".
The polyols employed are in general compounds containing at least two hydrogen atoms which are reactive toward isocyanate groups, for example polyether-, polyester- and amine-based compounds, and amino- and/or carboxyl- and/or thiol-containing compounds, generally h~ving 2 - 8 hydrogen atoms which are reactive toward polyisocyanates (US Patent 3,183,192). Hydroxyl-containing amino compounds ~aminopolyols3 are frequently employed here, either alone or in addition to amino-free polyols.
The reaction of the polyols and/or aminopolyols with the polyisocyanates is carried out with addition of a cata-lyst. The catalysts usually employed are amino compounds, in particular tertiary amino compounds (for example dimethylcyclohexylamine). These amino compounds are added to the abo~ementioned component A. However, it is also ~,3~3~
possible to employ amino-free compounds as cataly8t8, such a~, for example, organotin compounds, for example dibutyltin dilaurate.
However, it has been ~hown thiat the mixtures cont~ining cataly~ically active amino compounds and/or aminopolyols react with the hydrogen-cont:aining dichlorotrifluoro-ethanes HCFC 123 (CF3-CHCl~) and HCFC 123 a lCClF2-CHClF) with elimination of hydrogen chloride to give hydrogen rich hydrochlorofluoroalkan0s, in particular HCFC 133a (CF3-CH2Cl). The extent of lthis reaction depends on various parameters, such as pH, temperature and metal ion contents. The hydrogen chloride formed has a considerable adverse effect on the subsequent foaming reaction with the polyisocyanate. In some cases, the conditions mentioned also give rise to crystalline depolsits in the component A which interfere with the metering by means of precision metering pumps. HCFC 133a is an undesirable by-product due to its carcinogenic properties (in animal experiments).
Although it is in principle possible to use highly reactive polyols with amine-free formulations in which a dechlorination reaction does not normally occur, the catalysts which can be used here are org~nometallic compounds, such as, for example, dibutyltin dilaurate.
The object of the present invention is to make it pos-sible also to employ systems containing aminopolyols and/or other amino compounds in the presence of dichloro-trifluoroethane without formation of HCl or HGFC 133a occurring.
German Patent 1 207 626 (US Patent 3,183,192) discloses that unsaturated compounds such as butadiene, isoprene, styrene, alpha-methylstyrPne or l-alkenes having 4 to 18 carbon atoms can be employed as stabilizers for the (fully halogenated) chlorofluoroalkane compounds 2 t~ 3 n ) L
trichlorofluoromethane and trichlorotrifluoroethane in foamablecompositionsofthistype. German Patent 3 139 401 (us Patent 4,463,189) discloses that 2,4-diphenyl-4-methylpentene (DMP) also fiuppresses the undesired reaction of aminopolyols with these chlorofluoroalkanes.
It has been found that DMP also suppresses the dechlori-nation reactions of the (hydrogen-containing~ dichloro-trifluoroethanes to a certain extent. It has furthermore been found that 4-~ert.-butylpyrocatechol likewi~e hinders these dachlorination reactions to a certain extent.
Surprisingly, it h~s been found that mixtures of 4-tert.~
butylpyrocatechol and DMP completely suppress this dechlorination reaction, so that, in particular, the formation of HCFC 133a (CF3~CH2Cl) and HCl is prevented.
The in~ention relates ~o a mixture which essentially comprises DMP, 4-tert.-butylpyrocatechol and at least one of the two dichlorotrifluoroethanes CF3-CHCl2 and CClF2-CHClF. In general, the mixture contains an amount of DMP
and 4-tert.-butylpyrocatechol which is sufficient to suppress said dechlorination reaction of the dichloro~ri-fluoroethanes if they are employed together with amino-polyols and/or other amino compounds in the foaming of polyurethane, but the content of D~P and 4-tert.-butyl-pyrocatechol is normally at most 10% by weight. Themixture preferably contains from 0.1 to 5~ by weight of DMP and from 0.02 to 2% by weight of 4-tert.-butylpyro-catechol, in particular from 0.2 to 2% by weight of DNP
and from 0.05 to 1~ by weight of 4-tert.-butylp~rocate-- 30 chol, based on the total amount of dichlorotrifluoro-ethanes.
The invention furthermore relates to a process for the stabilization of mixtures containing at least one of the dichlorotrifluoroethanes CF3-CHCl2 and CClF2~CHClF and 2~$~3S i aminopolyols and/or primary, secondary or tertiary amines, which comprises adding an effective amount of 2,4-diphenyl-4-methylpentene and 4-te:rt.-butylpyrocate-- chol to the mixtures. The preferred and particularly preferred amounts of DMP and 4-tert.-butylpyrocatechol are the same as in ths mixture ~ust mentioned.
The mixtures of 4-tert.-butylpyrocatechol and DMP are soluble in dichlorotrifluoroethane and do not affect the foaming reaction.
DMP is a commercially available product under the name 'dimeric alpha-methylstyrene`~ ~CAS No. 6144-04-3~ and can be prepared, for example, as described in US Patent 2,429,719.
It generally comprises the two isomers 2,4-diphenyl-4-methyl-l-pentene and 2,4-diphenyl-4-methyl-2-pentene. The l-pentene/2-pentene isomer ratio is generally from about 1:1 to 9:1.
Instead of the mixture of the two pentenes, it is also possible to employ a technical-grade mixture which, in addition to these two isomers, also contains a small amount of 1,1,3-trLmethyl-3-phenylindane. A mixture of this type iæ obtainable, for example, by the process of US Patent 2,429,719 and generally contains from 45 to ~9%
by weight of 2,4-diphenyl-4-methyl~1-pentene, from 10 to 45~ by weight of 2,4-diphenyl-4-methyl-2-pentene and from 1 to 20~ by weight of 1,1,3-trimethyl-3-phenylindane. If a technical-grade mixture of this type is used, the amount must naturally be selected so that the above-- mentioned percentages of pure DMP are achieved.
It is of course also possible to employ the pure isomers individually, but separation of the isomer mixture formed in the preparation of DMP would be an unnecessary expense.
r~
4-tert.-Butylpyrocatechol (with the C~S Mo. 98-29-3) is a known polymerization inhibitor for monomeric olefins and is a commercially a~ailable compound tBeilstein E III
6:4671~.
It is in principle possible for other hydrochlorofluoro-alkanes, such as chlorotetrafluoroethane, l,l-dichloro-1-fluoroethane or l-chloro-l,1-difluoroethane, which are suitable as blowing agents for the same applications as the dichlorotrifluoroethanes for foaming polyurethane~, to be stabilized in the same way.
The invention i8 illustr~ted in greater detail by means of the examples below. In the tables, 4-tert.-butyl-pyrocatechol is ab~reviated to ~'But".
Examples Experimental procedure:
To carry out the tests, in each case 50 g of the mixtures described in the examples below were weighed out into aerosol glass bottles, which were Lmmediately sealed in a gas-tight manner and stored at a temperature of 50C.
Although the elimination products (hydrogen chloride and CF3-CH2Cl) appear even at storage temperatures of about 20C, a temperature of 50C was selected for accelerated testing since, as is known, a temperature increase of 30~C accelerates chemical reactions considerably. The mixtures were assessed as to visual appearance after the time specified in each case and analyzed for elLmination products.
The amounts of elimin~tion products are given in % by weight, based on the total weighed out mixture, with hydrogen chloride being determined as chloride.
The tertia~ amino compollnds investigated, which would act as catalysts in a reaction with polyisocyanate, were v ~J ~
dLmethylcyclohexylamine and d~lethylaminoethanol.
Example 1:
a) 70~ by weight of dimethylcyclohexylamine (DMCHA~ and 30~ by weight of CHCl2-CF3 were mixed and stored at 50C for 14 days. The anialytical re~ults are shown in Table 1.
b) The procedure was as in Example la), but the CHCl2-CF3 was replaced by a mixture of 93% by weight of CHCl2-CF3 and 7% by weight of CClF2-CHClF. The analytical resul~s are shown in Table 2.
c) The procedure was as in ~xample la), but addition-ally with 1~ by weight of DMP, based on the content of CHCl2-CF3. The results are shown in Table 1.
d) The procedure was as in Example lb), but addition-ally with 1% by weight of DMP, based on the total amount of dichlorotrifluoroethane mixture comprising 93% by weight of CHCl2-CF3 and 7% by weight of CClF2-CHClF. The results are shown in Table 2.
e) The procedure was as in Example la), but addition-ally with 1~ by weight of ~-tert.-butylpyrocatechol, based on the content of CHCl2-CF3. The results are shown in Table 1.
f3 The procedure was as in Example lb), but addition-- ally with 1% by weight of 4-tert.-butylpyrocatechol, based on the total amount of dichlorotrifluoroethane mixture comprising 93% by weight of CHCl2-CF3 and 7%
by weight of CClF2-CHClF. The results are shown in Table 2.
g) The procedure was as in Example la), but addition-ally with 1% by weight of a stabilizer mixture comprising 50% by weight of DMP and 50% by weight o~
s~ ~3 ~ ~ ~3 r' ~
~ 8 ~
4-tPrt.-butylpyrocat~chol, based on the content of CHCl2-CF3. The xesult~ are shown in Tabl~ 1.
h) The procedure was as in Example lb), but addition~
ally with 1~ by weight of a s~abilizer mixture comp~ising 50~ by weight of DMæ and 504 by weight of 4-tert.-butylpyrocatecho], based on the tot~l amount of dichlorotrifluoroethane mixture comprising 93% by weight of CHCl2-CF3 and 7~ by weight of CClE2-CHClF.
The results are shown in Table 2.
~xample 2:
a) A mixture of 70~ by weight of dimethylaminoethanol (DMEA) and 30% by weight of CHCl2-CF3 was investi-ga~ed. The results are shown in Table 3.
b) The procedure was as in Example 2a), but the CHCl2-CF3 was replaced by a mixture of 93~ by weight of CHCl2-CF3 and 7% by weight of CClF2-CHClF. The analytical results are shown in Table 4.
c) The procedure was as in Example 2a), but addition-ally with 1~ by weight of DMP, based on the content of CHCl2-CF3. The results are shown in Table 3.
d) The procedure was as in Example 2b), but addition ally with 1% by weight of DNP, based on the total amount of dichlorotrifluoroethane mixture comprising 93~ by weight of CHC12-CF3 and 7~ by weight o~ CClF2-CHClF. The results are shown in Table 4.
e) The procedure was ~s in Example 2a), but addition-ally with 1~ by weight of 4-tert.-butylpyrocatechol, based on the content of CMCl2-CF3. The results are shown i.n Table 3.
0 f) The procedure was as in Example 2b), but addition-ally with 1% by weight of 4-tert.-butylpyrocatechol, 2 ~ & J ~
_ 9 _ bas~d on the total amount of dichlorotrifluoro2thane mixture comp~ising 93% by weight of CHCl2-CF3 and 7%
by weight of CClF2-CHClF. The results are ~hown in Table 4.
g) The procedure was as in Example 2a), but addition-ally with 1~ by weight of a stabilizer mixture comprising 50% by weight of DMP and 50~ by weight of 4-tert.-butylpyrocatecho.l, based on the conten$ of CHCl2-CF3. The results are shown in Table 3~
h) The procedure was as in Example 2b), but addition-ally with 1% by weight of a stabilizer mixture comprising 50% by weight of DMP and ~0% by weight of 4-tert.-butylpyrocatechol, based on the total ~mount of dichlorotrifluoroethane mixture comprising 93% by weight of CHCl2~-CF3 and 7% by weight of CClF2-CHClF.
The results are shown in Table 4.
Example 3:
a) A mixture of 70% by wPight of aminopolyol based on ethylenediamine and propylene oxide having a hydroxyl number of 450 and 30% by weight of CHCl2-CF3 was investigated after l day, after 7 days and after 14 days. The results are shown in Table 5.
b) The procedure was as in Example 3a), but the CHC12-CF3 was replaced by a mixture of 93% by weight of CHCl2 CF3 and 7% by weight of CClF2-CHClF. The results are shown in Table 6.
c) The procedure was as in Example 3a), but addition-ally w:ith 1% by weight of DMP, based on the content of CHC:L2-CF3. The results after 14 days are shown in Table 5.
d) The procedure was as in Example 3b), but addition-ally with 1~ by weight of DMP, based on the total .
2 ~ 5 1 - ln-amount of dichlorotrifluoroethane mixture comprising g3~ by weight of CHC12-CF3 and 7% by weight of CClF2-CHClF. The analytical results after 14 days are shown in Table 6.
e) The procedure was as in E,xample 3G ), but with 1% by weight of 4-tert.-butylpyrocatechol, based on the con~ent of CHC12-CF3. The results are shown in Table 5.
f) The procedure was as in Example 3d~, but with 1~ by weight of 4-tert.-butylpyrocatechol, based on the total amount of dichlorotrifluoroethane mixture comprising 93% by weight of CHCl2-CF3 and 7% ~y weight of CClF2-CHClF. The results are shown in Table 6.
5 g) The procedure was as in Example 3~), but with 1~ by weight of a stabilizer mixture comprising 50% by weight of DMP and 50~ by weight of 4-tert.-butyl-pyrocatechol, based on the content of dichlorotri-fluoroethane. The results are shown in Table 5.
0 h) The procedure was as in Example 3d), but with 1% by weight of a stabilizer mixture comprising 50% ~y weight of DNP and 50% by weight of 4-tert.-butyl-pyrocatechol, based on the total amount of dichlorotrifluoroethane mixture comprising 93% by weight of CHClz-CF3 and 7~ by weight of CClF2-CHClF.
The results are shown in Table 6.
Example 4:
a) A mixture of 73~ by weight of the aminopolyol used in Example 3, 1.5~ by weight of DMCHA and 25.5~ by weight of CHCl2-CF3 was investigated. The results are shown in Table 7.
2 ~
b ) The procedure was as in Example 4a~, but the CHCl2-CF3 was replaced by a mixture of 93% by weight of CHClz-CF3 and 7~ by we:ight of CClF2-CHClE. The results are shown in Table 8.
c) The procedure wa~ as in Example 4a), but addition-ally with 1% by weight of DNP, based on the content of CHCl2-CF3. The results are shown in Tabla 7.
d) The procedure was as in ~xample 4b)/ but addition-ally with 1~ by weight of DMoe, based on the total amount of dichlorotrifluoroethane mixture comprising 93% by weight of CHCl2-CF3 and 7% by weight of CClF~-CHClF. The results are shown in Tablo 8.
e) The procedure was as in Example 4a), but addition-ally with 1~ by weight of 4-tert.-butylpyrocatechol, based on the content of CHCl2-CF3. The results are shown in Table 7.
f) The procedure was as in Example 4b), but addition-ally with 1~ by weight of 4-tert.-butylpyrocatechol, based on the total amount o~ dichlorotrifluoroethane mixture comprising 93~ by weight of CHCl2-CF3 and 7%
by weight of CClF2-CHClF. The results are shown in Tabl~ 8.
g) The procedure was as in Example 4a), but addition-ally with 1% by weight of a stabilizer mixture comprising 50% by weight of DMP and 50~ by weight of 4-tert.-butylpyrocatechol, based on the content of CHCl2-CF3. The analytical results aftex 14 and 26 days are shown in Table 7.
h) The procedure was as in Example 4b), but addition-ally with 1% by weight of a stabilizer mixture comprising 50% by weight of DNP and 50% by weight o~
4-tert.-butylpyrocatechol, ba~ed on the total amount :
2 (~
of dichlorotri~luoroethane mixture comprising 93~ by weight of CHC12-CF3 and 7~ by weight of CClF2-CHClF.
~he analytical results after 14 and 26 days are shown in Table 8.
Example 5:
The mixture described in Ex~mple 4a) was mixed with various amounts of DMP and 4-tert.-butylpyrocatechol and stored a~ in the examples above. The stabili2er content~
and the results are shown in l'able 9.
Table 1 .
Example Storage Stabili~er Elimination tLme products (days) ~1~, based on CHCl2-CF3) ~ of C2H2ClF3 ~ofCl la 14 - 0.13 0.04 lc 14 DMP 0.10 0.03 le 14 But O . 05 n.m.
lg 14 DMP/But 1:1 n.d. n.d.
Table 2 Example Storage Stabilizer ElLmination time (1%, based on CHCl2-CF3/ products (days) CC12F-CHClF3 % of C2H2ClF3 ~ o~Cl lb 14 - 0.11 0.03 ld 14 DMP 0.0~ n.m~
lf 14 But 0.10 n.m.
lh 14 DMP~But 1:1 n.d. n.d.
.
n.d. = not detectable (detection limit 0.001~) n.m. = not measured 2 3,~,~ d~J ~ ~3 ~
Table 3 , . . _ . _ Example Storage Stabilizer Elimination time products (days) (1~, based on CHCl2-CF3) % of C2H2ClF3 ~ o~
.. . .. _ _ _ 2a 14 - 0.19 0.06 2c 14 DMP 0.13 0.04 2e 14 But 0.13 n.m.
2g 14 DMP/But 1:1 n.d. n.d.
.
Table 4 Example Stora~e Stabilizer Elimination time (1%, based on CHCl2-CF3/ products - (days) CClF2-CHClF)% of C2H2ClF3 % o~Cl -2b 14 - 0.06 0.05 2d 14 DMP 0.02 n.m.
2f 14 But 0.02 0.01 2h 14 DMP/But 1:1 n.d. n.d.
_ n.d. = not detectable (detection limit 0.001%) n.m. = not measured 2 Q '~ ~ ~J`~
Table 5 Example Storage S-tabilizer Ellmination time products (days) (1~, based on CHCl2-CF3) % of C2H2ClE3 % ofCl 3a 1 - 0.020 n.d.
7 - 0.055 ~.0018 l~ - 0.549 0.013 3c 14 DMP 0.134 0.036 3e 14 But n.d. 0.003 3g 14 DMP/But l:l n.d. n.d.
Table 6 Example Storage Stabilizer Elimination time (l~, ba~ed on CHCl2-CF3/ products (days) CClF2-CHClF) ~ of C2H2ClF3 ~ ofCl 3b 1 - 0.034 n.d.
7 - ~.067 0.002 14 - 0.477 D.015 3d 14 DMP 0.20~ 0.023 3f 14 But n.d. 0.001 3h 14 DMP/But l:l n.d. n.d.
.
n.d. = not detectable (detection limit O.OD1%3 n.m. = not measured - 15 - s~
Table 7 .
Example Storage Stabilizer Elimination - time products (days) (1~, based on CHCl2-CF3) % of C2H2ClF3 % ofCl , 4a 14 - 0.88 n.m.
4c 14 DMP O . 45 0 . 036 4e 14 But 0.015 0.008 4g 14 DMP/But 1:1 n.d. n.d.
26 DMP/But 1:1 n.d. n.d.
Table 8 15 Example Storage Stabili~er Elimination time (1~, based on CHCl2-CF3/ products (days) CClF2-CHClF)% of C2HzClF3 % of . ~, .. . _ _ _ - 4b 14 - 1.09 n.m.
20 4d 14 DMP O.54 n.m.
4f 14 But 0.019 n.d.
4h 14 DMP/But 1:1 n.d. n.d.
~6 DMP/But 1:1 n.d. n.d.
n.d. = not detectable (detection limit 0.001%) n.m. = not measured :`
Table 9 Example Storage Stabilizer contents Elimination time (~ by we~ight) product (days) tbased on CHCl2-CF3) % of C2H2ClF3 DMP But 5a 14 0~05 n . ol o . 040 5b 20 0.1 1.0 0.002 5c 20 0.2 0.5 n.d.
Sd 20 0.2 1.0 n.d.
5e 14 0.5 0.2 n.d.
5f 14 1.0 0.05 n.d.
5g 14 1.0 0.1 n.d.
5h 14 1.0 0.5 n.d.
5k 14 2.0 0.1 n.d.
HOECHST AKTIENGESELLSCHAFT HOE 91/F 163 Dr.MA/rh Description Stabilization of dichlorotrifluoroethane-containing mixtures The invention relates to the stabilization of dichloro-trifluoroethane-containing mixtures which are used for the preparation of polyurethane foam.
Dichlorotrifluoroethane (CF3-CHCl2 and CClF2-CHClF) is intended as a replacement for trichlorofluoromethane (CFC
11), which will soon b~ unavailable due to presumed damage to the ozone layer in the atmosphere and which i8 used as a blowing agent in the production of foams based on polyisocyanates, in particular polyurethane and polyisocyanurate foams (US Patent 3,183,19~). The produc-tion of such foams is known and is described, forexample, in ~uns~stoff-Handbuch, Volume YII, Polyure-thane, Carl Hanser Verlag, Munich, Vienna (1983), pages 246 to 331, and in EP-A-0 077 964, EP-A-0 334 059, and DE-B 1 694 138 t= ~ritish Patent 1,209,243).
Ullmanns Enzyklopadie der technischen Chemie (1980), Volume 19, pages 301 ~o 341, gives a review of the raw materials which can be used and the possible processes for the production of rigid polyurethane foams.
In addition, corresponding information can be found in Kirk-Othmer, Encycl. of Chem. Technology, 3rd edition, Vol. 11 (1980), pages 87 - 89, and Yol. 23 (1983), pages 576 - 607.
Por the production of polyurethane foams, a mixture of polyols, catalysts, foam stabilizers, dichlorotrifluoro-ethane as blowing agent, water and, if desired, flame-proofing agents and other additives ~this mixture is referred to below as component A), is in many cases supplied in ready-mixed form to the user. In this case, the dichlorotrifluoroethane is in contact with th~ other constituents of component A for some time before the reaction with polyisocyanate (refexred to below as component B) taXes place to give the polyurethane foam.
An alternative is the preparation of component A from the abovementioned individual co]mponents or from partial mixtures of these directly by the foam maker. Again, component A must in this case be stored before foaming.
Polyisocyanates which are suitable for foaming are alipha~ic, cycloaliphatic and aromatic diisocyanates or polyisocyanates. Preference is given to 2,4- and 2,6-tolylene diisocyanates, diphenylmethane diisocyanate, polymethylene-polyphenyl isocyanate and mixtures thereof.
It is also possible to use polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups, which ar~ known as ~modified polyisocyanates~ or "isocyana~e prepolymers".
The polyols employed are in general compounds containing at least two hydrogen atoms which are reactive toward isocyanate groups, for example polyether-, polyester- and amine-based compounds, and amino- and/or carboxyl- and/or thiol-containing compounds, generally h~ving 2 - 8 hydrogen atoms which are reactive toward polyisocyanates (US Patent 3,183,192). Hydroxyl-containing amino compounds ~aminopolyols3 are frequently employed here, either alone or in addition to amino-free polyols.
The reaction of the polyols and/or aminopolyols with the polyisocyanates is carried out with addition of a cata-lyst. The catalysts usually employed are amino compounds, in particular tertiary amino compounds (for example dimethylcyclohexylamine). These amino compounds are added to the abo~ementioned component A. However, it is also ~,3~3~
possible to employ amino-free compounds as cataly8t8, such a~, for example, organotin compounds, for example dibutyltin dilaurate.
However, it has been ~hown thiat the mixtures cont~ining cataly~ically active amino compounds and/or aminopolyols react with the hydrogen-cont:aining dichlorotrifluoro-ethanes HCFC 123 (CF3-CHCl~) and HCFC 123 a lCClF2-CHClF) with elimination of hydrogen chloride to give hydrogen rich hydrochlorofluoroalkan0s, in particular HCFC 133a (CF3-CH2Cl). The extent of lthis reaction depends on various parameters, such as pH, temperature and metal ion contents. The hydrogen chloride formed has a considerable adverse effect on the subsequent foaming reaction with the polyisocyanate. In some cases, the conditions mentioned also give rise to crystalline depolsits in the component A which interfere with the metering by means of precision metering pumps. HCFC 133a is an undesirable by-product due to its carcinogenic properties (in animal experiments).
Although it is in principle possible to use highly reactive polyols with amine-free formulations in which a dechlorination reaction does not normally occur, the catalysts which can be used here are org~nometallic compounds, such as, for example, dibutyltin dilaurate.
The object of the present invention is to make it pos-sible also to employ systems containing aminopolyols and/or other amino compounds in the presence of dichloro-trifluoroethane without formation of HCl or HGFC 133a occurring.
German Patent 1 207 626 (US Patent 3,183,192) discloses that unsaturated compounds such as butadiene, isoprene, styrene, alpha-methylstyrPne or l-alkenes having 4 to 18 carbon atoms can be employed as stabilizers for the (fully halogenated) chlorofluoroalkane compounds 2 t~ 3 n ) L
trichlorofluoromethane and trichlorotrifluoroethane in foamablecompositionsofthistype. German Patent 3 139 401 (us Patent 4,463,189) discloses that 2,4-diphenyl-4-methylpentene (DMP) also fiuppresses the undesired reaction of aminopolyols with these chlorofluoroalkanes.
It has been found that DMP also suppresses the dechlori-nation reactions of the (hydrogen-containing~ dichloro-trifluoroethanes to a certain extent. It has furthermore been found that 4-~ert.-butylpyrocatechol likewi~e hinders these dachlorination reactions to a certain extent.
Surprisingly, it h~s been found that mixtures of 4-tert.~
butylpyrocatechol and DMP completely suppress this dechlorination reaction, so that, in particular, the formation of HCFC 133a (CF3~CH2Cl) and HCl is prevented.
The in~ention relates ~o a mixture which essentially comprises DMP, 4-tert.-butylpyrocatechol and at least one of the two dichlorotrifluoroethanes CF3-CHCl2 and CClF2-CHClF. In general, the mixture contains an amount of DMP
and 4-tert.-butylpyrocatechol which is sufficient to suppress said dechlorination reaction of the dichloro~ri-fluoroethanes if they are employed together with amino-polyols and/or other amino compounds in the foaming of polyurethane, but the content of D~P and 4-tert.-butyl-pyrocatechol is normally at most 10% by weight. Themixture preferably contains from 0.1 to 5~ by weight of DMP and from 0.02 to 2% by weight of 4-tert.-butylpyro-catechol, in particular from 0.2 to 2% by weight of DNP
and from 0.05 to 1~ by weight of 4-tert.-butylp~rocate-- 30 chol, based on the total amount of dichlorotrifluoro-ethanes.
The invention furthermore relates to a process for the stabilization of mixtures containing at least one of the dichlorotrifluoroethanes CF3-CHCl2 and CClF2~CHClF and 2~$~3S i aminopolyols and/or primary, secondary or tertiary amines, which comprises adding an effective amount of 2,4-diphenyl-4-methylpentene and 4-te:rt.-butylpyrocate-- chol to the mixtures. The preferred and particularly preferred amounts of DMP and 4-tert.-butylpyrocatechol are the same as in ths mixture ~ust mentioned.
The mixtures of 4-tert.-butylpyrocatechol and DMP are soluble in dichlorotrifluoroethane and do not affect the foaming reaction.
DMP is a commercially available product under the name 'dimeric alpha-methylstyrene`~ ~CAS No. 6144-04-3~ and can be prepared, for example, as described in US Patent 2,429,719.
It generally comprises the two isomers 2,4-diphenyl-4-methyl-l-pentene and 2,4-diphenyl-4-methyl-2-pentene. The l-pentene/2-pentene isomer ratio is generally from about 1:1 to 9:1.
Instead of the mixture of the two pentenes, it is also possible to employ a technical-grade mixture which, in addition to these two isomers, also contains a small amount of 1,1,3-trLmethyl-3-phenylindane. A mixture of this type iæ obtainable, for example, by the process of US Patent 2,429,719 and generally contains from 45 to ~9%
by weight of 2,4-diphenyl-4-methyl~1-pentene, from 10 to 45~ by weight of 2,4-diphenyl-4-methyl-2-pentene and from 1 to 20~ by weight of 1,1,3-trimethyl-3-phenylindane. If a technical-grade mixture of this type is used, the amount must naturally be selected so that the above-- mentioned percentages of pure DMP are achieved.
It is of course also possible to employ the pure isomers individually, but separation of the isomer mixture formed in the preparation of DMP would be an unnecessary expense.
r~
4-tert.-Butylpyrocatechol (with the C~S Mo. 98-29-3) is a known polymerization inhibitor for monomeric olefins and is a commercially a~ailable compound tBeilstein E III
6:4671~.
It is in principle possible for other hydrochlorofluoro-alkanes, such as chlorotetrafluoroethane, l,l-dichloro-1-fluoroethane or l-chloro-l,1-difluoroethane, which are suitable as blowing agents for the same applications as the dichlorotrifluoroethanes for foaming polyurethane~, to be stabilized in the same way.
The invention i8 illustr~ted in greater detail by means of the examples below. In the tables, 4-tert.-butyl-pyrocatechol is ab~reviated to ~'But".
Examples Experimental procedure:
To carry out the tests, in each case 50 g of the mixtures described in the examples below were weighed out into aerosol glass bottles, which were Lmmediately sealed in a gas-tight manner and stored at a temperature of 50C.
Although the elimination products (hydrogen chloride and CF3-CH2Cl) appear even at storage temperatures of about 20C, a temperature of 50C was selected for accelerated testing since, as is known, a temperature increase of 30~C accelerates chemical reactions considerably. The mixtures were assessed as to visual appearance after the time specified in each case and analyzed for elLmination products.
The amounts of elimin~tion products are given in % by weight, based on the total weighed out mixture, with hydrogen chloride being determined as chloride.
The tertia~ amino compollnds investigated, which would act as catalysts in a reaction with polyisocyanate, were v ~J ~
dLmethylcyclohexylamine and d~lethylaminoethanol.
Example 1:
a) 70~ by weight of dimethylcyclohexylamine (DMCHA~ and 30~ by weight of CHCl2-CF3 were mixed and stored at 50C for 14 days. The anialytical re~ults are shown in Table 1.
b) The procedure was as in Example la), but the CHCl2-CF3 was replaced by a mixture of 93% by weight of CHCl2-CF3 and 7% by weight of CClF2-CHClF. The analytical resul~s are shown in Table 2.
c) The procedure was as in ~xample la), but addition-ally with 1~ by weight of DMP, based on the content of CHCl2-CF3. The results are shown in Table 1.
d) The procedure was as in Example lb), but addition-ally with 1% by weight of DMP, based on the total amount of dichlorotrifluoroethane mixture comprising 93% by weight of CHCl2-CF3 and 7% by weight of CClF2-CHClF. The results are shown in Table 2.
e) The procedure was as in Example la), but addition-ally with 1~ by weight of ~-tert.-butylpyrocatechol, based on the content of CHCl2-CF3. The results are shown in Table 1.
f3 The procedure was as in Example lb), but addition-- ally with 1% by weight of 4-tert.-butylpyrocatechol, based on the total amount of dichlorotrifluoroethane mixture comprising 93% by weight of CHCl2-CF3 and 7%
by weight of CClF2-CHClF. The results are shown in Table 2.
g) The procedure was as in Example la), but addition-ally with 1% by weight of a stabilizer mixture comprising 50% by weight of DMP and 50% by weight o~
s~ ~3 ~ ~ ~3 r' ~
~ 8 ~
4-tPrt.-butylpyrocat~chol, based on the content of CHCl2-CF3. The xesult~ are shown in Tabl~ 1.
h) The procedure was as in Example lb), but addition~
ally with 1~ by weight of a s~abilizer mixture comp~ising 50~ by weight of DMæ and 504 by weight of 4-tert.-butylpyrocatecho], based on the tot~l amount of dichlorotrifluoroethane mixture comprising 93% by weight of CHCl2-CF3 and 7~ by weight of CClE2-CHClF.
The results are shown in Table 2.
~xample 2:
a) A mixture of 70~ by weight of dimethylaminoethanol (DMEA) and 30% by weight of CHCl2-CF3 was investi-ga~ed. The results are shown in Table 3.
b) The procedure was as in Example 2a), but the CHCl2-CF3 was replaced by a mixture of 93~ by weight of CHCl2-CF3 and 7% by weight of CClF2-CHClF. The analytical results are shown in Table 4.
c) The procedure was as in Example 2a), but addition-ally with 1~ by weight of DMP, based on the content of CHCl2-CF3. The results are shown in Table 3.
d) The procedure was as in Example 2b), but addition ally with 1% by weight of DNP, based on the total amount of dichlorotrifluoroethane mixture comprising 93~ by weight of CHC12-CF3 and 7~ by weight o~ CClF2-CHClF. The results are shown in Table 4.
e) The procedure was ~s in Example 2a), but addition-ally with 1~ by weight of 4-tert.-butylpyrocatechol, based on the content of CMCl2-CF3. The results are shown i.n Table 3.
0 f) The procedure was as in Example 2b), but addition-ally with 1% by weight of 4-tert.-butylpyrocatechol, 2 ~ & J ~
_ 9 _ bas~d on the total amount of dichlorotrifluoro2thane mixture comp~ising 93% by weight of CHCl2-CF3 and 7%
by weight of CClF2-CHClF. The results are ~hown in Table 4.
g) The procedure was as in Example 2a), but addition-ally with 1~ by weight of a stabilizer mixture comprising 50% by weight of DMP and 50~ by weight of 4-tert.-butylpyrocatecho.l, based on the conten$ of CHCl2-CF3. The results are shown in Table 3~
h) The procedure was as in Example 2b), but addition-ally with 1% by weight of a stabilizer mixture comprising 50% by weight of DMP and ~0% by weight of 4-tert.-butylpyrocatechol, based on the total ~mount of dichlorotrifluoroethane mixture comprising 93% by weight of CHCl2~-CF3 and 7% by weight of CClF2-CHClF.
The results are shown in Table 4.
Example 3:
a) A mixture of 70% by wPight of aminopolyol based on ethylenediamine and propylene oxide having a hydroxyl number of 450 and 30% by weight of CHCl2-CF3 was investigated after l day, after 7 days and after 14 days. The results are shown in Table 5.
b) The procedure was as in Example 3a), but the CHC12-CF3 was replaced by a mixture of 93% by weight of CHCl2 CF3 and 7% by weight of CClF2-CHClF. The results are shown in Table 6.
c) The procedure was as in Example 3a), but addition-ally w:ith 1% by weight of DMP, based on the content of CHC:L2-CF3. The results after 14 days are shown in Table 5.
d) The procedure was as in Example 3b), but addition-ally with 1~ by weight of DMP, based on the total .
2 ~ 5 1 - ln-amount of dichlorotrifluoroethane mixture comprising g3~ by weight of CHC12-CF3 and 7% by weight of CClF2-CHClF. The analytical results after 14 days are shown in Table 6.
e) The procedure was as in E,xample 3G ), but with 1% by weight of 4-tert.-butylpyrocatechol, based on the con~ent of CHC12-CF3. The results are shown in Table 5.
f) The procedure was as in Example 3d~, but with 1~ by weight of 4-tert.-butylpyrocatechol, based on the total amount of dichlorotrifluoroethane mixture comprising 93% by weight of CHCl2-CF3 and 7% ~y weight of CClF2-CHClF. The results are shown in Table 6.
5 g) The procedure was as in Example 3~), but with 1~ by weight of a stabilizer mixture comprising 50% by weight of DMP and 50~ by weight of 4-tert.-butyl-pyrocatechol, based on the content of dichlorotri-fluoroethane. The results are shown in Table 5.
0 h) The procedure was as in Example 3d), but with 1% by weight of a stabilizer mixture comprising 50% ~y weight of DNP and 50% by weight of 4-tert.-butyl-pyrocatechol, based on the total amount of dichlorotrifluoroethane mixture comprising 93% by weight of CHClz-CF3 and 7~ by weight of CClF2-CHClF.
The results are shown in Table 6.
Example 4:
a) A mixture of 73~ by weight of the aminopolyol used in Example 3, 1.5~ by weight of DMCHA and 25.5~ by weight of CHCl2-CF3 was investigated. The results are shown in Table 7.
2 ~
b ) The procedure was as in Example 4a~, but the CHCl2-CF3 was replaced by a mixture of 93% by weight of CHClz-CF3 and 7~ by we:ight of CClF2-CHClE. The results are shown in Table 8.
c) The procedure wa~ as in Example 4a), but addition-ally with 1% by weight of DNP, based on the content of CHCl2-CF3. The results are shown in Tabla 7.
d) The procedure was as in ~xample 4b)/ but addition-ally with 1~ by weight of DMoe, based on the total amount of dichlorotrifluoroethane mixture comprising 93% by weight of CHCl2-CF3 and 7% by weight of CClF~-CHClF. The results are shown in Tablo 8.
e) The procedure was as in Example 4a), but addition-ally with 1~ by weight of 4-tert.-butylpyrocatechol, based on the content of CHCl2-CF3. The results are shown in Table 7.
f) The procedure was as in Example 4b), but addition-ally with 1~ by weight of 4-tert.-butylpyrocatechol, based on the total amount o~ dichlorotrifluoroethane mixture comprising 93~ by weight of CHCl2-CF3 and 7%
by weight of CClF2-CHClF. The results are shown in Tabl~ 8.
g) The procedure was as in Example 4a), but addition-ally with 1% by weight of a stabilizer mixture comprising 50% by weight of DMP and 50~ by weight of 4-tert.-butylpyrocatechol, based on the content of CHCl2-CF3. The analytical results aftex 14 and 26 days are shown in Table 7.
h) The procedure was as in Example 4b), but addition-ally with 1% by weight of a stabilizer mixture comprising 50% by weight of DNP and 50% by weight o~
4-tert.-butylpyrocatechol, ba~ed on the total amount :
2 (~
of dichlorotri~luoroethane mixture comprising 93~ by weight of CHC12-CF3 and 7~ by weight of CClF2-CHClF.
~he analytical results after 14 and 26 days are shown in Table 8.
Example 5:
The mixture described in Ex~mple 4a) was mixed with various amounts of DMP and 4-tert.-butylpyrocatechol and stored a~ in the examples above. The stabili2er content~
and the results are shown in l'able 9.
Table 1 .
Example Storage Stabili~er Elimination tLme products (days) ~1~, based on CHCl2-CF3) ~ of C2H2ClF3 ~ofCl la 14 - 0.13 0.04 lc 14 DMP 0.10 0.03 le 14 But O . 05 n.m.
lg 14 DMP/But 1:1 n.d. n.d.
Table 2 Example Storage Stabilizer ElLmination time (1%, based on CHCl2-CF3/ products (days) CC12F-CHClF3 % of C2H2ClF3 ~ o~Cl lb 14 - 0.11 0.03 ld 14 DMP 0.0~ n.m~
lf 14 But 0.10 n.m.
lh 14 DMP~But 1:1 n.d. n.d.
.
n.d. = not detectable (detection limit 0.001~) n.m. = not measured 2 3,~,~ d~J ~ ~3 ~
Table 3 , . . _ . _ Example Storage Stabilizer Elimination time products (days) (1~, based on CHCl2-CF3) % of C2H2ClF3 ~ o~
.. . .. _ _ _ 2a 14 - 0.19 0.06 2c 14 DMP 0.13 0.04 2e 14 But 0.13 n.m.
2g 14 DMP/But 1:1 n.d. n.d.
.
Table 4 Example Stora~e Stabilizer Elimination time (1%, based on CHCl2-CF3/ products - (days) CClF2-CHClF)% of C2H2ClF3 % o~Cl -2b 14 - 0.06 0.05 2d 14 DMP 0.02 n.m.
2f 14 But 0.02 0.01 2h 14 DMP/But 1:1 n.d. n.d.
_ n.d. = not detectable (detection limit 0.001%) n.m. = not measured 2 Q '~ ~ ~J`~
Table 5 Example Storage S-tabilizer Ellmination time products (days) (1~, based on CHCl2-CF3) % of C2H2ClE3 % ofCl 3a 1 - 0.020 n.d.
7 - 0.055 ~.0018 l~ - 0.549 0.013 3c 14 DMP 0.134 0.036 3e 14 But n.d. 0.003 3g 14 DMP/But l:l n.d. n.d.
Table 6 Example Storage Stabilizer Elimination time (l~, ba~ed on CHCl2-CF3/ products (days) CClF2-CHClF) ~ of C2H2ClF3 ~ ofCl 3b 1 - 0.034 n.d.
7 - ~.067 0.002 14 - 0.477 D.015 3d 14 DMP 0.20~ 0.023 3f 14 But n.d. 0.001 3h 14 DMP/But l:l n.d. n.d.
.
n.d. = not detectable (detection limit O.OD1%3 n.m. = not measured - 15 - s~
Table 7 .
Example Storage Stabilizer Elimination - time products (days) (1~, based on CHCl2-CF3) % of C2H2ClF3 % ofCl , 4a 14 - 0.88 n.m.
4c 14 DMP O . 45 0 . 036 4e 14 But 0.015 0.008 4g 14 DMP/But 1:1 n.d. n.d.
26 DMP/But 1:1 n.d. n.d.
Table 8 15 Example Storage Stabili~er Elimination time (1~, based on CHCl2-CF3/ products (days) CClF2-CHClF)% of C2HzClF3 % of . ~, .. . _ _ _ - 4b 14 - 1.09 n.m.
20 4d 14 DMP O.54 n.m.
4f 14 But 0.019 n.d.
4h 14 DMP/But 1:1 n.d. n.d.
~6 DMP/But 1:1 n.d. n.d.
n.d. = not detectable (detection limit 0.001%) n.m. = not measured :`
Table 9 Example Storage Stabilizer contents Elimination time (~ by we~ight) product (days) tbased on CHCl2-CF3) % of C2H2ClF3 DMP But 5a 14 0~05 n . ol o . 040 5b 20 0.1 1.0 0.002 5c 20 0.2 0.5 n.d.
Sd 20 0.2 1.0 n.d.
5e 14 0.5 0.2 n.d.
5f 14 1.0 0.05 n.d.
5g 14 1.0 0.1 n.d.
5h 14 1.0 0.5 n.d.
5k 14 2.0 0.1 n.d.
Claims (7)
1. A mixture essentially comprising 2,4-diphenyl-4-methylpentene, 4-tert.-butylpyrocatechol and at least one of the two dichlorotrifluoroethanes CF3-CHCl2 and CClF2-CHClF.
2. A mixture as claimed in claim 1 containing from 0.1 to 5% by weight of 2,4-diphenyl-4-methylpentene and from 0.02 to 2% by weight of 4-tert.-butylpyrocate-chol, based on the amount of dichlorotrifluoro-ethanes.
3. A mixture as claimed in claim 1 containing from 0.2 to 2% by weight of 2,4-diphenyl-4-methylpentene and from 0.05 to 1% by weight of 4-tert.-butylpyrocate-chol, based on the amount of dichlorotrifluoro-ethanes.
4. A process for the stabilization of mixtures contain-ing at least one of the dichlorotrifluoroethanes CF3-CHCl2 and CClF2-CHClF and at least one amino-polyol and/or amine, which comprises adding an effective amount of 2,4-diphenyl-4-methylpentene and 4-tert.-butylpyrocatechol to the mixtures.
5. The process as claimed in claim 4, wherein from 0.1 to 5% by weight of 2,4-diphenyl-4-methylpentene and from 0.02 to 2% by weight of 4-tert.-butylpyrocate-chol, in particular from 0.2 to 2% by weight of 2,4-diphenyl-4-methylpentene and from 0.05 to 1% by weight of 4-tert.-butylpyrocatechol, based on the amount of dichlorotrifluoroethanes, are added to the mixtures.
6. The process as claimed in claim 4 or 5, wherein the mixtures are used for the production of polyurethane foams.
7. The process as claimed in claim 4 or 5, wherein the mixtures contain in addition to the polyisocyanate one or more other components which are customary in the production of polyurethane foam.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4117379.1 | 1991-05-28 | ||
| DE4117379 | 1991-05-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2069651A1 true CA2069651A1 (en) | 1992-11-29 |
Family
ID=6432589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2069651 Abandoned CA2069651A1 (en) | 1991-05-28 | 1992-05-27 | Stabilization of dichlorotrifluoroethane-containing mixtures |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0516020A2 (en) |
| JP (1) | JPH05178771A (en) |
| BR (1) | BR9202014A (en) |
| CA (1) | CA2069651A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6441220B2 (en) * | 2012-09-24 | 2018-12-19 | アーケマ・インコーポレイテッド | Improved stability of polyurethane polyol blends containing halogenated olefin blowing agents |
-
1992
- 1992-05-25 EP EP19920108790 patent/EP0516020A2/en not_active Withdrawn
- 1992-05-27 CA CA 2069651 patent/CA2069651A1/en not_active Abandoned
- 1992-05-27 JP JP4135333A patent/JPH05178771A/en not_active Withdrawn
- 1992-05-27 BR BR929202014A patent/BR9202014A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05178771A (en) | 1993-07-20 |
| BR9202014A (en) | 1993-01-12 |
| EP0516020A2 (en) | 1992-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2009169C (en) | C3 to c5 polyfluoroalkanes propellants | |
| JPH05179043A (en) | Blowing agent comprising fluorobutene and production of plastic foam | |
| JPH05239251A (en) | Blowing agent comprising fluoropropane and production of plastic foam | |
| CA2031970A1 (en) | Process for producing foams with the aid of fluoroalkanes | |
| ES2200033T3 (en) | PREMIXES FOR THE PREPARATION OF POLYURETHANE FOAMS. | |
| US5840779A (en) | Catalysts which stabilize hydrohalocarbon blowing agent in polyurethane foam formulations | |
| US5395859A (en) | Catalysts which stabilize hydrohalocarbon blowing agent in polyisocyanurate foam formulations during polymerization | |
| CA2069651A1 (en) | Stabilization of dichlorotrifluoroethane-containing mixtures | |
| US5169996A (en) | Stabilized 141b | |
| US5135680A (en) | Stabilized 14 lb | |
| EP0539719B1 (en) | Stabilized 141b | |
| US5169997A (en) | Stabilized 1,1-dichloro-1-fluoroethane | |
| ZA200307626B (en) | Non-combustible polyesterpolyol and/or polyetherpolyol preblend for producing foamed products. | |
| US5169874A (en) | Stabilized 141b | |
| JPH05179045A (en) | Foaming agent composed of fluorobutene and production of plastic foam | |
| JPH06200070A (en) | Stabilized composition containing hydrofluoroalkane, premix for production of polymer foam and polymer foam obtained therefrom | |
| US5177270A (en) | Stabilized 141b | |
| US5221697A (en) | Stabilized 14lb | |
| US5464882A (en) | Method for inhibiting the degradation of hydrochlorofluorocarbons utilized as foaming agents in the preparation of foamed polyurethanes and polyisocyanurates | |
| US5246625A (en) | Stabilized 141B | |
| US5246626A (en) | Stabilized 141b | |
| JPH05179039A (en) | Blowing agent comprising cyclobutane | |
| JPH05179041A (en) | Blowing agent comprising fluoromethylpropane | |
| JPH05214149A (en) | Blowing agent consisting of fluorobutane | |
| IL170449A (en) | Hydrofluorocarbon compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |