EP0000021B1 - Process for the preparation of sulfonic acid groups and phosphonate groups bearing polyisocyanate mixtures - Google Patents
Process for the preparation of sulfonic acid groups and phosphonate groups bearing polyisocyanate mixtures Download PDFInfo
- Publication number
- EP0000021B1 EP0000021B1 EP78100033A EP78100033A EP0000021B1 EP 0000021 B1 EP0000021 B1 EP 0000021B1 EP 78100033 A EP78100033 A EP 78100033A EP 78100033 A EP78100033 A EP 78100033A EP 0000021 B1 EP0000021 B1 EP 0000021B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- phosphite
- groups
- acid
- gew
- 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.)
- Expired
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- 229920001228 polyisocyanate Polymers 0.000 title claims description 49
- 239000005056 polyisocyanate Substances 0.000 title claims description 47
- 238000000034 method Methods 0.000 title claims description 26
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title claims description 19
- 239000000203 mixture Substances 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 title description 7
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 12
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical compound NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 claims description 5
- LUVCTYHBTXSAMX-UHFFFAOYSA-N tris(2-chloroethyl) phosphite Chemical compound ClCCOP(OCCCl)OCCCl LUVCTYHBTXSAMX-UHFFFAOYSA-N 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 239000005864 Sulphur Substances 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 17
- 239000000047 product Substances 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- 238000004821 distillation Methods 0.000 description 8
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- DXDUKPXLDUXKGB-UHFFFAOYSA-N sulfuroisocyanatidic acid Chemical class OS(=O)(=O)N=C=O DXDUKPXLDUXKGB-UHFFFAOYSA-N 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 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 2
- -1 trichtorethane Chemical compound 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- 0 **(NC(Cl)=O)(N=C=O)S(O)(=O)=O Chemical compound **(NC(Cl)=O)(N=C=O)S(O)(=O)=O 0.000 description 1
- KDLIYVDINLSKGR-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanatophenoxy)benzene Chemical compound C1=CC(N=C=O)=CC=C1OC1=CC=C(N=C=O)C=C1 KDLIYVDINLSKGR-UHFFFAOYSA-N 0.000 description 1
- 241001136792 Alle Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- LNWBFIVSTXCJJG-UHFFFAOYSA-N [diisocyanato(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(N=C=O)(N=C=O)C1=CC=CC=C1 LNWBFIVSTXCJJG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001448 anilines Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000000618 carbamic acid halide group Chemical group 0.000 description 1
- 150000001714 carbamic acid halides Chemical class 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- AAYGSSGHJGVNSK-UHFFFAOYSA-N hexane-1,3,6-triol Chemical compound OCCCC(O)CCO AAYGSSGHJGVNSK-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- KKFOMYPMTJLQGA-UHFFFAOYSA-N tribenzyl phosphite Chemical compound C=1C=CC=CC=1COP(OCC=1C=CC=CC=1)OCC1=CC=CC=C1 KKFOMYPMTJLQGA-UHFFFAOYSA-N 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-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 compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4062—Esters of acids containing the structure -C(=X)-P(=X)(XR)2 or NC-P(=X)(XR)2, (X = O, S, Se)
- C07F9/4065—Esters of acids containing the structure -C(=X)-P(=X)(XR)2, (X = O, S, Se)
-
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/776—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur phosphorus
Definitions
- Polyisocyanates with sulfonic acid groups are known (German Offenlegungsschriften 2 227 111, 2 359 614, 2 359 615, 2 524 476, 1 939911). Their manufacture is characterized in that e.g. liquid multicomponent mixtures of aromatic polyisocyanates mixed with heavy field trioxide or an equivalent amount of oleum, sulfuric acid or chlorosulfonic acid and allowed to react.
- Polyisocyanates containing phosphonate groups are also known (DT-OS 1 127 583).
- the production of these phosphorus-containing isocyanates takes place e.g. in that polyisocyanates are converted into carbamic acid halides by the action of hydrogen halide and, based on the carbamic acid halide groups, these are reacted with equivalent amounts of trialkyl phosphites in the manner of an Arbusow reaction.
- Phosgenation products of condensates of aniline and aldehydes or ketones such as e.g. Acetaldehyde, propionaldehyde, butyraldehyde, acetone, methyl ethyl ketone.
- reaction products of the above aromatic polyisocyanate mixtures with from 0.2 to 50 ⁇ quivending- 9 6 of polyols are, provided that the viscosity of the reaction products 30000 cP thus obtained at 25 ° C does not exceed the NCO content of the reaction products at least 15 weight % is.
- Suitable polyols for modifying the starting materials are, in particular, the polyether and / or polyester polyols of the molecular weight range 200 to 6000, preferably 300 to 4000, and low molecular weight polyols of the molecular weight range 62 to 200 known in polyurethane chemistry. Examples of such low molecular weight polyols are ethylene glycol, propylene glycol, glycerin, Trimethylolpropane, 1,4,6-hexanetriol.
- the aromatic polyisocyanates suitable according to the invention generally have an NCO content of 15-53, preferably 25-48 and particularly preferably 25-35% by weight.
- Liquid multi-component mixtures of aromatic polyisocyanates with an NCO content of 20 to 48, preferably 25 to 35% by weight and an average NCO functionality of 2.0 are particularly suitable for the process according to the invention.
- Preferred liquid aromatic polyisocyanate mixtures to be used in the process according to the invention are, in particular, the phosgenation products of aniline / formaldehyde condensates which have a dinuclear diisocyanate content of 20 to 90% by weight, trinuclear triisocyanates of 3 to 40% by weight, tetranuclear tetraisocyanates of 1 to Have 20 wt .-% and higher core polyisocyanates of 1 to 40 wt.
- Technical tolylene diisocyanate mixtures are also suitable for the process according to the invention.
- Technical distillation residues such as those obtained in the distillation of technical tolylene diisocyanate mixtures and which have a free tolylene diisocyanate isomer content of less than 70% by weight, are also outstandingly suitable.
- Such distillation residues can be obtained, for example, by the process of DT-OS 2,035,731 .
- Also particularly suitable are the distillation residues described in DT-OS 2 123 183, as well as their solutions in phosgenation products of aniline / formaldehyde condensates, which are also described in this last-mentioned German patent application.
- phosphites of the formula mentioned which have different reset R are of course also suitable for the process according to the invention.
- suitable phosphites are trimethyl phosphite, triethyl phosphite, tris (2-chloroethyl) phosphite, tributyl phosphite, trioctyl phosphite, tribenzyl phosphite or 0.0'-dimethyl-O "- (2-chloroethyl) phosphite.
- the trialkyl phosphites mentioned by way of example are preferably used.
- Tris (halogenoalkyl) phosphites such as, in particular, tris (2-chloroethyl) phosphite are particularly preferred.
- the reaction partners mentioned by way of example are preferably used in amounts such that 0.01 to 0.5, preferably 0.02 to 0.3 and particularly preferably 0.03 to 0.2 mol are used per mole of aromatically bound isocyanate groups Chlorosulfonic acid and 0.01 to 0.5, preferably 0.02 to 0.3 and in particular 0.03 to 0.2 mol of phosphite Implementation.
- equimolar amounts of phosphite and chlorosulfonic acid are used, but it is also possible to use chlorosulfonic acid or phosphite in different molar amounts.
- the process according to the invention is carried out in the temperature range between -10 to + 150 ° C., preferably between 0 and 100 ° C.
- the reaction according to the invention can be carried out either by directly mixing the three reaction components or in a two-stage process, in which case the polyisocyanate is first reacted with the chlorosulfonic acid and then the reaction with the phosphite is carried out.
- the process according to the invention can be carried out both in the presence and, in particular, when using low-viscosity starting materials in the absence of solvents which are inert under the reaction conditions to the starting materials and end products of the process according to the invention.
- Particularly preferred solvents are halogenated hydrocarbons, e.g. Dichloroethane, trichtorethane, fluorotrichloromethane, methylene chloride or chlorobenzene.
- the solvents preferably have a boiling point between 0 and 140 ° C. If necessary, the invention. Implementation can also be carried out under pressure.
- the concentration of the reactants in this solvent can vary within wide ranges, in general the solvent is used in such amounts that 20-100% strength by weight solutions of the reactants are present during the reaction according to the invention, the Specify the stated concentration as a percentage of the amount by weight of all reactants based on the weight of the total solution.
- the polyisocyanate is preferably mixed with the phosphite and any solvent to be used, and the chlorosulfonic acid, which may also be dissolved in an inert solvent, is added to this mixture in a period of a few minutes to several hours with stirring.
- the chlorosulfonic acid is preferably added at room temperature, after which the reaction mixture is heated to 50-100 ° C. to complete the reaction.
- the process products according to the invention are liquid even when tolylene diisocyanate and phosgenation products of the aniline-formaldehyde condensation with a high content of 4,4 '- two-core product are used, in particular if not more than 0.2 mol of chlorosulfonic acid per 1 NCO equivalent and not more than 0.2 mol of organic phosphite are used.
- the isocyanate groups in the process products according to the invention are partly in the form of carbamic acid chloride groups.
- the numerical values mentioned with regard to the NCO content of the products according to the invention also include such NCO groups which may be in the form of carbamic acid chloride groups, the molecular weight of the NCO group (42) also being used in this case when calculating the NCO contents has been. Since the sulfonic acid groups can be at least partially neutralized or esterified without difficulty after the reaction according to the invention, as explained below, the stated sulfur content relates to the sulfonic acid groups which are optionally at least partially neutralized or esterified.
- the aromatic polyisocyanates containing sulfonic acid and phosphonate groups according to the invention are valuable starting materials for the production of moldings and compact plastics. They can be processed without difficulty by customary techniques, such as casting processes, and by means of the customary conveying and metering systems.
- the aromatic phosphonated isocyanatosulfonic acids obtainable by the process according to the invention can, after their preparation, be converted completely or partially into the corresponding isocyanatosulfonates by a neutralization reaction.
- Suitable neutralizing agents are organic or inorganic bases, such as trimethylamine, triethylamine, tributylamine, dimethylaniline, urotropin, sodium hydrogen carbonate, sodium hydroxide, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, magnesium oxide, zinc oxide, sodium phosphate.
- Inorganic neutralizing agents which themselves do not react strongly basic, such as calcium carbonate, magnesium carbonate, dolomite, chalk, sodium phosphate, can also be used in a large excess as filler.
- the hydrophilicity and reactivity of the products according to the invention is increased by converting the sulfonic acid groups into the corresponding sulfonate groups.
- epoxides include: ethylene oxide, propylene oxide, epichlorohydrin.
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Description
Polyisocyanate mit Sulfonsäuregruppen sind bekannt (Deutsche Offenlegungsschriften 2 227 111, 2 359 614, 2 359 615, 2 524 476, 1 939911). Ihre Herstellung ist dadurch gekennzeichnet, daß man z.B. flüssige Mehrkomponentengemische aromatischer Polyisocyanate mit Schwerfeltrioxid oder einer äquivalenten Menge Oleum, Schwefelsäure bzw. Chlorsulfonsäure vermischt und ausreagieren läßt.Polyisocyanates with sulfonic acid groups are known (German Offenlegungsschriften 2 227 111, 2 359 614, 2 359 615, 2 524 476, 1 939911). Their manufacture is characterized in that e.g. liquid multicomponent mixtures of aromatic polyisocyanates mixed with heavy field trioxide or an equivalent amount of oleum, sulfuric acid or chlorosulfonic acid and allowed to react.
Phosphonatgruppen enthaltende Polyisocyanate sind ebenfalls bekannt (DT-OS 1 127 583). Die Herstellung dieser Phosphor enthaltenden Isocyanate erfolgt z.B. dadurch, daß man Polyisocyanate durch Einwirkung von Halogenwasserstoff in Carbaminsäurehalogenide überführt und diese, bezogen auf die Carbaminsäurehalogenidgruppen, mit äquivalenten Mengen an Trialkylphosphiten nach Art einer Arbusow-Reaktion umsetzt.Polyisocyanates containing phosphonate groups are also known (DT-OS 1 127 583). The production of these phosphorus-containing isocyanates takes place e.g. in that polyisocyanates are converted into carbamic acid halides by the action of hydrogen halide and, based on the carbamic acid halide groups, these are reacted with equivalent amounts of trialkyl phosphites in the manner of an Arbusow reaction.
Polyisocyanate die Sulfonsäure- und Phosphonatgruppen enthalten, sind jedoch noch nicht bekannt geworden. Daher ist man z.B. bei der Herstellung anorganisch-organischer Kunststoffe gemäß DT-OS 2 227 -147 gezwungen, die Flammfestigkeit der Kunststoffe durch Zumischen nicht reaktionsfähiger, niedermolekularer Phosphorsäureester, wie z.B. Trichloräthylphosphat, während des Herstellungsprozesses zu erhöhen. Das Verfahren hat jedoch insofern wesentliche Nachteile, als einerseits zum Erzielen der gewünschten mechanischen Werte nur begrenzte und damit für einen vollkommenen Flammschutz nicht ausreichende Mengen an diesen niedermolekularen Verbindungen zugesetzt werden können und andererseits die zugesetzten niedermolekularen Verbindungen wegen ihres niederen Molekulargewichts dazu neigen,- wieder aus dem Kunststoff herauszuwandern.However, polyisocyanates containing sulfonic acid and phosphonate groups have not yet been disclosed. Therefore, it is eg 2 227 in the production of inorganic-organic plastics according to DT-OS - forced 147, the flame resistance of plastics are not reactive by admixture, low molecular weight organophosphate such as Trichloräthylphosphat as to increase the manufacturing process. However, the process has significant disadvantages in that, on the one hand, only limited amounts of these low-molecular compounds can be added in order to achieve the desired mechanical values and thus insufficient for complete flame protection, and on the other hand the added low-molecular compounds tend to - due to their low molecular weight - again to migrate out of the plastic.
Es war daher die Aufgabe der vorliegenden Erfindung neue Polyisocyanate zur Verfügung zu stellen, welche sowohl Sulfonsäuregruppen als auch chemisch fixierten Phosphor enthalten. Diese Aufgabe konnte durch das nachstehend beschriebene erfindungsgemäße Verfahren gelöst werden.It was therefore the object of the present invention to provide new polyisocyanates which contain both sulfonic acid groups and chemically fixed phosphorus. This problem could be solved by the inventive method described below.
Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von Raumtemperatur flüssigen Polyisocyanatgemischen, die
- a) einen Gehalt an aromatisch gebundenen gegebenenfalls teilweise als Carbamidsäurechlorid vorliegenden Isocyanatgruppen von 10 bis 42 Gew.-%,
- b) einen Gehalt an in Form von gegebenenfalls zumindest teilweise neutralisierten oder veresterten Sulfonsäuregruppen vorliegendem Schwefel von 0,5 bis 5 Gew.-%,
- c) einen Gehalt an in Form von Phosphonsäurealkylester- oder Phosphonsäurearalkylester-Gruppen vorliegendem Phosphor von 0,5 bis 5 Gew.-% und
- d) eine Viskosität von 10 bis 50.000 cP bei 25°C aufweisen, dadurch gekennzeichnet, daß man flüssige Mehrkomponentengemische aromatischer Polyisocyanate eines NCO-Gehalts von 20 bis 48 Gew.-% in Gegenwart eines gegebenenfalls Halogen-substituierten Trialkylphosphits oder Tris-(aralkyl)-phosphits mit Chlorsulfonsäure bei -10 bis +150°C zur Reaktion bringt, wobei die Mengen des Phosphits und der Chlorsulfonsäure so bemessen werden, daß pro Mol aromatisch gebundener Isocyanatgruppen 0,01 bis 0,5 Mol Chlorsulfonsäure und 0,01 bis 0,5 Mol Phosphit eingesetztwerden. Geeignete Ausgangsmaterialien für das erfindungsgemäße Verfahren sind alle beliebigen organischen Verbindungen, welche mindestens 2 aromatisch gebundene Isocyanatgruppen aufweisen, mindestens in einer o- oder p-Stellung zu einer aromatisch gebundenen Isocyanatgruppe unsubstituiert sind, welche von den Isocyanatgruppen und den substituierbaren aromatischen Ringen abgesehen unter den Reaktionsbedingungen inert sind und welche schließlich einen unter 70°C liegenden Schmelz- bzw. Erweichungspunkt aufweisen, sowie Gemische derartiger Polyisocyanate mit einem unter 40°C liegenden Schmeltz- bzw. Erweichungspunkt, wobei einzelne Komponenten des Gemischs auch einen über 70°C liegenden Schmelz- bzw. Erweichungspunkt aufweisen können. Beispiele geeigneter aromatischer Polyisocyanate sind 3,3' - bzw. 2,2' - Dimethyl - 4,4' - diisocyanato - diphenylmethan, 2,5,2',5' - Tetramethyl - 4,4' - diisocyanatodiphenylmethan, 3,3' - Dimethoxy - 4,4' - diisocyanato - diphenyl - methan, 3,3' - Dichlor - 4,4' - diisocyanato - diphenylmethan, 4,4' - Diisocyanato - diphenylsulfon, 4,4' - Diisocyanato-diphenyläther, 4,4' - Diisocyanato - 3,3' - dibromdiphenylmethan, 4,4' - Diisocyanato - 3,3' - diäthyl - diphenylmethan, 4,4' - Diisocyanato - diphenyl-sulfid, 1,3 - und 1,4 - Phenylendiisocyanat, 2,4 - und 2,6 - Toluylendiisocyanat sowie beliebige Gemische dieser Isomeren, Diphenylmethan - 2,4' - und/oder - 4,4' - diisocyanat, Naphthylen - 1,5 - diisocyanat, Triphenylmethan - 4,4' - 4" - triisocyanat, Polyphenylpoly - methylen - polyisocyanate, wie sie durch Anilin - Formaldehyd - Kondensation und anschließende Phosgenierung erhalten und z.B. in den britischen Patentschriften 874 430 und 848- 671 beschrieben werden, Carbodiimidgruppen aufweisende Polyisocyanate, wie sie in der deutschen Patentschrift 1 092 007 beschrieben werden, Diisocyanate, wie sie in der amerikanischen Patentschrift 3 492 330 beschrieben werden, Allophanatgruppen aufweisende Polyisocyanate, wie sie z.B. in der britischen Patentschrift 994 890, der belgischen Patentschrift 761 626 und der veröffentlichten holländischen Patentanmeldung 7 102 524 beschrieben werden, Isocyanuratgruppen aufweisende PoIyìsocyante,. wie sie z.B. in den deutschen Patentschriften 1 022 789, 1 222067 und 1 027 394, sowie in den deutschen Offenlegungsschriften 1 929 034 und 2 004 048 beschrieben werden, acylierte Harnstoffgruppen aufweisende Polyisocyanate gemäß der deutschen Patentschrift 1 230 778, Biuretgruppen aufweisende Polyisocyanate, wie sie z.B. in der deutschen Patentschrift 1 101 394, in der britischen Patentschrift 889 050 und in der französischen Patentschrift 7 017 514 beschrieben werden. Es ist auch möglich, die bei der technischen Isocyanatherstellung anfallenden Isocyanatgruppen aufweisenden Destillationsrückstände, gegebenenfalls gelöst in einem oder mehreren der vorgenannten Polyisocyanate, einzusetzen. Ferner ist es möglich, beliebige, der o.g. Bedingung bezüglich des Schmelz- oder Erweichungspunktes entsprechende Mischungen der vorgenannten Polyisocyanate zu verwenden.
- a) a content of 10 to 42% by weight of aromatically bound isocyanate groups, optionally present in part as carbamic acid chloride,
- b) a content of from 0.5 to 5% by weight of sulfur present in the form of optionally at least partially neutralized or esterified sulfonic acid groups,
- c) a content of phosphorus present in the form of alkyl phosphate groups or aryl alkyl phosphate groups of 0.5 to 5% by weight and
- d) have a viscosity of 10 to 50,000 cP at 25 ° C, characterized in that liquid multicomponent mixtures of aromatic polyisocyanates with an NCO content of 20 to 48% by weight in the presence of an optionally halogen-substituted trialkyl phosphite or tris (aralkyl) -phosphites with chlorosulfonic acid at -10 to + 150 ° C to react, the amounts of phosphite and chlorosulfonic acid being such that per mole of aromatically bound isocyanate groups 0.01 to 0.5 moles of chlorosulfonic acid and 0.01 to 0, 5 moles of phosphite are used. Suitable starting materials for the process according to the invention are any organic compounds which have at least 2 aromatically bound isocyanate groups, are unsubstituted at least in an o- or p-position to an aromatically bound isocyanate group, which apart from the isocyanate groups and the substitutable aromatic rings under the reaction conditions are inert and which ultimately have a melting or softening point below 70 ° C, and mixtures of such polyisocyanates with a melting or softening point below 40 ° C, individual components of the mixture also having a melting or softening point above 70 ° C May have softening point. Examples of suitable aromatic polyisocyanates are 3,3 '- or 2,2' - dimethyl - 4,4 '- diisocyanatodiphenylmethane, 2,5,2', 5 '- tetramethyl - 4,4' - diisocyanatodiphenylmethane, 3,3 '- Dimethoxy - 4,4' - diisocyanato - diphenyl methane, 3,3 '- dichloro - 4,4' - diisocyanato - diphenyl methane, 4,4 '- diisocyanato - diphenyl sulfone, 4,4' - diisocyanato diphenyl ether, 4 , 4 '- diisocyanato - 3,3' - dibromodiphenylmethane, 4,4 '- diisocyanato - 3,3' - diethyl - diphenylmethane, 4,4 '- diisocyanato - diphenyl sulfide, 1,3 - and 1,4 - phenylene diisocyanate , 2,4 - and 2,6 - tolylene diisocyanate and any mixtures of these isomers, diphenylmethane - 2,4 '- and / or - 4,4' - diisocyanate, naphthylene - 1,5 - diisocyanate, triphenylmethane - 4,4 '- 4 "- triisocyanate, polyphenylpolymethylene polyisocyanates, as obtained by aniline / formaldehyde condensation and subsequent phosgenation and described, for example, in British Patents 874,430 and 848-671, carbodiimide groups containing polyisocyanates as described in German Patent 1,092,007, diisocyanates as described in American Patent 3,492,330, allophanate-containing polyisocyanates as described, for example, in British Patent 994,890, Belgian Patent 761 626 and published Dutch patent application 7 102 524, polyisocyanate containing isocyanurate groups. as described, for example, in German Patents 1,022,789, 1,220,667 and 1,027,394, and in German Laid-Open Patent Nos. 1,929,034 and 2,004,048, polyisocyanates containing urea groups according to German Patent 1,230,778, polyisocyanates containing biuret groups, such as they are described, for example, in German Patent 1 101 394, British Patent 889 050 and French Patent 7 017 514. It is also possible to use the distillation residues containing isocyanate groups obtained in the technical production of isocyanates, optionally dissolved in one or more of the aforementioned polyisocyanates. It is also possible to use any mixtures of the aforementioned polyisocyanates which correspond to the above-mentioned condition with regard to the melting or softening point.
Geeignet sind auch Phosgenierungsprodukte von Kondensaten von Anilin und Aldehyden oder Ketonen, wie z.B. Acetaldehyd, Propionaldehyd, Butyraldehyd, Aceton, Methyläthylketon. Fern geeignet sind die Phosgenierungsprodukte von Kondensaten von am Kern Alkyl substituierten Anilinen, insbesondere Toluidinen mit Aldehyden oder Ketonen, wie z.B. Formaldehyd, Acetaldehyd, Butyraldehyd, Aceton, Methyläthylketon.Phosgenation products of condensates of aniline and aldehydes or ketones, such as e.g. Acetaldehyde, propionaldehyde, butyraldehyde, acetone, methyl ethyl ketone. The phosgenation products of condensates of anilines substituted on the nucleus alkyl, in particular toluidines with aldehydes or ketones, such as e.g. Formaldehyde, acetaldehyde, butyraldehyde, acetone, methyl ethyl ketone.
Weiterhin geeignet sind Umsetzungsprodukte der genannten aromatischen Polyisocyanatgemische mit 0,2 bis 50 Äquivaient-96 an Polyolen, vorausgesetzt, daß die Viskosität der so erhaltenen Umsetzungsprodukte 30000 cP bei 25°C nicht überschreitet und der NCO-Gehalt der Umsetzungsprodukte mindestens 15 Gew.-% beträgt. Geeignete Polyole zur Modifizierung der Ausgangsmaterialien sind insbesondere die in der Polyurethanchemie bekannten Polyäther-und/oder Polyesterpolyole des Molekulargewichtsbereichs 200 bis 6000, vorzugsweise 300 bis 4000, sowie niedermolekulare Polyole des Molekulargewichtsbereichs 62 bis 200. Beispiele derartiger niedermolekularer Polyole sind Äthylenglykol, Propylenglykol, Glyzerin, Trimethylolpropan, 1,4,6-Hexantriol.Also suitable are reaction products of the above aromatic polyisocyanate mixtures with from 0.2 to 50 Äquivaient- 9 6 of polyols, provided that the viscosity of the reaction products 30000 cP thus obtained at 25 ° C does not exceed the NCO content of the reaction products at least 15 weight % is. Suitable polyols for modifying the starting materials are, in particular, the polyether and / or polyester polyols of the molecular weight range 200 to 6000, preferably 300 to 4000, and low molecular weight polyols of the molecular weight range 62 to 200 known in polyurethane chemistry. Examples of such low molecular weight polyols are ethylene glycol, propylene glycol, glycerin, Trimethylolpropane, 1,4,6-hexanetriol.
Die erfindungsgemäß geeigneten aromatischen Polyisocyanate weisen im allgemeinen einen NCO-Gehalt von 15-53, vorzugsweise 25-48 und besonders bevorzugt von 25-35 Gew.-%, auf.The aromatic polyisocyanates suitable according to the invention generally have an NCO content of 15-53, preferably 25-48 and particularly preferably 25-35% by weight.
Für das erfindungsgemäße Verfahren besonders geeignet sind flüssige Mehrkomponentengemische aromatischer Polyisocyanate eines NCO-Gehaltes von 20 bis 48, vorzugsweise 25 bis 35 Gew.-% und einer mittleren NCO-Funktionalitat 2,0.Liquid multi-component mixtures of aromatic polyisocyanates with an NCO content of 20 to 48, preferably 25 to 35% by weight and an average NCO functionality of 2.0 are particularly suitable for the process according to the invention.
Bevorzugt beim erfindungsgemäßen Verfahren einzusetzende flüssige aromatische Polyisocyanatgemische sind insbesondere die Phosgenierungsprodukte von Anilin/Formaldehyd-Kondensaten, welche einen Gehalt an zweikernigen Diisocyanaten von 20 bis 90 Gew.-%, dreikernigen Triisocyanaten von 3 bis 40 Gew.-%, vierkernigen Tetraisocyanaten von 1 bis 20 Gew.-% und höherkernigen Polyisocyanaten von 1 bis 40 Gew.-P aufweisen.Preferred liquid aromatic polyisocyanate mixtures to be used in the process according to the invention are, in particular, the phosgenation products of aniline / formaldehyde condensates which have a dinuclear diisocyanate content of 20 to 90% by weight, trinuclear triisocyanates of 3 to 40% by weight, tetranuclear tetraisocyanates of 1 to Have 20 wt .-% and higher core polyisocyanates of 1 to 40 wt.
Für das erindungsgemäß Verfahren weiterhin geeignet sind technische Toluylendiisocyanatgemische. Weiterhin hervorragend geeignet sind technische Destillationsrückstände, wie sie bei der Destillation von technischen Toluylendiisocyanatgemischen erhalten werden und welche einen Gehalt an freien Toluylendiisocyant-isomeren von unter 70 Gew.-% aufweisen.Derartige Destillationsrückstände sind beispielsweise nach dem Verfahren der DT-OS 2 035 731 zugänglich. Geeignet sind insbesondere auch die in der DT-OS 2 123 183 beschriebenen Destillationsrückstände, sowie deren ebenfalls in dieser letztgenannten deutschen Patentanmeldung beschriebenen Lösungen in Phosgenierungsprodukten von Anilin/ Formaldehyd-Kondensaten.Technical tolylene diisocyanate mixtures are also suitable for the process according to the invention. Technical distillation residues, such as those obtained in the distillation of technical tolylene diisocyanate mixtures and which have a free tolylene diisocyanate isomer content of less than 70% by weight, are also outstandingly suitable. Such distillation residues can be obtained, for example, by the process of DT-OS 2,035,731 . Also particularly suitable are the distillation residues described in DT-OS 2 123 183, as well as their solutions in phosgenation products of aniline / formaldehyde condensates, which are also described in this last-mentioned German patent application.
Neben den beispielt genannten aromatischen Polyisocyanaten und Chlorsulfonsäure kommen beim erfindungsgemäßen Verfahren gegebenenfalls halogensubstituierte Trialkylphosphite oder Tris-(aralkyl)-phosphite zum Einsatz, d.h. Verbindungen der Formel
- R für einen gegebenenfalls halogen- vorzugsweise chlorsubstituierten aliphatischen Kohlenwasserstoffrest mit 1-18, vorzugsweise 1-4, Kohlenstoffatomen oder einen gegebenenfalls halogen- vorzugsweise chlorsubstituierten araliphatischen Kohlenwasserstoffrest mit insgesamt 7-15 Kohlenstoffatomen, vorzugsweise 7-8 Kohlenstoffatomen, steht.
- R represents an optionally halogen-preferably chlorine-substituted aliphatic hydrocarbon radical having 1-18, preferably 1-4, carbon atoms or an optionally halogen-preferably chlorine-substituted araliphatic hydrocarbon radical having a total of 7-15 carbon atoms, preferably 7-8 carbon atoms.
Für das erfindungsgemäße Verfahren ebenfalls geeignet sind selbstverständlich solche Phosphite der genannten Formel, welche unterschiedliche Reset R aufweisen. Beispiele geeigneter Phosphite sind Trimethylphosphit, Triäthylphosphit, Tris-(2-chloräthyl)-phosphit, Tributylphosphit, Trioctylphosphit, Tribenzylphosphit oder 0,0'-Dimethyl-O"-(2-chloräthyl)-phosphit. Bevorzugt werden die beispielhaft genannten Trialkylphosphite eingesetzt. Besonders bevorzugt sind Tris(halogenalkyl)-phosphite wie insbesondere Tris-(2-chloräthyl)-phosphit.Those phosphites of the formula mentioned which have different reset R are of course also suitable for the process according to the invention. Examples of suitable phosphites are trimethyl phosphite, triethyl phosphite, tris (2-chloroethyl) phosphite, tributyl phosphite, trioctyl phosphite, tribenzyl phosphite or 0.0'-dimethyl-O "- (2-chloroethyl) phosphite. The trialkyl phosphites mentioned by way of example are preferably used. Tris (halogenoalkyl) phosphites such as, in particular, tris (2-chloroethyl) phosphite are particularly preferred.
Bei der Durchführung des erfindungsgemäßen Verfahrens werden die beispielhaft genannten Reaktionspartner vorzugsweise in solchen Mengen eingesetzt, daß pro Mol aromatisch gebundener Isocyanatgruppen 0,01 bis 0,5, vorzugsweise 0,02 bis 0,3 und besonders bevorzugt 0,03 bis 0,2 Mol Chlorsulfonsäure und 0,01 bis 0,5, vorzugsweise 0,02 bis 0,3 und insbesondere 0,03 bis 0,2 Mol Phosphit zur Umsetzung gelangen. Im allgemeinen werden äquimolare Mengen Phosphit und Chlorsulfonsäure eingesetzt, jedoch ist es auch möglich, Chlorsulfonsäure bzw. Phosphit in unterschiedlichen molaren Mengen einzusetzen.When carrying out the process according to the invention, the reaction partners mentioned by way of example are preferably used in amounts such that 0.01 to 0.5, preferably 0.02 to 0.3 and particularly preferably 0.03 to 0.2 mol are used per mole of aromatically bound isocyanate groups Chlorosulfonic acid and 0.01 to 0.5, preferably 0.02 to 0.3 and in particular 0.03 to 0.2 mol of phosphite Implementation. In general, equimolar amounts of phosphite and chlorosulfonic acid are used, but it is also possible to use chlorosulfonic acid or phosphite in different molar amounts.
Die Durchführung des erfindungsgemäßen Verfahrens erfolgt im Temperaturbereich zwischen -10 bis +150°C, vorzugsweise zwischen 0 und 100°C.The process according to the invention is carried out in the temperature range between -10 to + 150 ° C., preferably between 0 and 100 ° C.
Die erfindungsgemäße Umsetzung kann sowohl durch unmittelbare Vermischung der drei Reaktionskomponenten als auch in einem Zweistufen-Prozeß durchgeführt werden, wobei im letztgenannten Fall zunächst das Polyisocyanat mit der Chlorsulfonsäure zur Umsetzung gebracht wird und anschließend die Umsetzung mit dem Phosphit erfolgt. Das erfindungsgemäße Verfahren kann sowohl in Anwesenheit als auch insbesondere bei Verwendung von niedrigviskosen Ausgangsmaterialien in Abwesenheit von unter den Reaktionsbedingung gegenüber den Ausgangsmaterialien und Endprodukten des erfindungsgemäßen Verfahrens inerten Lösungsmitteln durchgeführt werden besonders bevorzugte Lösungsmittel sind Halogenkohlenwasserstoffe wie z.B. Dichloräthan, Trichtoräthan, Fluortrichlormethan, Methylenchloride oder Chlorbenzol. Die Lösungsmittel weisen vorzugsweise einen zwischen 0 und 140°C liegenden Siedepunkt auf. Gegebenenfalls kann die erfindungsgemäße. Umsetzung auch unter Druck durchgeführt werden. Im Falle der Mitverwendung von inerten Lösungsmitteln kann die Konzentration der Reaktanten in diesem Lösungsmittel innerhalb weiter Bereiche schwanken, im allgemeinen wird das Lösungsmittel in solchen Mengen eingesetzt, daß 20-100 gew.-%ige Lösungen der Reaktionspartner während der erfindungsgemäßen Umsetzung vorliegen, wobei die genannte Konzentration den Prozentsatz der Gewichtsmenge aller Reaktionspartner bezogen auf das Gewicht der Gesamtlösung angeben.The reaction according to the invention can be carried out either by directly mixing the three reaction components or in a two-stage process, in which case the polyisocyanate is first reacted with the chlorosulfonic acid and then the reaction with the phosphite is carried out. The process according to the invention can be carried out both in the presence and, in particular, when using low-viscosity starting materials in the absence of solvents which are inert under the reaction conditions to the starting materials and end products of the process according to the invention. Particularly preferred solvents are halogenated hydrocarbons, e.g. Dichloroethane, trichtorethane, fluorotrichloromethane, methylene chloride or chlorobenzene. The solvents preferably have a boiling point between 0 and 140 ° C. If necessary, the invention. Implementation can also be carried out under pressure. In the case of the use of inert solvents, the concentration of the reactants in this solvent can vary within wide ranges, in general the solvent is used in such amounts that 20-100% strength by weight solutions of the reactants are present during the reaction according to the invention, the Specify the stated concentration as a percentage of the amount by weight of all reactants based on the weight of the total solution.
Bei der Durchführung des erfindungsgemäßen Verfahrens wird vorzugsweise das Polyisocyanat mit dem Phosphit und dem gegebenenfalls mitzuverwendenden Lösungsmittel vermischt und die Chlorsulfonsäure, welche ebenfalls in einem inerten Lösungsmittel gelöst sein kann, zu diesem vorgelegten Gemisch innerhalb einer Zeitspanne von wenigen Minuten bis mehreren Stunden unter Rühren zugegeben. Vorzugsweise erfolgt hierbei die Zugabe der Chlorsulfonsäure bei Raumtemperatur, wonach sich zur Vervollständigung der Reaktion eine Erhitzung des Reaktionsgemisches auf 50-100°C anschließt.When carrying out the process according to the invention, the polyisocyanate is preferably mixed with the phosphite and any solvent to be used, and the chlorosulfonic acid, which may also be dissolved in an inert solvent, is added to this mixture in a period of a few minutes to several hours with stirring. The chlorosulfonic acid is preferably added at room temperature, after which the reaction mixture is heated to 50-100 ° C. to complete the reaction.
Die beim erfindungsgemäßen Verfahren ablaufenden chemischen Reaktionen seien am Beispeil der Umsetzung zwischen einem aromatischen Diisocyanat R' (NCO)z (R' steht für den aromatischen Kohlenwasserstoffrest eines aromatischen Diisocyanats), Chlorsulfonsäure und einem Phosphit P (OR)3 (R hat die oben angegebene Bedeutung) erläutert:
Es wird vermutet, daß die Chlorsulfonsäure zu sulfonierten Carbamidsäurechloriden reagiert, die anschließend im Sinne einer Arbusow-Reaktion zu den erfindungsgemäßen Produkten reagieren. Überraschenderweise erfolgen die Umsetzungen unter den genannten Bedigungen einheitlich, obwohl mit verschiedenen Nebenreaktionen zu rechnen ist, die sich, wie dem Fachmann bekannt ist, aus der Kombination Phosphit/Chlorsulfonsäure ergeben (z.B. Houben Weyl, Vierte Auflage Band XII/2 1964, S. 79 ff).It is assumed that the chlorosulfonic acid reacts to sulfonated carbamic acid chlorides, which then react in the sense of an Arbusow reaction to the products according to the invention. Surprisingly, the reactions take place uniformly under the conditions mentioned, although various side reactions are to be expected, which, as is known to the person skilled in the art, result from the combination of phosphite / chlorosulfonic acid (for example Houben Weyl, fourth edition volume XII / 2 1964, p. 79 ff).
Besonders überraschend ist, daß auch bei Verwendung von Toluylendiisocyanat sowie Phosgenierungsprodukten der AnilinFormaldehyd-Kondensation mit hohem Gehalt 4,4' - Zweikern-Produkt die erfindungsgemäßen Verfahrensprodukte flüssig sind, insbesondere, wenn auf 1 NCO Äquivalent nicht mehr als 0,2 Mol Chlorsulfonsäure und nicht mehr als 0,2 Mol organisches Phosphit eingesetzt werden.It is particularly surprising that the process products according to the invention are liquid even when tolylene diisocyanate and phosgenation products of the aniline-formaldehyde condensation with a high content of 4,4 '- two-core product are used, in particular if not more than 0.2 mol of chlorosulfonic acid per 1 NCO equivalent and not more than 0.2 mol of organic phosphite are used.
Die nach dem erfindungsgemäßen Verfahren zugänglichen Sulfonsäure- und Phosphonatgruppen aufweisenden, vzw. flüssigen Polyisocyanate sind gekennzeichnet durch
- a) einen NCO-Gehalt von 10 bis 42 Gew.-%, vorzugsweise 25 bis 35 Gew.-%,
- b) einen Schwefelgehalt von 0,5-5 Gew.-%,
- c) einen Phosphorgehalt von 0,5-5 Gew.-% und
- d) eine Viskosität von 10 bis 50 000, vorzugsweise 100 bis 20 000 cP bei 25°C.
- a) an NCO content of 10 to 42% by weight, preferably 25 to 35% by weight,
- b) a sulfur content of 0.5-5% by weight,
- c) a phosphorus content of 0.5-5 wt .-% and
- d) a viscosity of 10 to 50,000, preferably 100 to 20,000 cP at 25 ° C.
Im Falle der Verwendung eines molaren Überschusses an Chlorsulfonsäure bezogen auf das eingesetzte Phosphite liegen die Isocyanatgruppen in den erfindungsgemäßen Verfahrensprodukten teilweise in Form von Carbamidsäure-chlorid-Gruppen vor. Die genannten Zahlenwerte bezüglich des NCO-Gehaltes der erfindungsgemäßen Produkte umfassen auch derartige gegebenenfalls in Form von Carbamidsäure-chlorid-Gruppen vorliegende NCO-Gruppen, wobei bei der Berechnung der NCO-Gehalte auch in diesem Fall das Molekulargewicht der NCO-Gruppe (42) zugrundegelegt wurde. Da die Sulfonsäuregruppen im Anschluß an die erfindungsgemäße Umsetzung, wie weiter unten ausgeführt, ohne Schwierigkeiten zumindest teilweise neutralisiert oder verestert werden könne, bezieht sich der angegebenen Schwefelgehalt auf die in den Verfahrensprodukten vorliegenden gegebenenfalls zumindest teilweise neutralisierten oder veresterten Sulfonsäuregruppen.If a molar excess of chlorosulfonic acid, based on the phosphite used, is used, the isocyanate groups in the process products according to the invention are partly in the form of carbamic acid chloride groups. The numerical values mentioned with regard to the NCO content of the products according to the invention also include such NCO groups which may be in the form of carbamic acid chloride groups, the molecular weight of the NCO group (42) also being used in this case when calculating the NCO contents has been. Since the sulfonic acid groups can be at least partially neutralized or esterified without difficulty after the reaction according to the invention, as explained below, the stated sulfur content relates to the sulfonic acid groups which are optionally at least partially neutralized or esterified.
Die erfindungsgemäßen Sulfonsäure- und Phosphonatgruppen aufweisenden aromatischen Polyisocyanate stellen wertvolle Ausgangsmaterialien zur Herstellung von Formstoffen un kompakten Kunststoffen dar. Sie lassen sich ohne Schwierigkeiten nach üblichen Techniken, wie Gießverfahren, sowie über die üblichen Förder- und Dosiersysteme verarbeiten. Die nach dem erfindungsgemäßen Verfahren zugänglichen aromatischen phosphonatisierten Isocyanatosulfonsäuren können im Anschluß an ihre Herstellung durch eine Neutralisationsreaktion ganz- oder teilweise in die entsprechenden Isocyanatosulfonate überführt werden.The aromatic polyisocyanates containing sulfonic acid and phosphonate groups according to the invention are valuable starting materials for the production of moldings and compact plastics. They can be processed without difficulty by customary techniques, such as casting processes, and by means of the customary conveying and metering systems. The aromatic phosphonated isocyanatosulfonic acids obtainable by the process according to the invention can, after their preparation, be converted completely or partially into the corresponding isocyanatosulfonates by a neutralization reaction.
Geeignete Neutralisationsmittel sind organische oder anorganische Basen, wie zum Beispiel Trimethylamin, Triäthylamin, Tributylamin, Dimethylanilin, Urotropin, Natriumhydrogencarbonat, Natriumhydroxid, Calciumcarbonat, Magnesiumcarbonat, Calciumhydroxid, Magnesiumhydroxid, Magnesiumoxid, Zinkoxid, Natriumphosphat. Dabei können anorganische Neutralisationsmittel, welche selbst nicht stark basisch reagieren, wie Calciumcarbonat, Magnesiumcarbonat, Dolomit, Kreide, Natriumphosphat, ohne weiteres auch in hohem Überschuß als Füllstoff eingesetzt werden. Durch die Überführung der Sulfonsäuregruppen in die entsprechenden Sulfonatgruppen wird die Hydrophilie und Reaktivität der erfindungsgemäßen Produkte gesteigert. Eine Überführung der entsprechenden phosphonatisierten isocyanatosulfonsäuren in die entsprechenden Sulfonsäure-ester mit Epoxiden bzw. Oxatonen kann ebenfalls mit Erfolg zur Reduzierung der sauren Anteile angewendet werden. Geeignete Epoxide sind z.B.: Äthylenoxid, Propylenoxid, Epichlorhydrin.Suitable neutralizing agents are organic or inorganic bases, such as trimethylamine, triethylamine, tributylamine, dimethylaniline, urotropin, sodium hydrogen carbonate, sodium hydroxide, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, magnesium oxide, zinc oxide, sodium phosphate. Inorganic neutralizing agents, which themselves do not react strongly basic, such as calcium carbonate, magnesium carbonate, dolomite, chalk, sodium phosphate, can also be used in a large excess as filler. The hydrophilicity and reactivity of the products according to the invention is increased by converting the sulfonic acid groups into the corresponding sulfonate groups. Conversion of the corresponding phosphonated isocyanatosulfonic acids into the corresponding sulfonic acid esters with epoxides or oxatones can also be used successfully to reduce the acidic content. Suitable epoxides include: ethylene oxide, propylene oxide, epichlorohydrin.
Ausgangsmaterialien für die nachstehend beschriebenen Beispiele:
- A,: Von rohem Phosgenierungsprodukt eines Anilin/Formaldehyd-Kondensats wird soviel Diisocyanatodiphenylmethan abdestilliert, daß der Destillationsrüchstand bei 25°C eine Viskositat von 100 cP aufweist. (2-Kernanteil: 59,7 Gew.-%; 3-Kernanteil: 21,3 Gew.-%; Anteil an höherkernigen Polyisocyanaten: 19,0 Gew.-%). NCO-Gehalt: 31,5 Gew.-%.
- AZ: Entsprechend hergestelltes Polyisocyanat mit einer Viskosität bei 25°C von 200 cP. (2-Kernanteil: 44,3 Gew.-%; 3-Kernanteil: 23,5 Gew.-%; Anteil an höher-kernigen Polyisocyanaten: 32,2 Gew-%). NCO-Gehalt: 31,1 Gew.-%.
- A3: Entsprechend hergestelltes Polyisocyanat mit einer Viskosität bei 25°C von 400 cP. (2-Kernanteil: 45,1 Gew-%; 3-Kernantiel: 22,3 Gew-%; Antiel an höherkernigen Polyisocyanaten: 32,6 Gew.-%). NCO-Gehalt: 30,9 Gew-%.
- A4: Gemisch aus Toluylen-2,4-diisocyanat und Toluylen-2,6-diisocyanat im Verhältnis 80:20. NCO-Gehalt: 48 Gew.-%.
- As: 40 %ige Lösung eines bei der Destillation von A4 anfallenden Destillationsrückstands in A4. NCO-Gehalt: 38,3 Gew.-%.
- Aµ: Präpolymer aus 90 Gew.-% A2 und 10 Gew.-% eines auf Trimethylolpropan gestarteten Polyäthylenglykols der OH-Zahl 250, mit einer Viskosität bei 25°C von 21 000 cP. NCO-Gehalt: 26,2 Gew.-%.
- A,: So much diisocyanatodiphenylmethane is distilled off from the crude phosgenation product of an aniline / formaldehyde condensate that the distillation residue at 25 ° C. has a viscosity of 100 cP. (2-core fraction: 59.7% by weight; 3-core fraction: 21.3% by weight; proportion of higher-core polyisocyanates: 19.0% by weight). NCO content: 31.5% by weight.
- A Z : Correspondingly produced polyisocyanate with a viscosity at 25 ° C of 200 cP. (2-core fraction: 44.3% by weight; 3-core fraction: 23.5% by weight; proportion of higher-core polyisocyanates: 32.2% by weight). NCO content: 31.1% by weight.
- A 3 : Correspondingly produced polyisocyanate with a viscosity at 25 ° C of 400 cP. (2-core content: 45.1% by weight; 3-core content: 22.3% by weight; content of higher-core polyisocyanates: 32.6% by weight). NCO content: 30.9% by weight.
- A 4 : mixture of tolylene-2,4-diisocyanate and toluene-2,6-diisocyanate in a ratio of 80:20. NCO content: 48% by weight.
- A s : 40% solution of a distillation residue in A 4 resulting from the distillation of A 4 . NCO content: 38.3% by weight.
- A µ : prepolymer of 90% by weight of A 2 and 10% by weight of a polyethylene glycol of OH number 250 started on trimethylolpropane, with a viscosity at 25 ° C. of 21,000 cP. NCO content: 26.2% by weight.
1000 g Polyisocyanat A3 und 78,5 g Tris-(2- chloräthyl)-phosphit werden vorgelegt. Bei 20-30°C läßt man innerhalb von 2 Stunden 41,3 g Chlorsulfonsäure in 17 g Methylenchlorid zutropfen. Man läßt 1 Stunde bei 100°C nachrühren und erhält ein Produkt mit folgenden Werten:
- Schwefelgehalt: 1,0 %
- Phosphorgehalt: 0,8 %
- NCO-Gehalt: 26,5 %
- Viskosität: 1200 cP
- (25°C)
- Sulfur content: 1.0%
- Phosphorus content: 0.8%
- NCO content: 26.5%
- Viscosity: 1200 cP
- (25 ° C)
Entsprechend hergestellte Produkte sind in Tabelle 1 aufgeführt. Dichloräthan wurde in einigen Beispielen als Lösungsmittel mitverwendet und nach Reaktionsende bei 50°C/20 Torr abdestilliert.
Claims (3)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19772725208 DE2725208A1 (en) | 1977-06-03 | 1977-06-03 | POLYISOCYANATE CONTAINING SULPHIC ACID AND PHOSPHONATE GROUPS |
DE2725208 | 1977-06-03 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0000021A1 EP0000021A1 (en) | 1978-12-20 |
EP0000021B1 true EP0000021B1 (en) | 1980-07-23 |
Family
ID=6010691
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78100033A Expired EP0000021B1 (en) | 1977-06-03 | 1978-06-01 | Process for the preparation of sulfonic acid groups and phosphonate groups bearing polyisocyanate mixtures |
Country Status (4)
Country | Link |
---|---|
US (1) | US4177206A (en) |
EP (1) | EP0000021B1 (en) |
DE (2) | DE2725208A1 (en) |
IT (1) | IT1104722B (en) |
Families Citing this family (2)
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EP1273172A1 (en) * | 2000-04-06 | 2003-01-08 | Koninklijke Philips Electronics N.V. | Object-conditional access system |
WO2015038579A1 (en) * | 2013-09-11 | 2015-03-19 | Equip, Llc | Discrete peg based dyes |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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DE1127583B (en) * | 1960-08-25 | 1962-04-12 | Bayer Ag | Process for the production of flame retardant plastics, including foams |
US3959329A (en) * | 1973-05-24 | 1976-05-25 | Bayer Aktiengesellschaft | Polyisocyanates containing sulphonic acid or sulphonate groups |
DE2359614A1 (en) * | 1973-11-30 | 1975-06-05 | Bayer Ag | POLYISOCYANATES CONTAINING SULPHONIC ACID AND / OR SULFONATE GROUPS |
-
1977
- 1977-06-03 DE DE19772725208 patent/DE2725208A1/en not_active Withdrawn
-
1978
- 1978-05-19 US US05/907,515 patent/US4177206A/en not_active Expired - Lifetime
- 1978-06-01 EP EP78100033A patent/EP0000021B1/en not_active Expired
- 1978-06-01 DE DE7878100033T patent/DE2860035D1/en not_active Expired
- 1978-06-02 IT IT49668/78A patent/IT1104722B/en active
Also Published As
Publication number | Publication date |
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DE2725208A1 (en) | 1978-12-14 |
US4177206A (en) | 1979-12-04 |
EP0000021A1 (en) | 1978-12-20 |
DE2860035D1 (en) | 1980-11-13 |
IT1104722B (en) | 1985-10-28 |
IT7849668A0 (en) | 1978-06-02 |
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