CA1318331C - Ion exchangers modified with mercapto amines - Google Patents
Ion exchangers modified with mercapto aminesInfo
- Publication number
- CA1318331C CA1318331C CA000539071A CA539071A CA1318331C CA 1318331 C CA1318331 C CA 1318331C CA 000539071 A CA000539071 A CA 000539071A CA 539071 A CA539071 A CA 539071A CA 1318331 C CA1318331 C CA 1318331C
- Authority
- CA
- Canada
- Prior art keywords
- phenol
- ion exchanger
- butylphenol
- compound
- formula
- 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 - Fee Related
Links
- -1 mercapto amines Chemical group 0.000 title claims abstract description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 19
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- RSPCKAHMRANGJZ-UHFFFAOYSA-N thiohydroxylamine Chemical compound SN RSPCKAHMRANGJZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims abstract description 3
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract 2
- 230000003472 neutralizing effect Effects 0.000 claims abstract 2
- 150000002500 ions Chemical class 0.000 claims description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 150000002989 phenols Chemical class 0.000 claims description 11
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims description 8
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 8
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 8
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 8
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 8
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 4
- PXSSNPBEHHJLDH-UHFFFAOYSA-N 2,3,4,5-tetramethylphenol Chemical compound CC1=CC(O)=C(C)C(C)=C1C PXSSNPBEHHJLDH-UHFFFAOYSA-N 0.000 claims description 4
- HOLHYSJJBXSLMV-UHFFFAOYSA-N 2,6-dichlorophenol Chemical compound OC1=C(Cl)C=CC=C1Cl HOLHYSJJBXSLMV-UHFFFAOYSA-N 0.000 claims description 4
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 claims description 4
- YPNZJHFXFVLXSE-UHFFFAOYSA-N 2-chloro-6-methylphenol Chemical compound CC1=CC=CC(Cl)=C1O YPNZJHFXFVLXSE-UHFFFAOYSA-N 0.000 claims description 4
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 4
- NGFPWHGISWUQOI-UHFFFAOYSA-N 2-sec-butylphenol Chemical compound CCC(C)C1=CC=CC=C1O NGFPWHGISWUQOI-UHFFFAOYSA-N 0.000 claims description 4
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims description 4
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 claims description 4
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000005915 C6-C14 aryl group Chemical group 0.000 claims description 4
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 235000010292 orthophenyl phenol Nutrition 0.000 claims description 4
- 125000006413 ring segment Chemical group 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 claims description 3
- FUEMCRRMXUJLCG-UHFFFAOYSA-N (4-aminophenyl)methanethiol Chemical compound NC1=CC=C(CS)C=C1 FUEMCRRMXUJLCG-UHFFFAOYSA-N 0.000 claims description 2
- GADCRQVORPKEQP-UHFFFAOYSA-N 2-aminoethyl(dimethyl)sulfanium Chemical compound C[S+](C)CCN GADCRQVORPKEQP-UHFFFAOYSA-N 0.000 claims description 2
- IYGAMTQMILRCCI-UHFFFAOYSA-N 3-aminopropane-1-thiol Chemical compound NCCCS IYGAMTQMILRCCI-UHFFFAOYSA-N 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 5
- RMGFZTZJGSLEIQ-UHFFFAOYSA-N 4-cyclohexylsulfanyl-n-ethylbutan-1-amine Chemical compound CCNCCCCSC1CCCCC1 RMGFZTZJGSLEIQ-UHFFFAOYSA-N 0.000 claims 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 9
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000875 corresponding effect Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 229960003151 mercaptamine Drugs 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 3
- KXYDGGNWZUHESZ-UHFFFAOYSA-N 4-(2,2,4-trimethyl-3h-chromen-4-yl)phenol Chemical compound C12=CC=CC=C2OC(C)(C)CC1(C)C1=CC=C(O)C=C1 KXYDGGNWZUHESZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- JHOPNNNTBHXSHY-UHFFFAOYSA-N 2-(4-hydroxyphenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1O JHOPNNNTBHXSHY-UHFFFAOYSA-N 0.000 description 1
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 150000003548 thiazolidines Chemical class 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/016—Modification or after-treatment of ion-exchangers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
ABSTRACT
This invention relates to a process for preparing an anhydrous ion exchanger modified with a mercapto amine, which process comprises drying an acid ion exchanger resin having a total capacity of acid functions of from 0.7 to 2.1 mval/ml of ion exchanger in the water-moist form with a water content of about 75 to 85% by weight or a total capacity of acid functions of from 3.5 to 5 mval or higher when based on 1 g of dry substance of ion exchanger, and thereafter rinsing with the phenol required for preparation of the bisphenol and thereafter neutralizing with at least 0.3 mol of a mercapto amine corresponding to formula (I) per mol of acid function of the ion exchanger at a temperature above the melting point of bisphenol.
(I)
This invention relates to a process for preparing an anhydrous ion exchanger modified with a mercapto amine, which process comprises drying an acid ion exchanger resin having a total capacity of acid functions of from 0.7 to 2.1 mval/ml of ion exchanger in the water-moist form with a water content of about 75 to 85% by weight or a total capacity of acid functions of from 3.5 to 5 mval or higher when based on 1 g of dry substance of ion exchanger, and thereafter rinsing with the phenol required for preparation of the bisphenol and thereafter neutralizing with at least 0.3 mol of a mercapto amine corresponding to formula (I) per mol of acid function of the ion exchanger at a temperature above the melting point of bisphenol.
(I)
Description
Ion exchangers modified with mercapto amines _ ._ The condensation of phenols and carbonyl compounds to produce bisphenols is known. A wide variety of catalysts has already been used for this reaction; for example, hydrochloric acid (US-PS 2 182 308 and 2 191 831), boron trifluoride (Chemical Abstracts 58, 3338 c1, perchloric ~ acid ~Chemical Abstracts 60, 1626 h), benzene sulphonic `~ acid (Chemical Abstracts 59, 511 h) and various cation exchanger resins (e.g. GB-PS 842 209, 849 565 and 883 391). The addition of compounds containing sulphur to the catalyst is also known, e.g. the use of thioglycollic acid and 3-mercaptopropionic acid has been disclosed in US-PS 2 468 982 and 2 623 908, the addition of thio-~; phenols in US-PS 2 359 242, the addition of alkylmercaptans in US-PS 2 775 620 and the addition of hydrogen sulphide in Chemical Abstracts 58, 1403 e.
These known catalysts containing sulphur give rise to considerable damage by corrosion in industrial practice.
Bisphenols prepared with the aid of these catalysts are contaminated crude products which contain unreacted phenol, carbonyl compounds, water of reaction and undesirable ; by-products in addition to bisphenol. Bisphenol A synthe-sized with these catalysts, for example, contains isomers of bisphenol A, in particular 2,2~~2,4'-dihydroxydiphenyl)-propane and 2,2-(2,2'-dihydroxydiphenyl)-propane and complex products such as the so-called "codimer", 2,2,4-trimethyl-4-p-hydroxyphenylchroman, condensation products such as triphenol or even higher condensation products in the form of tarry or high boiling substances as well Le A 24 214 as decomposition products and substances containing sulphur.
The presence of these by-products is undesirable as they tend to remain in the end product and give rise to discolour-ation. This impairs the usefulness of the end product even when a high degree of purity is not required~ In addition, the by-products present interfere with some of the usual reactions of bisphenol, in particular its further reaction to polycarbonates, US-PS 3 394 089 describes a process for the preparation of bisphenol A from acetone and phenol with the aid of a catalyst containing sulphonic acid groups in which 5 to 25 mols-% of the sulphonic acid groups are blocked with mercapto amines to form ammonium salts which are said to obviate these disadvantages. This modified ion exchanger resin which is obtained by neutralization in aqueous solution, for example with ~-mercaptoethylamine, is unsuitable for the production process because it is unstable and because the mercapto compound is washed out by the reaction medium in the course of time so that the catalyst loses its effect.
It has now been found that highly pure bisphenols may be prepared with the aid of highly acid ion exchangers in which the acid groups are neutralized to a very high degree, even quantitatively, this neutralization being carried out on a previously dried ion exchanger in an anhydrous medium.
The present invention relates to a process for the preparation of anhydrous ion exchangers modified with mercapto amines, characterised in that known acid ion exchanger.resins which have a total capacity of acid functions of from 0.7 to 2.1 mval/ml of ion exchanger when they have a water content of about 75 to 85% by weight or a total capacity of acid functions of from 3.5 to S mval or higher, based on 1 g of dry substance of ion exchanger, are dried and then rinsed with the phenol required for the preparation of the bisphenol and are then neutralized with at least 0.3 mol, preferably with 0.~ to 1 mol of mercapto amines of formula (I) per mol of acid f unction of the ion exchanger at temperatures above the meltin~ point of this phenol.
The present invention also relates to the ion exchangers modified with mercapto amines of formula (I) obtainable by the process according to the invention.
The acid functions of these modified ion exchangers are occupied with the mercapto amine of formula (I) to an extent of at least 30 mol-% and pref~erably 40 to 100 mol-%.
Suitable acid ion exchangers include, for example, the conventional reaction products of styrene-divinyl benzene copolymers with conventional sulphonating agents such as sulphuric acid, chlorosulphonic acid etc. These may be present in spherical form with particle diameters of 0.3 to 1.5 mm. They may be of the gel type or macro-porous. Their total capacity of acid functions ranges from 0.7 to 2.1 mval/ml of ion exchanger when they are moistened with a water content of about 75 to ~5% by weight or from 3.5 to 5 mval or higher, based on 1 g of the dry substance of ion exchanger.
Before the treatment or neutralization with the mercapto amines corresponding to formula (I) which are to be used according to the invention, these ion exchangers are dried, optionally by heat 9 optionally in a vacuum or optionally by washing with hydrophilic organic liquids such as alcohols or phenols or by azeotropic distilla-tion with organic liquids such as toluene, xylene, methylene chloride or others. The ion exchanger resin is then rinsed with the phenol required for the prepara-tion of the bisphenol, and the required quantity of mer-capto amine of formula (I) is then added in this medium at temperatures above the melting point of the phenol with stirring or in a fluidized bed layer.
In the mercapto amines corresponding to formula (I) " ~
.
R \
/ N - R - CH2 - S - H ~I), R denotes a C1-C6-alkylene, C5-C10-cycloalkylene or C6-C1~-arylene group, preferably a methylene group, and R2 and R3, which are independent of one another, denote C1-C6-alkyl groups or, preferably, hydrogen. The follow-ing are suitable mercapto amines corresponding to formula Dimethylmercaptoethylamine, ethyl-cyclohexylmercapto-butylamine, mercaptopropylamine, 1-amino-4-mercaptomethyl-benzene and B-mercaptoethylamine; p-mercaptoethylamine is preferred.
~' The mercapto amines of formula ~I) may be used as such or prepared in situ from thiazolidines such as 2,2-dimethyldiazolidine.
The cation exchanger resin which has been modified by neutralization may be used for the preparation of numerous bisphenols from phenols and carbonyl compounds.
Suitable phenols include those corresponding to formula ; (II) ~ ~ R1 R2 ;- HO ~ H (II) 3 ~ 4 R R
~ 20 wherein ; R1, R2, R3 and R4 denote, independently of one another, hydrogen (H), C1-C4-alkyl or halogen such as F, Cl or Br.
The following are given as examples: 2,6-Dimethyl-phenol, o- and m-cresol, o-sec.butylphenol, o-tert.-butylphenol, 1,3,5-xylenol, 2,6-ditert.-butylphenol, tetramethylphenol, 2-methyl-6-tert.-butylphenol, o-phenyl-phenol, o- and m-chlorophenol, o-bromophenol, 6-chloro-o-cresol and 2,6-dichlorophenol.
Unsubstituted phenol is preferred.
,, .
Suitable carbonyl compounds include those corres-ponding to formula (III) R - C = O (III), wherein R1 and R2 denote, independently of one another, hydrogen (H), Cl-C6-alkyl, C6-C10-cycloalkyl, C6-C14-aryl, C7-C20-aralkyl or C7-C20-alkylaryl or R and R together form a saturated rin~ with 5 to 6 ring atoms, The following are examples of suitable carbonyl com-pounds such as aldehydes and ketones: Formaldehyde, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, cyclohexanone, acetophenone, etc, Acetone is preferred, The process of preparation may be carried out contin-uously or batchwise by methods and with apparatus whichare known in the art, In the batchwise method, 80 to 200 g, preferably 100 to 150 g of dry substance of ion exchanger resin according to the invention are used per mol of carbonyl compound.
The reaction temperature employed for the preparation of the bisphenol is in the region of 40 to 120C and is preferably above the solidification point of the com-ponents.
The reaction time or dwell time is chosen to be sufficiently long for complete conversion of the-carbonyl compound put into the process and is preferably from 30 to 240 minutes.
The present invention accordingly also relates to the use of the ion exchangers modified with mercapto amines of formula (I) obtained by the process according to the invention for the preparation of bisphenols from phenols and carbonyl compounds.
The reaction mixture obtained from the reaction of phenol with carbonyl compound is worked up by the usual .
methods such as distillation, crystallisation, etc.
Thus, for example, the bisphenol prepared may be cooled in the reaction mixture until crystallisation sets in and the phenol may then be removed by distill-ation or extraction from the mixed crystals of bisphenoland phenol which have been filtered off.
The bisphenol prepared by this process is suitable for known fields of application without after-purification and is also suitable for applications in which an excep-tionally high standard of purity is required, such asthe preparation of optically highly pure polycarbonates..
Example 1 Preparation of the modified ion exchanger resin _ The water-moist ion exchanger as obt,ained from the supplier with a moisture content of about 80% by weight and a total capacity of 0.75 mval/ml is washed with distilled water. It is then dried for 24 hours in a water jet vacuum at 90 to 100C to reduce the water content to below 1~ by weight.
The remaining water is distilled off as an azeotropic mixture with toluene and the toluene adhering to the ion exchange resin is then distilled off in a water jet vacuum at 95C.
- 120 g of this pretreated ion exchanger resin are taken up with 1128 g of phenol in a stirrer apparatus and left to swell in the phenol at 65C for 24 hours with exclusion of moisture. The quantity of mercapto ethylamine required for blocking the mol-~ indicated in Examples 2 to 10 is then added with stirring.
Examples 2 - 10 Preparation of bisphenol A (BPA) .
The ion exchanger resin was modified with p-mercapto ethylamine by the process described in Example 1 so that 15 to 100% of ~he sulphonic acid groups were neutra~ed in nine different adjustments. 58 g of acetone were added at 65C to the solution prepared in Example 1 and the purity of the bisphenol and quantity of by~roducts were determined gas chromatographically after complete conversion of the acetone. The results obtained are sum-marized in the following Table in terms of the mean values obtained in each case from 5 experimental examples~
13183:~1 GC surface percentayes Example Mol-% BPA By-products occupied 2 15 93.6 6.4 (comparison) 3 20 93.8 6.2 ~comparison) 4 25 94.3 5.7 (comparison) ~4.5 5.5 6 ~0 94.7 5.3 7 50 95.1 4.9 8 60 95.7 4~3 9 80 96.2 3.~
100 96.7 3.3
These known catalysts containing sulphur give rise to considerable damage by corrosion in industrial practice.
Bisphenols prepared with the aid of these catalysts are contaminated crude products which contain unreacted phenol, carbonyl compounds, water of reaction and undesirable ; by-products in addition to bisphenol. Bisphenol A synthe-sized with these catalysts, for example, contains isomers of bisphenol A, in particular 2,2~~2,4'-dihydroxydiphenyl)-propane and 2,2-(2,2'-dihydroxydiphenyl)-propane and complex products such as the so-called "codimer", 2,2,4-trimethyl-4-p-hydroxyphenylchroman, condensation products such as triphenol or even higher condensation products in the form of tarry or high boiling substances as well Le A 24 214 as decomposition products and substances containing sulphur.
The presence of these by-products is undesirable as they tend to remain in the end product and give rise to discolour-ation. This impairs the usefulness of the end product even when a high degree of purity is not required~ In addition, the by-products present interfere with some of the usual reactions of bisphenol, in particular its further reaction to polycarbonates, US-PS 3 394 089 describes a process for the preparation of bisphenol A from acetone and phenol with the aid of a catalyst containing sulphonic acid groups in which 5 to 25 mols-% of the sulphonic acid groups are blocked with mercapto amines to form ammonium salts which are said to obviate these disadvantages. This modified ion exchanger resin which is obtained by neutralization in aqueous solution, for example with ~-mercaptoethylamine, is unsuitable for the production process because it is unstable and because the mercapto compound is washed out by the reaction medium in the course of time so that the catalyst loses its effect.
It has now been found that highly pure bisphenols may be prepared with the aid of highly acid ion exchangers in which the acid groups are neutralized to a very high degree, even quantitatively, this neutralization being carried out on a previously dried ion exchanger in an anhydrous medium.
The present invention relates to a process for the preparation of anhydrous ion exchangers modified with mercapto amines, characterised in that known acid ion exchanger.resins which have a total capacity of acid functions of from 0.7 to 2.1 mval/ml of ion exchanger when they have a water content of about 75 to 85% by weight or a total capacity of acid functions of from 3.5 to S mval or higher, based on 1 g of dry substance of ion exchanger, are dried and then rinsed with the phenol required for the preparation of the bisphenol and are then neutralized with at least 0.3 mol, preferably with 0.~ to 1 mol of mercapto amines of formula (I) per mol of acid f unction of the ion exchanger at temperatures above the meltin~ point of this phenol.
The present invention also relates to the ion exchangers modified with mercapto amines of formula (I) obtainable by the process according to the invention.
The acid functions of these modified ion exchangers are occupied with the mercapto amine of formula (I) to an extent of at least 30 mol-% and pref~erably 40 to 100 mol-%.
Suitable acid ion exchangers include, for example, the conventional reaction products of styrene-divinyl benzene copolymers with conventional sulphonating agents such as sulphuric acid, chlorosulphonic acid etc. These may be present in spherical form with particle diameters of 0.3 to 1.5 mm. They may be of the gel type or macro-porous. Their total capacity of acid functions ranges from 0.7 to 2.1 mval/ml of ion exchanger when they are moistened with a water content of about 75 to ~5% by weight or from 3.5 to 5 mval or higher, based on 1 g of the dry substance of ion exchanger.
Before the treatment or neutralization with the mercapto amines corresponding to formula (I) which are to be used according to the invention, these ion exchangers are dried, optionally by heat 9 optionally in a vacuum or optionally by washing with hydrophilic organic liquids such as alcohols or phenols or by azeotropic distilla-tion with organic liquids such as toluene, xylene, methylene chloride or others. The ion exchanger resin is then rinsed with the phenol required for the prepara-tion of the bisphenol, and the required quantity of mer-capto amine of formula (I) is then added in this medium at temperatures above the melting point of the phenol with stirring or in a fluidized bed layer.
In the mercapto amines corresponding to formula (I) " ~
.
R \
/ N - R - CH2 - S - H ~I), R denotes a C1-C6-alkylene, C5-C10-cycloalkylene or C6-C1~-arylene group, preferably a methylene group, and R2 and R3, which are independent of one another, denote C1-C6-alkyl groups or, preferably, hydrogen. The follow-ing are suitable mercapto amines corresponding to formula Dimethylmercaptoethylamine, ethyl-cyclohexylmercapto-butylamine, mercaptopropylamine, 1-amino-4-mercaptomethyl-benzene and B-mercaptoethylamine; p-mercaptoethylamine is preferred.
~' The mercapto amines of formula ~I) may be used as such or prepared in situ from thiazolidines such as 2,2-dimethyldiazolidine.
The cation exchanger resin which has been modified by neutralization may be used for the preparation of numerous bisphenols from phenols and carbonyl compounds.
Suitable phenols include those corresponding to formula ; (II) ~ ~ R1 R2 ;- HO ~ H (II) 3 ~ 4 R R
~ 20 wherein ; R1, R2, R3 and R4 denote, independently of one another, hydrogen (H), C1-C4-alkyl or halogen such as F, Cl or Br.
The following are given as examples: 2,6-Dimethyl-phenol, o- and m-cresol, o-sec.butylphenol, o-tert.-butylphenol, 1,3,5-xylenol, 2,6-ditert.-butylphenol, tetramethylphenol, 2-methyl-6-tert.-butylphenol, o-phenyl-phenol, o- and m-chlorophenol, o-bromophenol, 6-chloro-o-cresol and 2,6-dichlorophenol.
Unsubstituted phenol is preferred.
,, .
Suitable carbonyl compounds include those corres-ponding to formula (III) R - C = O (III), wherein R1 and R2 denote, independently of one another, hydrogen (H), Cl-C6-alkyl, C6-C10-cycloalkyl, C6-C14-aryl, C7-C20-aralkyl or C7-C20-alkylaryl or R and R together form a saturated rin~ with 5 to 6 ring atoms, The following are examples of suitable carbonyl com-pounds such as aldehydes and ketones: Formaldehyde, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, cyclohexanone, acetophenone, etc, Acetone is preferred, The process of preparation may be carried out contin-uously or batchwise by methods and with apparatus whichare known in the art, In the batchwise method, 80 to 200 g, preferably 100 to 150 g of dry substance of ion exchanger resin according to the invention are used per mol of carbonyl compound.
The reaction temperature employed for the preparation of the bisphenol is in the region of 40 to 120C and is preferably above the solidification point of the com-ponents.
The reaction time or dwell time is chosen to be sufficiently long for complete conversion of the-carbonyl compound put into the process and is preferably from 30 to 240 minutes.
The present invention accordingly also relates to the use of the ion exchangers modified with mercapto amines of formula (I) obtained by the process according to the invention for the preparation of bisphenols from phenols and carbonyl compounds.
The reaction mixture obtained from the reaction of phenol with carbonyl compound is worked up by the usual .
methods such as distillation, crystallisation, etc.
Thus, for example, the bisphenol prepared may be cooled in the reaction mixture until crystallisation sets in and the phenol may then be removed by distill-ation or extraction from the mixed crystals of bisphenoland phenol which have been filtered off.
The bisphenol prepared by this process is suitable for known fields of application without after-purification and is also suitable for applications in which an excep-tionally high standard of purity is required, such asthe preparation of optically highly pure polycarbonates..
Example 1 Preparation of the modified ion exchanger resin _ The water-moist ion exchanger as obt,ained from the supplier with a moisture content of about 80% by weight and a total capacity of 0.75 mval/ml is washed with distilled water. It is then dried for 24 hours in a water jet vacuum at 90 to 100C to reduce the water content to below 1~ by weight.
The remaining water is distilled off as an azeotropic mixture with toluene and the toluene adhering to the ion exchange resin is then distilled off in a water jet vacuum at 95C.
- 120 g of this pretreated ion exchanger resin are taken up with 1128 g of phenol in a stirrer apparatus and left to swell in the phenol at 65C for 24 hours with exclusion of moisture. The quantity of mercapto ethylamine required for blocking the mol-~ indicated in Examples 2 to 10 is then added with stirring.
Examples 2 - 10 Preparation of bisphenol A (BPA) .
The ion exchanger resin was modified with p-mercapto ethylamine by the process described in Example 1 so that 15 to 100% of ~he sulphonic acid groups were neutra~ed in nine different adjustments. 58 g of acetone were added at 65C to the solution prepared in Example 1 and the purity of the bisphenol and quantity of by~roducts were determined gas chromatographically after complete conversion of the acetone. The results obtained are sum-marized in the following Table in terms of the mean values obtained in each case from 5 experimental examples~
13183:~1 GC surface percentayes Example Mol-% BPA By-products occupied 2 15 93.6 6.4 (comparison) 3 20 93.8 6.2 ~comparison) 4 25 94.3 5.7 (comparison) ~4.5 5.5 6 ~0 94.7 5.3 7 50 95.1 4.9 8 60 95.7 4~3 9 80 96.2 3.~
100 96.7 3.3
Claims (15)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing an anhydrous ion exchanger modified with a mercapto amine, said ion exchanger suitable for preparing a bisphenol from a phenol and a carbonyl compound, which process comprises drying an acid ion exchanger resin having a total capacity of acid functions of from 0.7 to 2.1 mval/ml of ion exchanger in the water-moist form with a water content of about 75 to 85% by weight or a total capacity of acid functions of from 3.5 to 5 mval or higher when based on 1 g of dry substance of ion exchanger, and thereafter rinsing with said phenol and thereafter neutralizing with at least 0.3 mol of a mercapto amine corresponding to formula (I) per mol of acid function of the ion exchanger at a temperature above the melting point of said phenol, (I) in which formula (I), R1 stands for C1-C6-alkylene, C5-C10-cycloalkylene or C6-C14-arylene and R2 and R3 denote, independently of one another, C1-C6-alkyl or hydrogen.
2. A process according to claim 1 wherein R1 is methylene, R2 and R3 are each hydrogen.
3. A process according to claim 1 wherein the compound of formula I is selected from dimethylmercaptoethylamine, ethylcyclohexylmercaptobutylamine, mercaptopropylamine, 1-amino-4-mercaptomethylbenzene and .beta.-mercaptoethylamine.
4. A process according to claim 1 wherein the compound of formula I is .beta.-mercaptoethylamine.
5. A process according to any one of claims 1 to 4 wherein the phenol is a compound of formula II
(II) wherein R1, R2, R3 and R4 denote, independently of one another, hydrogen (H), C1-C4-alkyl or halogen and the carbonyl compound is a compound of formula III
(III), wherein R1 and R2 denote, independently of one another, hydrogen (H), C1-C6-alkyl, C6-C10-cycloalkyl, C6-C14-aryl, C7-C20 aralkyl or C7-C20-alkylaryl or R1 or R2 together form a saturated ring with 5 to 6 ring atoms.
(II) wherein R1, R2, R3 and R4 denote, independently of one another, hydrogen (H), C1-C4-alkyl or halogen and the carbonyl compound is a compound of formula III
(III), wherein R1 and R2 denote, independently of one another, hydrogen (H), C1-C6-alkyl, C6-C10-cycloalkyl, C6-C14-aryl, C7-C20 aralkyl or C7-C20-alkylaryl or R1 or R2 together form a saturated ring with 5 to 6 ring atoms.
6. A process according to any one of claims 1 to 4 wherein the phenol is selected from 2,6-dimethylphenol, o- and m-cresol, o-sec.butylphenol, o-tert.-butylphenol, 1,3,5-xylenol, 2,6-ditert.-butylphenol, tetramethylphenol, 2-methyl-6-tert.-butylphenol, o-phenylphenol, o- and m-chlorophenol, o-bromophenol, 6-chloro-o-cresol and 2,6-dichlorophenol and the carbonyl compound is formaldehyde, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, cyclohexanone, acetophenone or acetone.
7. A process according to any one of claims 1 to 4 wherein the phenol is unsubstituted phenol and the carbonyl compound is acetone.
8. An ion exchanger modified with a mercapto amine obtained according to any one of claims 1 to 4.
9. An ion exchanger modified with a mercapto amine obtained according to any one of claims 1 to 4 wherein the phenol is a compound of formulaII
(II) wherein R1, R2, R3 and R4 denot, independently of one another, hydrogen (H), C1-C4-alkyl or halogen and the compound is a compound of formula III
(III), wherein R1 and R2 denote, independently of one another, hydrogen (H), C1-C6-alkyl, C6-C10-cycloalkyl, C6-C14-aryl, C7-C20 aralkyl or C7-C20-alkylaryl or R1 and R2 together form a saturated ring with 5 to 6 ring atoms.
(II) wherein R1, R2, R3 and R4 denot, independently of one another, hydrogen (H), C1-C4-alkyl or halogen and the compound is a compound of formula III
(III), wherein R1 and R2 denote, independently of one another, hydrogen (H), C1-C6-alkyl, C6-C10-cycloalkyl, C6-C14-aryl, C7-C20 aralkyl or C7-C20-alkylaryl or R1 and R2 together form a saturated ring with 5 to 6 ring atoms.
10. An ion exchanger modified with a mercapto amine obtained according to any one of claims 1 to 4 wherein the phenol is selected from 2,6-dimethylphenol, o- and m-cresol, o-sec.butylphenol, o-tert.-butylphenol, 1,3,5-xylenol, 2,6-ditert.-butylphenol, tetramethylphenol, 2-methyl-6-tert.-butylphenol, o-phenylphenol, o- and m-chlorophenol, o-bromophenol, 6-chloro-o-cresol and 2,6-dichlorophenol and the carbonyl compound is formaldehyde, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, cyclohexanone, acteophenone or acetone.
11. An ion exchanger modified with a mercapto amine obtained according to any one of claims 1 to 4 wherein the phenol is unsubstituted phenol and the carbonyl compound is acetone.
12. A process for preparing a bisphenol comprising contacting a phenol and a carbonyl compound with an anhydrous ion exchanger prepared according to any one of claims 1 to 4.
13. A process according to claim 12 wherein the phenol is a compound of formula II
(II) wherein R1, R2, R3 and R4 denote, independently of one another, hydrogen (H), C1-C4-alkyl or halogen and the carbonyl compound is a compound of formula III
(III), whereln R1 and R2 denote, independently of one another, hydrogen (H), C1-C6-alkyl, C6-C10-cycloalkyl, C6-C14-aryl, C7-C20 aralkyl or C7-C20-alkylaryl or R1 and R2 together form a saturated ring with 5 to 6 ring atoms.
(II) wherein R1, R2, R3 and R4 denote, independently of one another, hydrogen (H), C1-C4-alkyl or halogen and the carbonyl compound is a compound of formula III
(III), whereln R1 and R2 denote, independently of one another, hydrogen (H), C1-C6-alkyl, C6-C10-cycloalkyl, C6-C14-aryl, C7-C20 aralkyl or C7-C20-alkylaryl or R1 and R2 together form a saturated ring with 5 to 6 ring atoms.
14. A process according to claim 12 wherein the phenol is selected from 2,6-dimethylphenol, o- and m-cresol, o-sec.butylphenol, o-tert.-butylphenol, 1,3,5-xylenol, 2,6-dltert.-butylphenol, tetramethylphenol, 2-methyl-6-tert.-butylphenol, o-phenylphenol, o- and m-chlorophenol, o-bromophenol, 6-chloro-o-cresol and 2,6-dichlorophenol and the carbonyl compound is formaldehyde, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, cyclohexanone, acetophenone or acetone.
15. A process according to claim 12 wherein the phenol is unsubstituted phenol and the carbonyl compound is acetone.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19863619450 DE3619450A1 (en) | 1986-06-10 | 1986-06-10 | ION EXCHANGERS MODIFIED WITH MERCAPTOAMINES |
| DEP3619450.6 | 1986-06-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1318331C true CA1318331C (en) | 1993-05-25 |
Family
ID=6302668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000539071A Expired - Fee Related CA1318331C (en) | 1986-06-10 | 1987-06-08 | Ion exchangers modified with mercapto amines |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0249102B1 (en) |
| JP (1) | JP2528469B2 (en) |
| CA (1) | CA1318331C (en) |
| DE (2) | DE3619450A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2630449B1 (en) * | 1988-04-26 | 1992-03-20 | Bp Chimie Sa | NOVEL ADDITION PRODUCT BETWEEN A THIOL AND A POLYBUTENE COMPRISING A DOUBLE CARBON-CARBON BINDING AND PREPARATION METHOD |
| US5780690A (en) * | 1992-04-28 | 1998-07-14 | Bayer Aktiengesellschaft | Bisphenol synthesis on modified ion-exchange resins using specially purified carbonyl compounds |
| DE4213870C2 (en) * | 1992-04-28 | 1996-07-04 | Bayer Ag | Bisphenol synthesis on modified ion exchange resins using specially purified carbonyl compounds |
| DE19539444A1 (en) * | 1995-10-24 | 1997-04-30 | Bayer Ag | Process for the preparation of bisphenols using new cocatalysts |
| DE19638888A1 (en) * | 1996-09-23 | 1998-03-26 | Bayer Ag | Production of cyclic aromatic bis:phenol compounds |
| BR0008481A (en) | 1999-02-26 | 2002-01-22 | Gen Electric | Ion exchange resin bed in combination for the synthesis of bisphenol-a |
| JP4723105B2 (en) | 2001-03-01 | 2011-07-13 | 出光興産株式会社 | Method for producing bisphenol A |
| US6703530B2 (en) | 2002-02-28 | 2004-03-09 | General Electric Company | Chemical reactor system and process |
| US7112702B2 (en) * | 2002-12-12 | 2006-09-26 | General Electric Company | Process for the synthesis of bisphenol |
| ES2432042T3 (en) * | 2004-07-02 | 2013-11-29 | Mitsui Chemicals, Inc. | Modified ion exchange resin and procedure to produce bisphenols |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3394089A (en) * | 1964-12-02 | 1968-07-23 | Dow Chemical Co | Ion exchange catalyst for the preparation of bisphenols |
| GB1539184A (en) * | 1975-08-01 | 1979-01-31 | Shell Int Research | Cation-exchange resins |
| GB1539463A (en) * | 1976-07-26 | 1979-01-31 | Shell Int Research | Preparation of a fixed bed catalyst |
| DE2931036A1 (en) * | 1979-07-31 | 1981-02-26 | Bayer Ag | CATALYST FOR THE PRODUCTION OF BISPHENOLS |
| US4346247A (en) * | 1979-12-13 | 1982-08-24 | General Electric Company | Method and catalyst for making bisphenol |
| US4595704A (en) * | 1984-08-13 | 1986-06-17 | The Dow Chemical Company | Preparation of ion-exchange catalysts |
-
1986
- 1986-06-10 DE DE19863619450 patent/DE3619450A1/en not_active Withdrawn
-
1987
- 1987-05-29 EP EP87107785A patent/EP0249102B1/en not_active Expired
- 1987-05-29 DE DE8787107785T patent/DE3760941D1/en not_active Expired
- 1987-06-08 CA CA000539071A patent/CA1318331C/en not_active Expired - Fee Related
- 1987-06-10 JP JP62143418A patent/JP2528469B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0249102A2 (en) | 1987-12-16 |
| DE3760941D1 (en) | 1989-12-14 |
| EP0249102A3 (en) | 1988-06-08 |
| EP0249102B1 (en) | 1989-11-08 |
| DE3619450A1 (en) | 1987-12-17 |
| JP2528469B2 (en) | 1996-08-28 |
| JPS62298454A (en) | 1987-12-25 |
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