US20020045726A1 - Process for the removal of dissolved oxygen from phenol - Google Patents
Process for the removal of dissolved oxygen from phenol Download PDFInfo
- Publication number
- US20020045726A1 US20020045726A1 US09/777,152 US77715201A US2002045726A1 US 20020045726 A1 US20020045726 A1 US 20020045726A1 US 77715201 A US77715201 A US 77715201A US 2002045726 A1 US2002045726 A1 US 2002045726A1
- Authority
- US
- United States
- Prior art keywords
- phenol
- platinum
- ion exchanger
- oxygen
- process according
- 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.)
- Granted
Links
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 18
- 239000001301 oxygen Substances 0.000 title claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000004417 polycarbonate Substances 0.000 claims abstract description 9
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 31
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 23
- 150000001450 anions Chemical group 0.000 claims description 20
- 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 description 18
- 150000002500 ions Chemical class 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000012458 free base Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 2
- 239000011369 resultant mixture Substances 0.000 claims 1
- 238000002845 discoloration Methods 0.000 abstract description 7
- -1 platinum group metals Chemical class 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 229940100198 alkylating agent Drugs 0.000 description 7
- 239000002168 alkylating agent Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229920006037 cross link polymer Polymers 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- JKGLRGGCGUQNEX-UHFFFAOYSA-N 2-(chloromethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCl)C(=O)C2=C1 JKGLRGGCGUQNEX-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- LBQJCDLKJGOHEA-UHFFFAOYSA-N 2-ethenylbut-3-enylbenzene Chemical compound C=CC(C=C)CC1=CC=CC=C1 LBQJCDLKJGOHEA-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 208000034874 Product colour issue Diseases 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical class 0.000 description 2
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 150000008050 dialkyl sulfates Chemical class 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- KTRQRAQRHBLCSQ-UHFFFAOYSA-N 1,2,4-tris(ethenyl)cyclohexane Chemical compound C=CC1CCC(C=C)C(C=C)C1 KTRQRAQRHBLCSQ-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- ZXHDVRATSGZISC-UHFFFAOYSA-N 1,2-bis(ethenoxy)ethane Chemical group C=COCCOC=C ZXHDVRATSGZISC-UHFFFAOYSA-N 0.000 description 1
- ZJQIXGGEADDPQB-UHFFFAOYSA-N 1,2-bis(ethenyl)-3,4-dimethylbenzene Chemical group CC1=CC=C(C=C)C(C=C)=C1C ZJQIXGGEADDPQB-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- NCXUNZWLEYGQAH-UHFFFAOYSA-N 1-(dimethylamino)propan-2-ol Chemical compound CC(O)CN(C)C NCXUNZWLEYGQAH-UHFFFAOYSA-N 0.000 description 1
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- DSAYAFZWRDYBQY-UHFFFAOYSA-N 2,5-dimethylhexa-1,5-diene Chemical compound CC(=C)CCC(C)=C DSAYAFZWRDYBQY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 230000010849 Ion Exchange Activity Effects 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910003244 Na2PdCl4 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 238000005902 aminomethylation reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229940045713 antineoplastic alkylating drug ethylene imines Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 1
- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 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
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 150000003956 methylamines Chemical group 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- AYGYHGXUJBFUJU-UHFFFAOYSA-N n-[2-(prop-2-enoylamino)ethyl]prop-2-enamide Chemical compound C=CC(=O)NCCNC(=O)C=C AYGYHGXUJBFUJU-UHFFFAOYSA-N 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical class CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical class C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
-
- 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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/86—Purification; separation; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification
-
- 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
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
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- 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
Definitions
- the invention relates to a process for the removal of dissolved oxygen from phenol by admixing water into the phenol, which is then passed over metals of the platinum group applied to supports in order to catalyze the reaction of hydrogen and oxygen to give water in accordance with the equation: 2H 2 +O 2 ⁇ 2H 2 O.
- the invention further relates to polycarbonate and bisphenol A that are prepared from oxygen-free phenol prepared by admixing water and subsequently passing the mixture over ion exchangers doped with platinum metal.
- Phenol is an important unit in the preparation of the plastic polycarbonate. Phenol is first reacted with acetone under acid conditions to give bisphenol A. The molar ratio of the reactants phenol:acetone here is in the range of 8:1 to 14:1, preferably in the region of 12:1. Bisphenol A is then reacted with either phosgene or diphenyl carbonate to give polycarbonate in the following step.
- This plastic is employed in a very wide-ranging spectrum of uses, inter alia in very demanding fields, such as in the preparation of high-quality optical materials and of compact discs and in the electronics field.
- the present invention relates to a process for the catalytic removal of dissolved oxygen from phenol comprising
- the platinum metals to be used according to the invention are the elements of the series ruthenium, rhodium, palladium, osmium, iridium, and platinum. Palladium and platinum are preferred for the process according to the invention.
- the ion exchangers to be used according to the invention are preferably anion exchangers and can contain weakly and/or strongly basic groups. Strongly basic anion exchangers in the Cl form or weakly basic anion exchangers in the free base form are particularly preferred.
- a crosslinked polymer of ethylenically unsaturated monomers is used as the base polymer.
- ethylenically monounsaturated monomers are, for example, styrene, vinyltoluene, ethylstyrene, ⁇ -methylstyrene, and derivatives thereof halogenated in the nucleus (such as chlorostyrene), vinylbenzyl chloride, acrylic acid and its salts and esters (particularly the methyl and ethyl esters), methacrylic acid and its salts and esters (particularly the methyl ester), and the nitriles and amides of acrylic and methacrylic acid.
- the polymers are crosslinked, preferably by copolymerization with crosslinking monomers having more than one (preferably 2 or 3) copolymerizable C ⁇ C double bonds per molecule.
- crosslinking monomers include, for example, polyfunctional vinylaromatics, such as di- or trivinylbenzenes, divinylethylbenzene, divinyltoluene, divinylxylene, divinylethylbenzene, or divinylnaphthalene; polyfunctional allylaromatics, such as di- or triallylbenzenes; polyfunctional vinyl- or allyl-heterocyclic compounds, such as trivinyl or triallyl cyanurate or trivinyl or triallyl isocyanurate; N,N′-C 1 -C 6 -alkylenediacrylamides or -dimethacrylamides, such as N,N′-methylenediacrylamide or -dimethacrylamide or N,N′-ethylened
- Divinylbenzene (as an isomer mixture) and mixtures of divinylbenzene and aliphatic C 6 -C 12 -hydrocarbons having 2 or 3 C ⁇ C double bonds have proved to be particularly suitable crosslinking monomers.
- the crosslinking monomers are in general employed in amounts of 2 to 20% by weight, preferably 2 to 12% by weight, based on the total amount of polymerizable monomers employed.
- crosslinking monomers do not have to be employed in pure form but can also be employed in the form of their technical grade mixtures of lower purity (such as, for example, divinylbenzene mixed with ethylstyrene).
- the crosslinked polymers can be further processed to give anion exchangers in a known manner.
- the anion exchangers can be prepared on the one hand by chloromethylation (cf. U.S. Pat. Nos. 2,642,417, 2,960,480, 2,597,492, 2,597,493, 3,311,602, and 2,616,877), preferably with chloromethyl ether, and subsequent amination (cf. U.S. Pat. Nos.
- a primary amine such as methyl- or ethylamine
- a secondary amine such as dimethylamine
- a tertiary amine such as trimethylamine or dimethylisopropanolamine
- the anion exchangers can be prepared by the aminomethylation process, in which (a) the crosslinked polymers are reacted with phthalimide derivatives and (b) the resulting imides are hydrated.
- the amidomethylation (a) can be carried out by reaction of the crosslinked polymers with N-chloromethyl-phthalimide in the presence of swelling agents for crosslinked polymers and Friedel-Crafts catalysts (DE-A 1,054,715), the phthalimile derivative being employed in amounts suitable for the desired level of substitution (0.3 to 2.0 substitutions per aromatic nucleus) of the aromatic nuclei present in the crosslinked polymer (or in an excess of up to 20%, preferably up to 10%).
- Suitable swelling agents include halogenated hydrocarbons, preferably chlorinated C 1 -C 4 -hydrocarbons.
- the most preferred swelling agent is 1,2-dichloroethane.
- Preferred Friedel-Crafts catalysts include, for example, AlCl 3 , BF 3 , FeCl 3 , ZnCl 2 , TiCl 4 , ZrCl 4 , SnCl 4 , H 3 PO 4 , HF, and HBF 4 .
- the catalysts can be employed in amounts of 0.01 to 0.1 mol per mole of N-chloromethylphthalimide.
- the reaction can be carried out, for example, by a procedure in which the crosslinked polymer is introduced into a solution of N-chloromethylphthalimide in a swelling agent and the reactants are allowed to act in the presence of the catalyst at elevated temperature, as a rule at 50 to 100° C., preferably 50 to 75° C., until the evolution of hydrogen chloride has substantially ended. This is in general the case after 2 to 20 hours. After separation of the substituted polymer and liquid reaction medium and inorganic products, it is advisable to take up the polymer in aqueous sodium chloride solution and to remove residues of swelling agent by distillation.
- the hydrolysis (b) of the substituted polymer can be carried out, for example, by subsequently hydrolyzing the product that has been isolated with an approximately 5 to 40% strength by weight aqueous or alcoholic solution of an alkali, such as sodium hydroxide or potassium hydroxide, or with an approximately 5 to 50% strength by weight aqueous solution of a mineral acid, such as hydrochloric acid, hydrobromic acid, or sulfuric acid, in an autoclave at temperatures between 100 and 250° C.
- the intermediate product can also be reacted with a 5 to 50% strength by weight aqueous or alcoholic solution of hydrazine hydrate at temperatures of 50 to 100° C.
- the solution described last can contain other alkalis, in particular caustic alkalis, in amounts of 1 to 20% by weight.
- the reaction product can be isolated, washed with water and then heated with an aqueous solution of mineral acid (preferably 5 to 20% strength by weight) to bring the hydrolysis to completion.
- the aminoalkyl compounds that can be obtained can be modified by alkylation.
- Known alkylating agents such as, for example, methyl, ethyl, or propyl chlorides and bromides, dialkyl sulfates, alkylene oxides, halogenohydrins, polyhalogen compounds, epihalohydrins, and ethyleneimines, can be used for this purpose.
- alkylation of the said amino derivatives can be effected by reaction thereof with alkylating agents in molar amounts at temperatures of between 20 and 125° C. If, for example, alkyl halides or dialkyl sulfates are used, it is advisable to add the amount of an alkaline agent, such as sodium hydroxide, calcium carbonate, magnesium oxide, and the like, required for neutralization of the hydrogen halide acids or alkylsulfuric acids formed. Secondary, tertiary, or quaternary amino derivatives or mixtures thereof are obtained depending on the amount of alkylating agent used.
- alkylating agents such as sodium hydroxide, calcium carbonate, magnesium oxide, and the like
- a mixture of formaldehyde with formic acid is another customary alkylating agent which is used in the form of an aqueous solution, if appropriate in the presence of mineral acids.
- the reaction can be carried out with these alkylating agents at temperatures of between 50 and 120° C.
- tertiary amino derivatives are obtained as the sole reaction products if an excess of alkylating agent is used.
- the tertiary amino derivatives can be converted completely or partly into quaternary derivatives by carrying out a further reaction with alkylating agents, such as, for example, methyl chloride, at temperatures of between 10 and 120° C.
- the anion exchangers used can be in gel form or, preferably, macroporous; those based on polystyrene are preferred. Strongly basic anion exchangers in the Cl form and weakly basic anion exchangers in the free base form are particularly preferred.
- Doping of the anion exchangers with platinum metals can be carried out, for example, by a procedure in which the platinum metal, preferably platinum or palladium, in a suitable salt form is taken up by the groups with ion exchange activity and is then reduced, or reducing substances are first applied and the platinum metal, preferably platinum or palladium, is then precipitated on the resin from a suitable solution. Finally, colloidally dispersed platinum metal that has already been reduced, preferably platinum or palladium, can also be taken up adsorptively by the resin from a corresponding solution or suspension.
- the application process which is particularly preferred in the present invention starts from the salt form of the resin, which is first treated with a palladium salt solution (for example, 2 to 20% strength by weight Na 2 PdCl 4 ), the anion on the resin being exchanged for the anionic palladium complex.
- a palladium salt solution for example, 2 to 20% strength by weight Na 2 PdCl 4
- the palladium complex is chiefly distributed in the surface region of the resin grain, so that the regions which are distinguished by rapid kinetics are affected above all.
- the reduction of the noble metal bonded ionogenically to the resin for example, of palladium to metallic palladium, can be carried out by reducing agents that are usual for this type of reduction, such as hydrazine, hydroxylamine, hydrogen, ascorbic acid, formalin, or formic acid, in strongly alkaline solution at elevated temperature. Hydrazine or formalin is preferably used.
- the noble metal content, preferably of platinum metal, of the ion exchangers to be used according to the invention is in general in the range from 0.3 to 10 g, preferably 0.5 to 1.2 g, per liter of anion exchanger.
- DE-A 25 24 722 discloses the use of polystyrenes containing copper ions or cobalt ions for reduction of oxygen dissolved in water.
- U.S. Pat. No. 4,789,488 recommends palladium- or platinum-doped anion exchangers for decreasing the oxygen content in aqueous systems with hydrogen.
- other reducing agents such as, for example, hydrazine
- the use of metal-doped anion exchangers for simultaneous removal of oxygen and undesirable ions has also already been discussed.
- the system pressure of the bisphenol A production was in the range of 3-10 bar at an oxygen feed concentration of 0.1 mg/l to 2 mg/l.
- the hydrogen-containing stream of phenol was passed through a reactor upstream of the bisphenol A production which was filled with a palladized weakly basic anion exchanger (0.5 m 3 Lewatit® catalyst K3433, manufacturer Bayer AG).
- the height of the resin was 0.5 mm, the specific load was 20 bed volumes/hour and the pressure loss was in the range of 0.08-0.2 bar.
- the oxygen concentration measured in the discharge of the catalyst bed was only 0.01 to 0.03 mg/l.
- the product discoloration index of the bisphenol A was 13 to 17 Hazen melt color index.
- the “Yellowness Index” of the polycarbonate changes accordingly from ⁇ 1.7 with phenol treated by the process according to the invention to ⁇ 1.7 without the treatment according to the invention.
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Abstract
The present invention relates to a method for avoiding undesirable discoloration in polycarbonate production by catalytic removal of dissolved oxygen from phenol by
(a) admixing hydrogen with phenol and
(b) passing the phenol stream over ion exchangers doped with platinum group metals.
Description
- The invention relates to a process for the removal of dissolved oxygen from phenol by admixing water into the phenol, which is then passed over metals of the platinum group applied to supports in order to catalyze the reaction of hydrogen and oxygen to give water in accordance with the equation: 2H2+O2→2H2O. The invention further relates to polycarbonate and bisphenol A that are prepared from oxygen-free phenol prepared by admixing water and subsequently passing the mixture over ion exchangers doped with platinum metal.
- Phenol is an important unit in the preparation of the plastic polycarbonate. Phenol is first reacted with acetone under acid conditions to give bisphenol A. The molar ratio of the reactants phenol:acetone here is in the range of 8:1 to 14:1, preferably in the region of 12:1. Bisphenol A is then reacted with either phosgene or diphenyl carbonate to give polycarbonate in the following step.
- This plastic is employed in a very wide-ranging spectrum of uses, inter alia in very demanding fields, such as in the preparation of high-quality optical materials and of compact discs and in the electronics field.
- However, discoloration of the plastics often prevent their use in these applications, even when a very great effort is made to keep the quality of the starting substances at a high level.
- It has now been found, surprisingly, that discoloration can be virtually completely avoided if hydrogen is added to the phenol and the mixture is then passed over a support, preferably an ion exchanger, doped with at least one metal of the platinum group.
- How the discoloration arises has not yet been clarified in detail. At the moment, however, it is assumed that discoloration is caused by the nonselective action of oxygen present in the starting substances.
- The use of anion exchangers doped with noble metals of the platinum group as catalysts for the catalytic removal of oxygen from water, for example, for use in the generation of steam, has been known for a relatively long time and is already practiced worldwide. See JP-A 58/079,590 and CN-A 1,098,384. In this process, hydrogen is fed stoichiometrically to the water in such way that the oxygen present is reacted away virtually quantitatively. Residual oxygen values of less than 0.1% of the feed value are obtainable in this manner.
- The present invention relates to a process for the catalytic removal of dissolved oxygen from phenol comprising
- (a) admixing hydrogen with phenol and
- (b) passing the phenol stream over ion exchangers doped with platinum group metals to catalyze the reaction 2H2+O2→2H2O.
- The platinum metals to be used according to the invention are the elements of the series ruthenium, rhodium, palladium, osmium, iridium, and platinum. Palladium and platinum are preferred for the process according to the invention.
- The ion exchangers to be used according to the invention are preferably anion exchangers and can contain weakly and/or strongly basic groups. Strongly basic anion exchangers in the Cl form or weakly basic anion exchangers in the free base form are particularly preferred. A crosslinked polymer of ethylenically unsaturated monomers is used as the base polymer. Examples of ethylenically monounsaturated monomers are, for example, styrene, vinyltoluene, ethylstyrene, α-methylstyrene, and derivatives thereof halogenated in the nucleus (such as chlorostyrene), vinylbenzyl chloride, acrylic acid and its salts and esters (particularly the methyl and ethyl esters), methacrylic acid and its salts and esters (particularly the methyl ester), and the nitriles and amides of acrylic and methacrylic acid.
- The polymers are crosslinked, preferably by copolymerization with crosslinking monomers having more than one (preferably 2 or 3) copolymerizable C═C double bonds per molecule. Such crosslinking monomers include, for example, polyfunctional vinylaromatics, such as di- or trivinylbenzenes, divinylethylbenzene, divinyltoluene, divinylxylene, divinylethylbenzene, or divinylnaphthalene; polyfunctional allylaromatics, such as di- or triallylbenzenes; polyfunctional vinyl- or allyl-heterocyclic compounds, such as trivinyl or triallyl cyanurate or trivinyl or triallyl isocyanurate; N,N′-C1-C6-alkylenediacrylamides or -dimethacrylamides, such as N,N′-methylenediacrylamide or -dimethacrylamide or N,N′-ethylenediacrylamide or -dimethacrylamide; polyvinyl or polyallyl ethers of saturated C2-C20-polyols having 2 to 4 OH groups per molecule, such as, for example, ethylene glycol divinyl or diallyl ether or diethylene glycol divinyl or diallyl ethers; esters of unsaturated C3-C12-alcohols or saturated C2-C20-polyols having 2 to 4 OH groups per molecule, such as allyl methacrylate, ethylene glycol di(meth)acrylate, glycerol tri(meth)acrylate, or pentaerythritol tetra(meth)acrylate; divinylethyleneurea, divinylpro-pyleneurea or divinyl adipate; or aliphatic or cycloaliphatic olefins having 2 or 3 isolated C═C double bonds, such as hexa-1,5-diene, 2,5-dimethylhexa-1,5-diene, octa-1,7-diene, or 1,2,4-trivinylcyclohexane. Divinylbenzene (as an isomer mixture) and mixtures of divinylbenzene and aliphatic C6-C12-hydrocarbons having 2 or 3 C═C double bonds have proved to be particularly suitable crosslinking monomers. The crosslinking monomers are in general employed in amounts of 2 to 20% by weight, preferably 2 to 12% by weight, based on the total amount of polymerizable monomers employed.
- The crosslinking monomers do not have to be employed in pure form but can also be employed in the form of their technical grade mixtures of lower purity (such as, for example, divinylbenzene mixed with ethylstyrene).
- The crosslinked polymers can be further processed to give anion exchangers in a known manner. The anion exchangers can be prepared on the one hand by chloromethylation (cf. U.S. Pat. Nos. 2,642,417, 2,960,480, 2,597,492, 2,597,493, 3,311,602, and 2,616,877), preferably with chloromethyl ether, and subsequent amination (cf. U.S. Pat. Nos. 2,632,000, 2,616,877, 2,642,417, 2,632,001, and 2,992,544) with ammonia, a primary amine, such as methyl- or ethylamine, a secondary amine, such as dimethylamine, or a tertiary amine, such as trimethylamine or dimethylisopropanolamine, at a temperature of as a rule 25 to 150° C.
- On the other hand, the anion exchangers can be prepared by the aminomethylation process, in which (a) the crosslinked polymers are reacted with phthalimide derivatives and (b) the resulting imides are hydrated. The amidomethylation (a) can be carried out by reaction of the crosslinked polymers with N-chloromethyl-phthalimide in the presence of swelling agents for crosslinked polymers and Friedel-Crafts catalysts (DE-A 1,054,715), the phthalimile derivative being employed in amounts suitable for the desired level of substitution (0.3 to 2.0 substitutions per aromatic nucleus) of the aromatic nuclei present in the crosslinked polymer (or in an excess of up to 20%, preferably up to 10%).
- Suitable swelling agents include halogenated hydrocarbons, preferably chlorinated C1-C4-hydrocarbons. The most preferred swelling agent is 1,2-dichloroethane.
- Preferred Friedel-Crafts catalysts include, for example, AlCl3, BF3, FeCl3, ZnCl2, TiCl4, ZrCl4, SnCl4, H3PO4, HF, and HBF4. The catalysts can be employed in amounts of 0.01 to 0.1 mol per mole of N-chloromethylphthalimide.
- The reaction can be carried out, for example, by a procedure in which the crosslinked polymer is introduced into a solution of N-chloromethylphthalimide in a swelling agent and the reactants are allowed to act in the presence of the catalyst at elevated temperature, as a rule at 50 to 100° C., preferably 50 to 75° C., until the evolution of hydrogen chloride has substantially ended. This is in general the case after 2 to 20 hours. After separation of the substituted polymer and liquid reaction medium and inorganic products, it is advisable to take up the polymer in aqueous sodium chloride solution and to remove residues of swelling agent by distillation.
- The hydrolysis (b) of the substituted polymer can be carried out, for example, by subsequently hydrolyzing the product that has been isolated with an approximately 5 to 40% strength by weight aqueous or alcoholic solution of an alkali, such as sodium hydroxide or potassium hydroxide, or with an approximately 5 to 50% strength by weight aqueous solution of a mineral acid, such as hydrochloric acid, hydrobromic acid, or sulfuric acid, in an autoclave at temperatures between 100 and 250° C. On the other hand, the intermediate product can also be reacted with a 5 to 50% strength by weight aqueous or alcoholic solution of hydrazine hydrate at temperatures of 50 to 100° C. In a preferred embodiment, the solution described last can contain other alkalis, in particular caustic alkalis, in amounts of 1 to 20% by weight. The reaction product can be isolated, washed with water and then heated with an aqueous solution of mineral acid (preferably 5 to 20% strength by weight) to bring the hydrolysis to completion.
- The aminoalkyl compounds that can be obtained can be modified by alkylation. Known alkylating agents, such as, for example, methyl, ethyl, or propyl chlorides and bromides, dialkyl sulfates, alkylene oxides, halogenohydrins, polyhalogen compounds, epihalohydrins, and ethyleneimines, can be used for this purpose.
- The above-mentioned alkylation of the said amino derivatives can be effected by reaction thereof with alkylating agents in molar amounts at temperatures of between 20 and 125° C. If, for example, alkyl halides or dialkyl sulfates are used, it is advisable to add the amount of an alkaline agent, such as sodium hydroxide, calcium carbonate, magnesium oxide, and the like, required for neutralization of the hydrogen halide acids or alkylsulfuric acids formed. Secondary, tertiary, or quaternary amino derivatives or mixtures thereof are obtained depending on the amount of alkylating agent used. A mixture of formaldehyde with formic acid is another customary alkylating agent which is used in the form of an aqueous solution, if appropriate in the presence of mineral acids. The reaction can be carried out with these alkylating agents at temperatures of between 50 and 120° C. In the latter case, tertiary amino derivatives are obtained as the sole reaction products if an excess of alkylating agent is used. The tertiary amino derivatives can be converted completely or partly into quaternary derivatives by carrying out a further reaction with alkylating agents, such as, for example, methyl chloride, at temperatures of between 10 and 120° C.
- The anion exchangers used can be in gel form or, preferably, macroporous; those based on polystyrene are preferred. Strongly basic anion exchangers in the Cl form and weakly basic anion exchangers in the free base form are particularly preferred.
- Doping of the anion exchangers with platinum metals, preferably platinum or palladium, can be carried out, for example, by a procedure in which the platinum metal, preferably platinum or palladium, in a suitable salt form is taken up by the groups with ion exchange activity and is then reduced, or reducing substances are first applied and the platinum metal, preferably platinum or palladium, is then precipitated on the resin from a suitable solution. Finally, colloidally dispersed platinum metal that has already been reduced, preferably platinum or palladium, can also be taken up adsorptively by the resin from a corresponding solution or suspension.
- The application process which is particularly preferred in the present invention starts from the salt form of the resin, which is first treated with a palladium salt solution (for example, 2 to 20% strength by weight Na2PdCl4), the anion on the resin being exchanged for the anionic palladium complex. The palladium complex is chiefly distributed in the surface region of the resin grain, so that the regions which are distinguished by rapid kinetics are affected above all.
- The reduction of the noble metal bonded ionogenically to the resin, for example, of palladium to metallic palladium, can be carried out by reducing agents that are usual for this type of reduction, such as hydrazine, hydroxylamine, hydrogen, ascorbic acid, formalin, or formic acid, in strongly alkaline solution at elevated temperature. Hydrazine or formalin is preferably used.
- The noble metal content, preferably of platinum metal, of the ion exchangers to be used according to the invention is in general in the range from 0.3 to 10 g, preferably 0.5 to 1.2 g, per liter of anion exchanger.
- DE-A 25 24 722 discloses the use of polystyrenes containing copper ions or cobalt ions for reduction of oxygen dissolved in water. U.S. Pat. No. 4,789,488 recommends palladium- or platinum-doped anion exchangers for decreasing the oxygen content in aqueous systems with hydrogen. In addition to hydrogen, other reducing agents, such as, for example, hydrazine, have also already been described for removal of oxygen from water. Cf. F. Martinola et al., VGB Kraftwerkstechnik 64 (1984), pages61-63. The use of metal-doped anion exchangers for simultaneous removal of oxygen and undesirable ions has also already been discussed. Cf. F. Martinola, loc. cit.
- It has now been found that this process is very effective in avoiding discoloration in polycarbonate production by catalytic reduction of oxygen. The theory described above that the discoloration is to be attributed to traces of oxygen is thereby substantiated. Since phenol not only is the main component of the polycarbonate but is also present in a large excess in the preparation of bisphenol A and is at the start of the production sequence it is appropriate to use this process on this starting material.
- Hydrogen at a rate of 50 to 100 l/hour was fed into a phenol stream having a 10 m3/hour feed rate in a reactor for the preparation of bisphenol A. The temperature of the phenol was 50° C. to 80° C.
- The system pressure of the bisphenol A production was in the range of 3-10 bar at an oxygen feed concentration of 0.1 mg/l to 2 mg/l. The hydrogen-containing stream of phenol was passed through a reactor upstream of the bisphenol A production which was filled with a palladized weakly basic anion exchanger (0.5 m3 Lewatit® catalyst K3433, manufacturer Bayer AG).
- The height of the resin was 0.5 mm, the specific load was 20 bed volumes/hour and the pressure loss was in the range of 0.08-0.2 bar.
- The oxygen concentration measured in the discharge of the catalyst bed was only 0.01 to 0.03 mg/l.
- In this procedure, the product discoloration index of the bisphenol A was 13 to 17 Hazen melt color index.
- If the hydrogen feed was stopped and the stream of phenol and the catalyst were bypassed, the product discoloration index of the bisphenol A rose to >17 Hazen melt color index.
- The “Yellowness Index” of the polycarbonate changes accordingly from ≦1.7 with phenol treated by the process according to the invention to ≧1.7 without the treatment according to the invention.
Claims (12)
1. A process for the catalytic removal of dissolved oxygen from phenol comprising
(a) admixing hydrogen with phenol and
(b) passing the phenol stream over an ion exchanger doped with a platinum group metal to catalyze the reaction 2H2+O2→2H2O2O.
2. A process according to claim 1 wherein the platinum group metal is an element selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, and platinum.
3. A process according to claim 1 wherein the platinum group metal is platinum or palladium.
4. A process according to claim 1 wherein the ion exchanger is an anion exchanger with weakly and/or strongly basic groups.
5. A process according to claim 4 wherein the anion exchanger is a strongly basic anion exchanger in the Cl form or a weakly basic anion exchanger in the free base form.
6. A process according to claim 1 wherein the ion exchanger is a gel form or macroporous ion exchanger.
7. A process according to claim 1 wherein the ion exchanger contains 0.3 to 10 g of platinum metal per liter of ion exchanger.
8. A process for the preparation of oxygen-free phenol comprising adding hydrogen to the phenol and passing the resultant mixture over an ion exchanger doped with a platinum group metal.
9. A method for preparing bispenol A comprising reacting acetone under acidic conditions with phenol prepared by the process of claim 1 .
10. A method for preparing a polycarbonate comprising reacting phosgene or diphenyl carbonate with bispenol A prepared by reacting acetone under acidic conditions with phenol prepared by the process of claim 1 .
11. Bisphenol A prepared from oxygen-free phenol obtained by the process of claim 1 .
12. A polycarbonate prepared from oxygen-free phenol obtained by the process of claim 1.
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DE10005770.5 | 2000-02-10 |
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US9217540B2 (en) | 2012-02-23 | 2015-12-22 | Organo Corporation | Device and method for removing dissolved oxygen in alcohol, alcohol supply apparatus and rinsing liquid supply apparatus |
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DE102004017983A1 (en) | 2004-04-14 | 2005-11-03 | Degussa Ag | Catalytic removal of dissolved oxygen from organic liquids |
SA113340468B1 (en) * | 2012-04-13 | 2015-07-07 | ميتسوي كيميكالز، انك. | Phenol purification process |
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-
2000
- 2000-02-10 DE DE10005770A patent/DE10005770A1/en not_active Withdrawn
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2001
- 2001-01-12 ZA ZA200100359A patent/ZA200100359B/en unknown
- 2001-01-29 EP EP01101656A patent/EP1123912B1/en not_active Expired - Lifetime
- 2001-01-29 DE DE50100505T patent/DE50100505D1/en not_active Expired - Fee Related
- 2001-01-29 ES ES01101656T patent/ES2204757T3/en not_active Expired - Lifetime
- 2001-02-02 JP JP2001026694A patent/JP2001278826A/en active Pending
- 2001-02-05 US US09/777,152 patent/US6417318B1/en not_active Expired - Fee Related
- 2001-02-07 CA CA002334473A patent/CA2334473A1/en not_active Abandoned
- 2001-02-08 TW TW90102699A patent/TW575549B/en active
- 2001-02-09 BR BR0100479-4A patent/BR0100479A/en not_active IP Right Cessation
- 2001-02-09 KR KR1020010006414A patent/KR20010080868A/en not_active Application Discontinuation
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US9217540B2 (en) | 2012-02-23 | 2015-12-22 | Organo Corporation | Device and method for removing dissolved oxygen in alcohol, alcohol supply apparatus and rinsing liquid supply apparatus |
Also Published As
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US6417318B1 (en) | 2002-07-09 |
DE10005770A1 (en) | 2001-08-16 |
TW575549B (en) | 2004-02-11 |
ES2204757T3 (en) | 2004-05-01 |
BR0100479A (en) | 2001-10-02 |
JP2001278826A (en) | 2001-10-10 |
KR20010080868A (en) | 2001-08-25 |
MXPA01001532A (en) | 2002-08-06 |
ZA200100359B (en) | 2001-08-10 |
EP1123912A1 (en) | 2001-08-16 |
DE50100505D1 (en) | 2003-09-25 |
CA2334473A1 (en) | 2001-08-10 |
EP1123912B1 (en) | 2003-08-20 |
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