TWI746688B - 製造三芳基有機硼酸鹽之方法 - Google Patents
製造三芳基有機硼酸鹽之方法 Download PDFInfo
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- TWI746688B TWI746688B TW106138383A TW106138383A TWI746688B TW I746688 B TWI746688 B TW I746688B TW 106138383 A TW106138383 A TW 106138383A TW 106138383 A TW106138383 A TW 106138383A TW I746688 B TWI746688 B TW I746688B
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000000203 mixture Substances 0.000 claims abstract description 17
- -1 trifluoromethoxy, phenyl Chemical group 0.000 claims description 55
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 150000002892 organic cations Chemical class 0.000 claims description 16
- 150000002367 halogens Chemical group 0.000 claims description 15
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052736 halogen Chemical group 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 150000004795 grignard reagents Chemical class 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 239000011877 solvent mixture Substances 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000007818 Grignard reagent Substances 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 125000002619 bicyclic group Chemical group 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 125000001979 organolithium group Chemical group 0.000 claims description 4
- 125000002524 organometallic group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017435 S2 In Inorganic materials 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 150000002896 organic halogen compounds Chemical class 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical group FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims 2
- 150000004703 alkoxides Chemical class 0.000 claims 1
- 150000007942 carboxylates Chemical class 0.000 claims 1
- 239000003999 initiator Substances 0.000 abstract description 12
- 150000002148 esters Chemical class 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000006384 oligomerization reaction Methods 0.000 description 12
- 150000004010 onium ions Chemical class 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- LIFMTDJMLRECMX-UHFFFAOYSA-N 4-bromo-2-chloro-1-methylbenzene Chemical compound CC1=CC=C(Br)C=C1Cl LIFMTDJMLRECMX-UHFFFAOYSA-N 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001408 amides Chemical group 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 239000011630 iodine Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 241000208340 Araliaceae Species 0.000 description 5
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 5
- 235000003140 Panax quinquefolius Nutrition 0.000 description 5
- 150000002170 ethers Chemical group 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 235000008434 ginseng Nutrition 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 5
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- JPBGLQJDCUZXEF-UHFFFAOYSA-N chromenylium Chemical compound [O+]1=CC=CC2=CC=CC=C21 JPBGLQJDCUZXEF-UHFFFAOYSA-N 0.000 description 3
- PGSRDLGPKTVELT-UHFFFAOYSA-N dibromoborane methylsulfanylmethane Chemical compound CSC.BrBBr PGSRDLGPKTVELT-UHFFFAOYSA-N 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 238000010653 organometallic reaction Methods 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 3
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical class C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 3
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- 241001550224 Apha Species 0.000 description 2
- XPEUGQIPWJTDMH-UHFFFAOYSA-N CC1=CC=C(CCCCCCOB(O)O)C=C1Cl Chemical compound CC1=CC=C(CCCCCCOB(O)O)C=C1Cl XPEUGQIPWJTDMH-UHFFFAOYSA-N 0.000 description 2
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KYIMHWNKQXQBDG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC Chemical compound N=C=O.N=C=O.CCCCCC KYIMHWNKQXQBDG-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-O hydron;pyrimidine Chemical compound C1=CN=C[NH+]=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-O 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-O hydron;quinoline Chemical compound [NH+]1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-O 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 2
- 150000003673 urethanes Chemical group 0.000 description 2
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004345 1-phenyl-2-propyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- HCNCDZZCOOYKAG-UHFFFAOYSA-N 10-oxoniapentacyclo[12.8.0.02,11.04,9.015,20]docosa-1(14),2,4,6,8,10,12,15,17,19,21-undecaene Chemical compound C1=C2C=CC3=C(C=CC=4[O+]=C5C=CC=CC5=CC3=4)C2=CC=C1 HCNCDZZCOOYKAG-UHFFFAOYSA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical compound C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 description 1
- FYRZOXZLXPDHOF-UHFFFAOYSA-N 2-[(3-methylsulfanylphenyl)carbamoyloxy]ethyl prop-2-enoate Chemical compound CSC1=CC=CC(NC(=O)OCCOC(=O)C=C)=C1 FYRZOXZLXPDHOF-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 125000004361 3,4,5-trifluorophenyl group Chemical group [H]C1=C(F)C(F)=C(F)C([H])=C1* 0.000 description 1
- 125000003762 3,4-dimethoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 1
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- DEEPVUMBLJVOEL-UHFFFAOYSA-N 3H-pyrazole Chemical compound C1C=CN=N1 DEEPVUMBLJVOEL-UHFFFAOYSA-N 0.000 description 1
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- NILYRCYRBPDITI-UHFFFAOYSA-N 4H-pyrazole Chemical compound C1C=NN=C1 NILYRCYRBPDITI-UHFFFAOYSA-N 0.000 description 1
- PJMDLNIAGSYXLA-UHFFFAOYSA-N 6-iminooxadiazine-4,5-dione Chemical compound N=C1ON=NC(=O)C1=O PJMDLNIAGSYXLA-UHFFFAOYSA-N 0.000 description 1
- ZSPKHTMRVHTHMA-UHFFFAOYSA-N CSC1=CC=CC(NCOCCOC(C=C)=O)=C1 Chemical compound CSC1=CC=CC(NCOCCOC(C=C)=O)=C1 ZSPKHTMRVHTHMA-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- CHJGTQMXQICNAD-UHFFFAOYSA-N FC(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)COC(=O)NCCC(C)CC(C)(C)CNC(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F Chemical compound FC(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)COC(=O)NCCC(C)CC(C)(C)CNC(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F CHJGTQMXQICNAD-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
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Abstract
本發明關於一種自硼酸酯製備三芳基有機硼酸鹽之方法,及關於此等物質於光引發系統之用途、包含此光引發系統之光聚合物組成物、包含該光聚合物組成物之全像介質以及各自之全像圖。
Description
本發明關於自硼酸酯製備三芳基有機硼酸鹽之方法及關於此等物質於光引發系統之用途、包含此光引發系統之光聚合物組成物、包含該光聚合物組成物之全像介質、及各自之全像圖。
三芳基有機硼酸鹽能夠與合適的敏化劑(如陽離子、陰離子或中性染料)一起形成光引發劑,其藉由光化輻射引發合適單體之自由基光聚合反應。三芳基有機硼酸鹽之製備已被廣泛記載,且選定的三芳基有機硼酸四烷基銨鹽為可商購得。
過去三芳基有機硼酸四烷基銨鹽之製造可藉由從昂貴、受限且高腐蝕性的二溴硼烷-二甲基硫化物開始,參見JP 2002226486 A。此外,該途徑導致固有量之非常不欲的四芳基硼酸鹽。因此,目標為開發一種可靠的、可規模的製造三芳基有機硼酸鹽之方法,避免使用二溴硼烷-二甲基硫化物。
美國專利4,076,756 A描述了三芳基單烷基硼化合物的四烷基銨鹽的合成,藉由鹼金屬(如鈉)與有機鹵化物(如氯苯)和原硼酸 酯(如硼酸三異丙酯)之反應。在芳環上存在多個鹵素取代基的情況下(如4-溴-2-氯甲苯),該方法不能控制反應的化學選擇性。而且,由於其自燃性,在較大規模下使用鈉分散體具有潛在危險。
美國專利5,151,520A揭示了用作光引發劑的三芳基單烷基硼化合物的四烷基銨鹽之合成,該方法是藉由使市售三苯基硼烷與烷基鋰在惰性氣體環境中反應,然後分離鋰鹽,並進一步在該鋰鹽和四烷基銨鹵化物之間進行離子交換反應。該方法的缺點包括難以分離空氣敏感性之鋰鹽中間體,其可能導致反應收率降低。此外,由於使用了市售的三苯基硼烷,因此排除了在芳環上具有各種其他有用的取代基的可能性。US 5,151,520 A進一步描述了在惰性條件下、藉由烯和二溴硼烷甲基硫醚錯合物(DBBS)溶液之間的反應,隨後與四烷基銨鹽進行離子交換反應來合成最終產物的第二種方法。由於三溴甲基硫醚(tribromo methylsulfide)的存在,該途徑將總是產生一些副產物四硼酸四芳基酯,因此必須有隨後的純化步驟。
因此,本發明著眼的問題為提供一種製造高純度三芳基有機硼酸鹽的方法,其遵循合成路線,其不允許形成不需要的四芳基硼酸鹽,並且其提供更有益的及改良的時空收率,從而實現更經濟的整體製程,包括改良的下游製程或後處理製程。
此問題係藉由如下方法解決:一種製造式(IX)之三芳基有機硼酸鹽之方法,其係藉由在溶劑或溶劑混合物S1中,使式B(OR2)3(I)的硼酸酯與式R1-E(II)之有機鋰-或格任亞試劑(Grignard-reagent)反應,在溶劑或溶劑混合物S2中添加預先形成 的式R3-M-X(V)之有機金屬試劑,進一步添加式1/m Am+ Y-(VIII)的鹽,並且分離沈澱之式的三芳基-烷基硼酸鹽產物而可獲得或獲得,其中A 代表基於氮、磷、氧、硫和/或碘的具有電荷m之經取代有機陽離子,B 代表硼E 代表鋰或鎂-單鹵化物,M 代表選自鎂、鈣、鋁、錫、鋅或鎘之金屬,X 代表氯、溴或碘,較佳為氯或溴,Y 代表鹵化物、烷氧化物(alkxyde)或硫化物,較佳為鹵化物,R1 代表C1-至C22-烷基-、C3-至C22-烯基-、C3-至C22-炔基-、C5-至C7-環烷基-或C7-至C15-芳烷基殘基,其可視需要經氧或氮或鹵素取代,R2 代表視需要分支的C1-至C22-烷基殘基或視需要經烷基取代的C3-至C7-環烷基殘基或視需要經芳基或雜芳基取代的C2-至C22-烷基殘基,或R2可形成視需要經烷基殘基及/或經氧原子取代的2-8-員雙環,或R2可形成視需要經烷基殘基及/或經氧原子取代的4-14-員三環,R3 代表C6-至C14-芳基殘基,其視需要經選自鹵素、C1-至C4-烷基、三氟甲基、C1-至C4-烷氧基、三氟甲氧基、苯基及/或苯氧基之至少一殘基取代, m 代表1、2或3,較佳為代表1或2,最佳為代表1,S1與S2 彼此獨立地代表質子有機溶劑或質子有機溶劑之混合物,在本發明方法之另一具體實例中,式之三芳基有機硼酸鹽之製造包含下列步驟:i)在溶劑或溶劑混合物S1中、於溫度或溫度範圍T1下,使式B-(O-R2)3(I)之硼酸酯與式R1-E(II)之有機鋰-或格任亞試劑反應,以生成式[R1B(OR2)3]-E+(III)的鹽,ii)在溶劑或溶劑混合物S2中、於溫度或溫度範圍T2下,使式R3-X(IV)之有機鹵素化合物與金屬M反應,以生成式R3-M-X(V)之有機金屬試劑,iii)在結合溶劑或溶劑混合物S1與S2中、於溫度或溫度範圍T3下,使化合物(III)與化合物(V)反應以生成式(VI)與式R2O-M-X(VII)的鹽,iv)添加式1/m Am+Y-(VIII)的鹽及水,以及v)分離式之沈澱產物,其中T1 代表-110℃至-50℃之溫度,較佳為-100℃至-60℃,最佳為-90℃至-70℃,T2 代表-20℃至100℃之溫度,較佳為0℃至80℃,最佳為25℃至70℃,且T3 代表0℃至100℃之溫度,較佳為10℃至80℃,最佳為25℃至70℃。
本發明之方法係藉由以下反應圖進一步描述。
較佳為R1代表C2-至C18-烷基-、C3-至C18-烯基-、C3-至C18-炔基-、C5-至C6-環烷基-或C7-至C13-芳烷基殘基,其視需要經氧及/或鹵素取代,並且最佳為R1代表C4-至C16-烷基-、C3-至C16-烯基-、C3-至C16-炔基-、環己基-或C7-至C13-芳烷基殘基,其視需要經氧及/或鹵素取代。
較佳為R2代表最終分支的C2-至C18-烷基殘基,或R2形成視需要經烷基殘基及/或經氧原子取代的2-6-員雙環,或R2可形成視需要經烷基殘基及/或經氧原子取代的4-10-員三環。
較佳為R3代表C6-至C10-芳基殘基,其可視需要經選自鹵素、C1-至C4-烷基、三氟甲基、C1-至C4-烷氧基、三氟甲氧基、苯基及/或苯氧基的至少一殘基取代,並且尤佳的R3代表C6-芳基殘基,其可視需要經選自鹵素、C1-至C4-烷基、三氟甲基、C1-至C4-烷氧基、三氟甲氧基、苯基及/或苯氧基的至少一殘基取代,並且最佳的R3代表C6-芳基殘基,其可視需要經選自鹵素、C1-至C4-烷基、三氟甲基、C1-至C4-烷氧基及/或三氟甲氧基的至少二殘基取代。
基於氮的具有電荷m之經取代有機陽離子A可為例如銨、吡啶鎓(pyridinium)、噠嗪鎓(pyridazinium)、嘧啶鎓(pyrimidinium)、吡嗪鎓 (pyrazinium)、咪唑鎓(imidazolium)、1H-吡唑鎓(pyrazolium)、3H-吡唑鎓、4H-吡唑鎓、1-吡唑啉鎓(pyrazolinium)、2-吡唑啉鎓、3-吡唑啉鎓、咪唑啉鎓(imidazolinium)、噻唑鎓(thiazolium)、1,2,4-***鎓(triazolium)、1,2,3-***鎓、吡咯烷鎓(pyrrolidinium)、喹啉鎓(quinolinium),其可進一步經視需要一或多個含如醚、酯、醯胺及/或胺基甲酸酯之官能基的側鏈取代,且其亦可具有寡聚或聚合或橋聯特性。較佳之基於氮的具有電荷m之經取代有機陽離子A為例如銨、吡啶鎓、噠嗪鎓、嘧啶鎓、吡嗪鎓、咪唑鎓、吡咯烷鎓,其可進一步經視需要一或多個含如醚、酯、醯胺及/或胺基甲酸酯之官能基的側鏈取代,且其亦可具有寡聚或聚合或橋聯特性。尤佳之基於氮的具有電荷m之經取代有機陽離子A為例如銨、吡啶鎓及咪唑鎓,其可進一步經視需要一或多個含如醚、酯、醯胺及/或胺基甲酸酯之官能基的側鏈取代,且其亦可具有寡聚或聚合或橋聯特性。此外,藉由以上描述也可以包括聚合物陽離子。
基於磷的具有電荷m之經取代有機陽離子A為具有配位數4之磷(IV)-化合物,例如經取代的四烷基-鏻-、三烷基-芳基-鏻-、二烷基-二芳基-鏻-、烷基-三芳基-鏻-或四芳基-鏻-鹽,其可進一步經視需要一或多個含如醚、酯、羰基、醯胺及/或胺基甲酸酯之官能基的側鏈取代,且其亦可具有寡聚或聚合或橋聯特性。芳族殘基可額外地經鹵素、硝基-、氰基-、三氟甲基-、酯-及/或醚殘基取代。該烷基-與芳基殘基可藉由碳-或單-及/或聚-醚鏈形成單-或多-環結構而連結。較佳的基於磷的具有電荷m之經取代有機陽離子B為例如經取代的四烷基-鏻-、三烷基-芳基-鏻-、二烷基-二芳基-鏻-、烷基-三芳基-鏻-、或四芳基-鏻-鹽,其可進一步經視需要一或多個含如羰基、醯 胺及/或胺基甲酸酯之官能基的側鏈取代,且其亦可具有寡聚或聚合或橋聯特性。芳族殘基可額外地經鹵素、酯-及/或醚殘基取代。該烷基-與芳基殘基可藉由碳-或單-及/或聚-醚鏈形成單-或多-環結構而連結。尤佳的基於磷的具有電荷m之經取代有機陽離子A為例如經取代的四烷基-鏻-、三烷基-芳基-鏻-、烷基-三芳基-鏻-、或四芳基-鏻-鹽,其可進一步經視需要一或多個含如羰基、醯胺及/或胺基甲酸酯之官能基的側鏈取代,且其亦可具有寡聚或聚合或橋聯特性。芳族殘基可額外地經鹵素取代。該烷基-與芳基殘基可藉由碳-或單-及/或聚-醚鏈形成單-或多-環結構而連結。此外,藉由以上描述也可以包括聚合物鏈。
基於氧的具有電荷m之經取代有機陽離子A為例如經取代的吡喃鎓(pyrylium),還包含如在苯并吡喃鎓(benzopyrylium)、黃烷鎓(flavylium)或萘并二苯并吡喃鎓(naphthoxanthenium)中的成環物(annulated exhibits)。較佳的基於氧的具有電荷m之經取代有機陽離子A為例如經取代的吡喃鎓,還包括如在苯并吡喃鎓或黃烷鎓中的成環物。此外,藉由以上描述也可以包括聚合物陽離子。
基於硫的具有電荷m之經取代有機陽離子A為例如鎓-化合物,其帶有相同或不同視需要經取代的C1-至C22-烷基-、C6-至C14-芳基-、C7-至C15-芳基烷基-或C5-至C7-環烷基殘基的,及/或連接至總電荷m為1n3之鎓離子的寡聚或聚合重複單位。較佳的基於硫的具有電荷m之經取代有機陽離子A為例如鎓-化合物,其帶有相同或不同視需要經取代的C1-至C14-烷基-、C6-至C10-芳基-、C7-至C12-芳基烷基-或C5-至C6-環烷基殘基,及/或連接至總電荷m為1n3之鎓離子的寡聚或聚合重複單位。尤佳的基於硫的具有電荷m之經取代 有機陽離子A為例如鎓-化合物,其帶有相同或不同視需要經取代的C1-至C12-烷基-、C6-至C10-芳基-、C7-至C12-芳基烷基-或C5-至C6-環烷基殘基,及/或連接至總電荷m為1n3之鎓離子的寡聚或聚合重複單位。此外,藉由以上描述也可以包括聚合物陽離子。
基於碘的具有電荷m之經取代有機陽離子A為例如鎓-化合物,其帶有相同或不同視需要經取代的C1-至C22-烷基-、C6-至C14-芳基-、C7-至C15-芳基烷基-或C5-至C7-環烷基殘基,及/或連接至總電荷m為1n3之鎓離子的寡聚或聚合重複單位。較佳的基於碘的具有電荷m之經取代有機陽離子A為例如鎓-化合物,其帶有相同或不同視需要經取代的C1-至C14-烷基-、C6-至C10-芳基-、C7-至C12-芳基烷基-或C5-至C6-環烷基殘基,及/或連接至總電荷m為1n3之鎓離子的寡聚或聚合重複單位。尤佳的基於碘的具有電荷m之經取代有機陽離子A為例如鎓-化合物,其帶有相同或不同視需要經取代的C1-至C12-烷基-、C6-至C10-芳基-、C7-至C12-芳基烷基-或C5-至C6-環烷基殘基,及/或連接至總電荷m為1n3之鎓離子的寡聚或聚合重複單位。此外,藉由以上描述也可以包括聚合物陽離子。
質子有機溶劑或質子有機溶劑之混合物S1或-彼此互相獨立-S2只能用強鹼去質子化(Reichardt,C.,Solvents and Solvent Effects in Organic Chemistry,3.Ed.;Wiley-VCH:Weinheim,(2003))。質子有機溶劑的實例為烷、烯、苯與具有脂族及/或芳族取代基的芳香族、羧酸酯、醚或其混合物。較佳的質子有機溶劑為烷、具有脂族及/或芳族取代基之芳族化合物、醚或其混合物。芳族烴,如溶劑石油腦、甲苯或二甲苯,或醚如四氫呋喃、甲基四氫呋喃、二***或二甲氧基乙烷可被用作為質子有機溶劑或質子有機溶劑之混合物S1或 S2。溶劑應實質上無水。
在本發明的具體實例中,M代表鎂、鈣或鋁,且較佳為M代表鎂。
在本發明中,C1-C22-烷基包含例如且不限於甲基、乙基、n-丙基、異丙基、n-丁基、sec.-丁基、tert.-丁基、n-戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、neo-戊基、1-乙基丙基、1,1-二甲基丙基、1,2-二甲基丙基、n-己基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1-乙基丁基、2-乙基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基-1-甲基-丙基、1-乙基-2-甲基丙基或1-乙基-2-甲基丙基、n-庚基、n-辛基、2-乙基己基、松油醯基(pinacoyl)、n-壬基、n-癸基、n-十二烷基、n-十三烷基、n-十四烷基、n-十六烷基、n-十八烷基、n-二十烷基、n-二十二烷基。
例如在烷基或烷基芳基、烷基苯基-或烷基羰基-基團中,相對應的烷基基團也適用。
經取代烷基殘基中的伸烷基殘基以及烯基殘基或炔基殘基例如代表對應上述烷基殘基的伸烷基殘基、烯基殘基或炔基殘基。實例為2-氯乙基、苄基、烯丙基、2-丁烯-1-基或炔丙基。
本發明全文中的環烷基例如代表環丙基、環丁基、環戊基、環己基、環庚基、金剛烷基或異構的亞蒽基。
芳基代表具有6至14個骨架碳原子的碳環芳族基團。同樣適用於芳基烷基基團的芳族部分,也稱為芳烷基,以及更複雜的基團如芳基羰基的芳基部分。
C6至C14-芳基的實例為苯基,鄰-、對-、間-甲苯基,鄰-、對-、間-乙基苯基,萘基,菲基(phenanthrenyl),蒽基,芴基,鄰-、對-、間-氟苯基,鄰-、對-、間-氯苯基,鄰-、對-、間-甲氧基苯基,鄰-、對-、間-三氟甲基苯基,鄰-、對-、間-三氟甲氧基苯基,鄰-、對-或間-聯苯,或鄰-、對-、間-苯氧基苯基,3,4-二甲基苯基,3,4-二氯甲基,3,4-二氟-苯基,3,4-二甲氧基苯基,4-甲基-3-氟苯基,4-甲基-3-氯苯基,3,4,5-三氟苯基。
芳基烷基或芳烷基各自獨立地代表如上定義的直鏈、環狀、分支或非分支烷基,其可以單獨、多個或全部被如上定義的芳基取代。實例為芐基、4-氯芐基、苯乙基、2-苯基-1-丙基、3-苯基-1-丙基、1-苯基-2-丙基或二苯基甲基。
視需要經烷基殘基及/或經氧原子取代的2-8員雙環之實例為-CH2-CH2-、-CH2-CH2-CH2-、-CH2-CH2-CH2-CH2-、-CH2-CH2-O-CH2-CH2-、或-CH2-CH(CH3)-。
反應通常在不施加壓力的情況下進行,即至少在自生壓力下進行。該反應較佳為在惰性氣體環境如氮或氬氣體環境下進行。
在整個反應過程中經由持續攪拌確保批料的良好混合,以及藉由選擇合適的溶劑S1來開始反應是有利的。
令人驚訝地發現:當施用產生鹽(III)的有機鋰或格任亞試劑 (II)時,試劑(II)的有機化合物似乎阻斷(I)的反應中心,從而抑制不需要的四芳基硼酸鹽形成並產生更純的產物(IX)。
藉由加入化合物(IV)總量的最多10%而方便地開始反應的步驟(b),然後將化合物(IV)以10-90%濃度,較佳為15-75%濃度,尤佳為20-50%濃度添加在溶劑S2中的溶液用於進一步反應,同時溫度T2保持在如上所述的程度,從而控制放熱反應。為了引發反應,還可以視需要添加之已知化合物為二溴乙烷、碘,或者可以通過超聲來活化金屬表面M。
在步驟(d)中向鹽(VI)和(VII)加入鹽(VIII)出乎意料地導致產物(IX)的沉澱,同時所有副產物保留在液相中。因此產物IX能夠以高收率分離,並且通常以高純度作為結晶固體分離。
本發明的進一步目的為根據本發明之方法獲得或可獲得之式的三芳基有機硼酸鹽。在本發明的具體實例 中,其包含少於10.000ppm之四芳基硼酸鹽,較佳為少於5.000ppm之四芳基硼酸鹽,最佳為少於1.000ppm之四芳基硼酸鹽。單位ppm指重量百萬分率。
本發明的進一步目的為一種光聚合物組成物,其包含可光聚合組分與光引發系統,該光引發系統包含根據本發明之方法獲得或可獲得之式之三芳基有機硼酸鹽。在本發明的具體實例中,其包含0.1-10.0重量%之硼酸鹽,較佳為0.2-8.0重 量%,最佳為0.3-5.0重量%。該光引發系統可進一步包含至少一種至少一種共引發劑,選自硼酸鹽引發劑、三氯甲基引發劑、芳基氧化物引發劑、雙咪唑引發劑、二茂鐵引發劑、胺基烷基引發劑、肟引發劑、硫醇引發劑、過氧化物引發劑。
本發明的另一目的為包含此光聚合物全像介質以及包含此全像介質的全像圖。此全像介質提供具有高折射對比(index contrasts)之全像圖。
圖1顯示折射率調節△n之代表性曲線。
異氰酸酯含量(NCO值)
記載的異氰酸酯含量根據DIN EN ISO 11909測定。
HPLC方法1(純度)HPLC分析在具有使用C18柱的二極管陣列檢測器的HPLC系統中進行。乙腈、三乙胺和冰醋酸的混合物、以及水、三乙胺和乙酸的各種組成用作流動相。藉由將色譜圖中的每個峰面積除以所有峰的總面積,經由對除了空白峰之外的所有峰進行積分來測量純度作為面積百分比。在14.7分鐘的滯留時間洗提參(3-氯-4-甲基-苯基)己基硼酸四丁基銨,及在12.1分鐘洗提四芳基取代的硼酸鹽雜質。
顏色(霧度)
將1.00g分析物溶於3.00g甲基乙基酮中,並根據DIN EN ISO 14782:1999測定顏色。
折射率調節△n:全息介質的全息特性△n係如WO2015091427中所述通過反射中的兩個光束干涉來測定,代表性曲線示於圖1中。
物質:
Desmodur® N 3900,Covestro AG,Leverkusen,DE的產品,己烷二異氰酸酯系聚異氰酸酯,亞胺基氧雜-二嗪二酮的量至少30%,NCO含量:23.5%。
Fomrez UL 28,催化劑,Momentive Performance Chemicals的產品,Wilton,CT,USA。
染料1,(3,7-雙(二乙胺基)-吩噁嗪-5-鎓雙(2-乙基己基)琥珀酸酯),如WO 2012062655所述般製備。
多元醇1為WO2015091427之多元醇1,且如其中所述製備。
胺甲酸酯丙烯酸酯1,(硫代磷醯基參(氧基苯醯-4,1-二基胺甲醯基氧基乙烷-2,1-二基)參丙烯酸酯,[1072454-85-3]),如WO2015091427所述製備。
胺甲酸酯丙烯酸酯2,(2-({[3-(甲基硫烷基)苯基]胺甲醯基}氧基)乙基丙-2-烯酸酯,[1207339-61-4]),如於WO2015091427所述製備。
添加劑1,雙(2,2,3,3,4,4,5,5,6,6,7,7-十二氟庚基)-(2,2,4-三甲基己烷-1,6-二基)雙胺基甲酸酯[1799437-41-4],如WO2015091427所述製備。
所使用的溶劑和試劑購自特化品貿易商。無水溶劑含<50ppm水。
1. 三異丙基(己基)硼酸鋰之合成(步驟a)
將67.5L無水THF加入反應器中並加入(4.125kg)三異丙基硼酸鹽,並用緩慢的氮氣流脫氣15分鐘。將反應器冷卻至-78±2℃,在此溫度下於攪拌下將7.5kg正己基鋰(2.3M)緩慢轉移至反應器中。在-78±2℃攪拌下繼續該反應2小時。隨後使反應物質逐漸達到8±2℃的溫度。
2. 格任亞反應(步驟b)
將60L無水THF加入反應器中,並加入1.8kg鎂和60g碘。將反應器加熱至48±2℃,並將(15kg)4-溴-2-氯甲苯以及30L無水THF加入滴液漏斗中。將來自反應器和滴液漏斗的溶液兩者用緩慢的氮氣流分別脫氣15分鐘。在攪拌下將來自滴液漏斗的脫氣的4-溴-2-氯甲苯溶液緩慢加入反應器中。在溫度升高之前加入最大量4.0L的4-溴-2-氯甲苯溶液,表明有機金屬反應開始。加完後,將反應器進一步加熱至65±2℃(或THF的回流溫度),並將反應混合物在攪拌下保持在該溫度3小時。然後,將反應混合物逐漸冷卻至13±2℃。
步驟a和b係同時進行,但在分開的反應器中進行,因為兩種中間體都不能穩定儲存。
3. 參(3-氯-4-甲基-苯基)己基硼酸四丁基銨之合成(步驟c & d)
將步驟(a)的溶液在13±2℃下在恆定的冷卻和攪拌下緩慢 加入到步驟(b)的溶液中。加入結束後,將反應器溫度緩慢升至室溫並繼續攪拌4小時(步驟c)。然後在27±2℃下用4.8公斤四丁基溴化銨在30L水中的溶液驟冷(quench)並繼續攪拌30分鐘。將90L乙酸乙酯加入反應物料中,並分離水相和有機相。棄去水相,並將有機相用水提取三次(3*90L)。然後濃縮有機相得到漿液。向漿料中加入150L甲醇並將其加熱至回流溫度(65-70℃)1-2小時,然後過濾熱甲醇溶液。接著將溶液冷卻至8±2℃ 10-12小時,過濾得到重結晶產物。用5-10L甲醇洗滌產物並在60±2℃真空乾燥直至達到所需的LOD值(<0.1%)。所得產物為白色固體,產量為6.3kg,產率為理論量的50%,純度~95%,APHA50。
1. 三異丙基(己基)硼酸鋰之合成(步驟a)
將67.5L無水THF加入反應器中並加入(4.125kg)三異丙基硼酸鹽,並用緩慢的氮氣流脫氣15分鐘。將反應器冷卻至-78±2℃,在此溫度下於攪拌下將7.5kg正己基鋰(2.3M)緩慢轉移至反應器中。在-78±2℃攪拌下繼續該反應2小時。隨後使反應物質逐漸達到8±2℃的溫度。
2. 格任亞反應(步驟b)
將60L無水THF裝入反應器中並加入1.8kg鎂以及60g碘。將反應器加熱至48±2℃,並將(15kg)4-溴-2-氯甲苯以及30L無水THF加入滴液漏斗中。將來自反應器和滴液漏斗的溶 液兩者用緩慢的氮氣流分別脫氣15分鐘。在攪拌下將來自滴液漏斗的脫氣的4-溴-2-氯甲苯溶液緩慢加入反應器中。在溫度升高之前加入最大量4.0L的4-溴-2-氯甲苯溶液,表明有機金屬反應開始。加完後,將反應器進一步加熱至65±2℃(或THF的回流溫度),並將反應混合物在該溫度下保持3小時。然後,將反應混合物逐漸冷卻至13±2℃。
步驟a和b係同時進行,但在分開的反應器中進行,因為兩種中間體都不能穩定儲存。
3. 參(3-氯-4-甲基-苯基)己基硼酸四丁基銨之合成(步驟c & d)
將步驟(a)的溶液在13±2℃下在恆定的冷卻和攪拌下緩慢加入到步驟(b)的溶液中。加入完成後,將反應器溫度緩慢升至室溫並繼續攪拌4小時(步驟c)。然後在27±2℃下用4.8kg四丁基溴化銨在30L水中的溶液驟冷,並繼續攪拌30分鐘。將90L乙酸乙酯加入反應物料中,並分離水相和有機相。棄去水相,將有機相用水提取三次(3*90L)。然後濃縮有機相得到漿液。向漿料中加入150L甲醇,將其加熱至回流溫度(65-70℃)1-2小時,然後在6小時內逐漸冷卻至25±2℃。經2小時將反應物質冷卻至10±1℃,過濾重結晶的產物。用5-10L甲醇洗滌產物。重結晶過程進行兩次,將產物在60±2℃真空乾燥,直至達到所需的LOD值(<0.1%)。所得產物為白色固體,產量5.6kg,產率為理 論值的45%,純度~97%,APHA 30。
1. 三異丙基(己基)硼酸鋰之合成(步驟a)
將180L無水THF加入反應器中,並加入(11kg)三異丙基硼酸鹽,並用緩慢的氮氣流脫氣15分鐘。將反應器冷卻至-78±2℃,並在攪拌下將20kg正己基鋰(2.3M)緩慢轉移至反應器中。使該反應在-78℃下繼續2小時。隨後,使反應物質逐漸達到8±2℃的溫度。
2. 格任亞反應(步驟b)
將160L無水THF加入反應器中,並加入4.8kg鎂和160g碘。將反應器加熱至48±2℃,並將(40kg)4-溴-2-氯甲苯以及80L無水THF裝入滴液漏斗中。將來自反應器和滴液漏斗的溶液兩者用緩慢的氮氣流分別脫氣15分鐘。在攪拌下將來自滴液漏斗的脫氣的4-溴-2-氯甲苯溶液緩慢加入反應器中。在溫度升高之前加入最大量4.0L的4-溴-2-氯甲苯溶液,表明有機金屬反應開始。添加完成後,將反應器進一步加熱至65±2℃(或THF的回流溫度),並將反應混合物在該溫度下保持3小時。然後,將反應混合物逐漸冷卻至13±2℃。
步驟a和b係同時進行,但在分開的反應器中進行,因為兩種中間體都不能穩定儲存。
3. 參(3-氯-4-甲基-苯基)己基硼酸四丁基銨之合成(步驟c & d)
將步驟a的溶液在13±2℃的恆定攪拌下緩慢加入到步驟b的溶液中。加入完成後,將反應器溫度緩慢升至室溫並繼續攪拌4小時(步驟c)。然後在27±2℃下用12.8kg四丁基溴化銨在80L水中的溶液中止反應並繼續攪拌另外30分鐘。將240L乙酸乙酯加入到反應物料中,分離水相和有機相。棄去水相,將有機相用水提取三次(3×240L)。然後濃縮有機相得到漿液。向漿料中加入400L甲醇並將其加熱至回流溫度(65-70℃)1-2h,然後在6h內逐漸冷卻至25±2℃。然後將反應混合物在2小時內冷卻至10±1℃,過濾重結晶的產物。產物用10-15L甲醇洗滌。將得到的粗產物溶於52L乙酸乙酯中,並通過0.2μm濾筒過濾。蒸發乙酸乙酯並將產物從60L甲醇中的濃縮物中沉澱出來。將沉澱的物質冷卻至10℃(30分鐘),藉由過濾分離產物。將產物在80±2℃真空乾燥直至達到所需的LOD值(<0.1%)。所得產物為白色固體,產量為18.46kg,理論產率為55%,純度~96%,APHA 40
如表1所示,實施例1、2及3可以根據包含步驟a)-d)的本發明方法以極好的收率和純度來生產。
將3.38g多元醇組分1與2.00g丙烯酸酯1、2.00g丙烯酸酯2、1.50g添加劑1、0.10g參(3-氯-4-甲基-苯基)己基硼酸四丁基銨(實施例1)、0.018g染料1、0.09g實施例1和0.35g乙酸乙酯在40℃混合,得到澄清溶液。然後將溶液冷卻至30℃,在重新混合之前加入0.65g Desmodur® N3900(來自德國Leverkusen的Covestro AG的商業產品,己烷二異氰酸酯系聚異氰酸酯,至少30%的亞胺基氧雜-二嗪二酮部分,NCO含量:23.5%)。最後,加入0.01g Fomrez UL 28(胺基甲酸酯化催化劑,Momentive Performance Chemicals,Wilton,CT,USA的商業產品),並再次短暫混入。將混合的光聚合物調配物施加在36μm厚的聚對苯二甲酸乙二醇酯膜上。將塗佈膜在80℃下乾燥5.8分鐘,最後用40μm聚乙烯膜覆蓋。達成的感光聚合物層厚度約為14μm。
使用來自實施例2與實施例3的0.10g參(3-氯-4-甲基-苯基)己基硼酸四丁基銨,類似地製備介質M2與M3。
如表2所示,具有根據本發明之含步驟a)-d)方法製造的實施例 1、2及3之全像介質提供具有高折射對比的全像介質。
Claims (7)
- 一種製造式之三芳基有機硼酸鹽之方法,其係藉由下列步驟獲得或可獲得:在溶劑或溶劑混合物S1中使式B(OR2)3(I)之硼酸酯與式R1-E(II)之有機鋰-或格任亞試劑反應,添加預先形成之式R3-M-X(V)的有機金屬試劑於溶劑或溶劑混合物S2中,進一步添加式1/m Am+Y-(VIII)的鹽,並且分離沈澱的式之三芳基-烷基硼酸鹽產物,其中A 代表具有基於氮、磷、氧、硫和/或碘的電荷m之經取代有機陽離子,B 代表硼,E 代表鋰或鎂-單鹵化物,M 代表選自鎂、鈣、鋁、錫、鋅或鎘之金屬,X 代表氯、溴或碘,Y 代表鹵化物、烷氧化物、或硫化物,R1 代表C1-至C22-烷基-、C3-至C22-烯基-、C3-至C22-炔基-、C5-至C7-環烷基-或C7-至C15-芳烷基殘基,其可視需要經氧或氮或鹵素取代,R2 代表視需要分支的C1-至C22-烷基殘基或視需要經烷基取代的C3-至C7-環烷基殘基或視需要經芳基或雜芳基取代的C2-至C22-烷基殘基,或R2可形成視需要經烷基殘基及/或經氧原子取代的2-8-員雙環,或R2可形成視需要經烷基殘基及/或經氧原子取代的4-14-員三環, R3 代表C6-至C14-芳基殘基,其視需要經至少一選自鹵素、C1-至C4-烷基、三氟甲基、C1-至C4-烷氧基、三氟甲氧基、苯基及/或苯氧基的殘基取代,m 代表1、2或3,S1與S2 彼此獨立地代表質子有機溶劑或質子有機溶劑之混合物。
- 如請求項1之方法,其包含下列步驟:i)於溶劑或溶劑混合物S1中、在溫度或溫度範圍T1下,使式B(OR2)3(I)之硼酸酯與式R1-E(II)之有機鋰-或格任亞試劑反應,以生成式[R1B(OR2)3]-E+(III)的鹽,ii)於溶劑或溶劑混合物S2中、在溫度或溫度範圍T2下,使式R3-X(IV)之有機鹵素化合物與金屬M反應,以生成式R3-M-X(V)之有機金屬試劑,iii)於結合的溶劑或溶劑混合物S1與S2中、在溫度或溫度範圍T3下,使化合物(III)與化合物(V)反應,以生成式之鹽與式R2O-M-X(VII)之鹽,iv)添加式1/m Am+Y-(VIII)的鹽及水,以及v)分離式之沈澱產物,其中T1 代表-110℃至-50℃之溫度,T2 代表-20℃至100℃之溫度,並且T3 代表0℃至100℃之溫度。
- 如請求項1或2之方法,其特徵在於R1代表視需要經氧及/或鹵素取代的C2-至C18-烷基-、C3-至C18-烯基-、C3-至C18-炔基-、C5- 至C6-環烷基-或C7-至C13-芳烷基殘基。
- 如請求項1或2之方法,其特徵在於R2代表最終分支的C2-至C18-烷基殘基,或R2形成視需要經烷基殘基及/或經氧原子取代的2-6-員雙環,或R2可形成視需要經烷基殘基及/或經氧原子取代的4-10-員三環。
- 如請求項1或2之方法,其特徵在於R3代表C6-至C10-芳基殘基,其可視需要經至少一選自鹵素、C1-至C4-烷基、三氟甲基、C1-至C4-烷氧基、三氟甲氧基、苯基及/或苯氧基的殘基取代。
- 如請求項1或2之方法,其特徵在於S1與S2係彼此獨立地代表烷、烯、苯與具有脂族及/或芳族取代基的芳香族、羧酸酯、醚或其混合物。
- 如請求項1或2之方法,其特徵在於M代表鎂、鈣或鋁。
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
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??16197986.9 | 2016-11-09 | ||
EP16197986 | 2016-11-09 | ||
EP16197986.9 | 2016-11-09 | ||
EP17185207 | 2017-08-08 | ||
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EP (1) | EP3538532B1 (zh) |
JP (1) | JP2019535692A (zh) |
KR (1) | KR102499972B1 (zh) |
CN (1) | CN109890830A (zh) |
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TW201833122A (zh) | 2016-11-09 | 2018-09-16 | 德商科思創德意志股份有限公司 | 製備三芳基有機硼酸鹽的方法 |
US20220231336A1 (en) * | 2019-03-14 | 2022-07-21 | Mitsui Chemicals, Inc. | Lithium borate compound, additive for lithium secondary battery, nonaqueous electrolytic solution for lithium secondary battery, precursor for lithium secondary battery, and production method for lithium secondary battery |
WO2023156482A1 (de) | 2022-02-21 | 2023-08-24 | Covestro Deutschland Ag | Thermostabile photopolymere im sichtbaren spektralbereich und photopolymer-zusammensetzungen damit |
WO2023156485A1 (de) | 2022-02-21 | 2023-08-24 | Covestro Deutschland Ag | Triarylalkylboratsalze als coinitiatoren in nir-photopolymerzusammensetzungen |
WO2023156484A1 (de) | 2022-02-21 | 2023-08-24 | Covestro Deutschland Ag | Photopolymerzusammensetzungen für thermostabile photopolymere im sichtbaren spektralbereich |
CN115353577B (zh) * | 2022-08-17 | 2024-02-13 | 山东大学 | 一种聚合氮化碳和有机硼酸盐光引发剂体系及其在引发自由基聚合反应中的应用 |
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- 2017-11-07 CN CN201780069513.XA patent/CN109890830A/zh active Pending
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TW201831498A (zh) | 2018-09-01 |
US11242360B2 (en) | 2022-02-08 |
WO2018099698A1 (en) | 2018-06-07 |
EP3538532A1 (en) | 2019-09-18 |
CN109890830A (zh) | 2019-06-14 |
JP2019535692A (ja) | 2019-12-12 |
KR102499972B1 (ko) | 2023-02-15 |
US20200062786A1 (en) | 2020-02-27 |
EP3538532B1 (en) | 2020-09-16 |
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