JPH0725860A - Production of tris(tribromophenoxy)-s-triazine - Google Patents
Production of tris(tribromophenoxy)-s-triazineInfo
- Publication number
- JPH0725860A JPH0725860A JP5168833A JP16883393A JPH0725860A JP H0725860 A JPH0725860 A JP H0725860A JP 5168833 A JP5168833 A JP 5168833A JP 16883393 A JP16883393 A JP 16883393A JP H0725860 A JPH0725860 A JP H0725860A
- Authority
- JP
- Japan
- Prior art keywords
- tribromophenolate
- chloride
- cyanuric chloride
- added
- tribromophenoxy
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- BDFBPPCACYFGFA-UHFFFAOYSA-N 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine Chemical compound BrC1=CC(Br)=CC(Br)=C1OC1=NC(OC=2C(=CC(Br)=CC=2Br)Br)=NC(OC=2C(=CC(Br)=CC=2Br)Br)=N1 BDFBPPCACYFGFA-UHFFFAOYSA-N 0.000 title abstract description 10
- OUCSIUCEQVCDEL-UHFFFAOYSA-N 2,3,4-tribromophenol Chemical compound OC1=CC=C(Br)C(Br)=C1Br OUCSIUCEQVCDEL-UHFFFAOYSA-N 0.000 claims abstract description 45
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 18
- -1 tribromophenoxy Chemical group 0.000 claims description 9
- 239000007983 Tris buffer Substances 0.000 claims description 6
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000001816 cooling Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- XDCQNYYELACHOT-UHFFFAOYSA-M (2-methylphenyl)methyl-triphenylphosphanium;bromide Chemical compound [Br-].CC1=CC=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 XDCQNYYELACHOT-UHFFFAOYSA-M 0.000 description 1
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 1
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical group C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical group C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- FNAKEOXYWBWIRT-UHFFFAOYSA-N 2,3-dibromophenol Chemical compound OC1=CC=CC(Br)=C1Br FNAKEOXYWBWIRT-UHFFFAOYSA-N 0.000 description 1
- QBFHSEQNGHSFLZ-UHFFFAOYSA-N 2,4,6-tris(2,3,4-tribromophenoxy)-1,3,5-triazine Chemical class BrC1=C(Br)C(Br)=CC=C1OC1=NC(OC=2C(=C(Br)C(Br)=CC=2)Br)=NC(OC=2C(=C(Br)C(Br)=CC=2)Br)=N1 QBFHSEQNGHSFLZ-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- UDYGXWPMSJPFDG-UHFFFAOYSA-M benzyl(tributyl)azanium;bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 UDYGXWPMSJPFDG-UHFFFAOYSA-M 0.000 description 1
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 1
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- FFZVILRAPIUNAA-UHFFFAOYSA-N benzyl-dimethyl-phenylazanium Chemical compound C=1C=CC=CC=1[N+](C)(C)CC1=CC=CC=C1 FFZVILRAPIUNAA-UHFFFAOYSA-N 0.000 description 1
- CLCOXQROCAMRQO-UHFFFAOYSA-M benzyl-dimethyl-phenylazanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[N+](C)(C)CC1=CC=CC=C1 CLCOXQROCAMRQO-UHFFFAOYSA-M 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- MFIUDWFSVDFDDY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 MFIUDWFSVDFDDY-UHFFFAOYSA-M 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- MMQWEMMTKXBCLU-UHFFFAOYSA-M cyclohexyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)C1CCCCC1 MMQWEMMTKXBCLU-UHFFFAOYSA-M 0.000 description 1
- OXGUSHVFNQIABV-UHFFFAOYSA-M cyclohexyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)C1CCCCC1 OXGUSHVFNQIABV-UHFFFAOYSA-M 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical group O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 1
- UNTITLLXXOKDTB-UHFFFAOYSA-N dibenzo-24-crown-8 Chemical group O1CCOCCOCCOC2=CC=CC=C2OCCOCCOCCOC2=CC=CC=C21 UNTITLLXXOKDTB-UHFFFAOYSA-N 0.000 description 1
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical group O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 1
- QMLGNDFKJAFKGZ-UHFFFAOYSA-N dicyclohexano-24-crown-8 Chemical group O1CCOCCOCCOC2CCCCC2OCCOCCOCCOC2CCCCC21 QMLGNDFKJAFKGZ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- CBPVAIUOSQZRCK-UHFFFAOYSA-N hexyl(triphenyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCCC)C1=CC=CC=C1 CBPVAIUOSQZRCK-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QLPMKRZYJPNIRP-UHFFFAOYSA-M methyl(trioctyl)azanium;bromide Chemical compound [Br-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC QLPMKRZYJPNIRP-UHFFFAOYSA-M 0.000 description 1
- JNMIXMFEVJHFNY-UHFFFAOYSA-M methyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 JNMIXMFEVJHFNY-UHFFFAOYSA-M 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical group 0.000 description 1
- OBLXVLWZBMAMHE-UHFFFAOYSA-M octyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCCCCC)C1=CC=CC=C1 OBLXVLWZBMAMHE-UHFFFAOYSA-M 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical group 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- KBOPQCLKSDUBAZ-UHFFFAOYSA-M tetrabenzylazanium;bromide Chemical compound [Br-].C=1C=CC=CC=1C[N+](CC=1C=CC=CC=1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 KBOPQCLKSDUBAZ-UHFFFAOYSA-M 0.000 description 1
- CCBCJOPAGXYIQL-UHFFFAOYSA-M tetrabenzylazanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1C[N+](CC=1C=CC=CC=1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 CCBCJOPAGXYIQL-UHFFFAOYSA-M 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 description 1
- HMJWAKCBJWAMPL-UHFFFAOYSA-M triethyl(phenyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)C1=CC=CC=C1 HMJWAKCBJWAMPL-UHFFFAOYSA-M 0.000 description 1
- ICTMDIORIDZWQN-UHFFFAOYSA-M triethyl(phenyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)C1=CC=CC=C1 ICTMDIORIDZWQN-UHFFFAOYSA-M 0.000 description 1
- GNMJFQWRASXXMS-UHFFFAOYSA-M trimethyl(phenyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)C1=CC=CC=C1 GNMJFQWRASXXMS-UHFFFAOYSA-M 0.000 description 1
- MQAYPFVXSPHGJM-UHFFFAOYSA-M trimethyl(phenyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)C1=CC=CC=C1 MQAYPFVXSPHGJM-UHFFFAOYSA-M 0.000 description 1
- FWYKRJUVEOBFGH-UHFFFAOYSA-M triphenyl(prop-2-enyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC=C)C1=CC=CC=C1 FWYKRJUVEOBFGH-UHFFFAOYSA-M 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、トリス（トリブロモフ
ェノキシ）−ｓ−トリアジンの製造方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing tris (tribromophenoxy) -s-triazine.
【０００２】[0002]
【従来の技術と発明が解決しようとする課題】トリス
（トリブロモフェノキシ）−ｓ−トリアジン化合物は、
フランス特許１５６６６７５号によって公知であり、米
国特許３８４３６５０号および特開昭４７−２５２３２
号によって合成樹脂用難燃剤として優れた特性を有する
ことが公知となっている。しかし、フランス特許１５６
６６７５号に記載のトリス（トリブロモフェノキシ）−
ｓ−トリアジン化合物は、純度が低く、収率も低い。2. Description of the Related Art Tris (tribromophenoxy) -s-triazine compounds are
Known from French Patent No. 1566675, U.S. Pat. No. 3,843,650 and JP 47-25232.
It is known from the publication that it has excellent properties as a flame retardant for synthetic resins. However, French patent 156
Tris (tribromophenoxy)-described in 6675
The s-triazine compound has low purity and low yield.
【０００３】従来は、トリス（トリブロモフェノキシ）
−ｓ−トリアジンの製造方法として、例えば特開昭４７
−２５２３２号および米国特許３８４３６５０号に記載
されているように、塩化シアヌルをケトン系溶剤または
環状エーテル系溶剤に溶解し、トリブロモフェノラート
の水溶液またはエタノール溶液を添加する方法がとられ
ている。また、特開昭５３−１１６３９０号に記載され
ているように、水と有機溶剤との不均一混合溶剤で、相
間移動触媒の存在下、アルカリにて処理する方法が知ら
れている。Conventionally, tris (tribromophenoxy)
As a method for producing -s-triazine, for example, Japanese Patent Laid-Open No.
No. 25232 and US Pat. No. 3,843,650, cyanuric chloride is dissolved in a ketone solvent or a cyclic ether solvent, and an aqueous solution of tribromophenolate or an ethanol solution is added. Further, as described in JP-A-53-116390, a method of treating with an alkali in a heterogeneous mixed solvent of water and an organic solvent in the presence of a phase transfer catalyst is known.
【０００４】しかしながら、親水性溶剤を使用する製造
方法では、溶剤回収時に水との共沸により水分が含まれ
ることとなり回収溶剤から水分を除去することが困難で
あるため、回収溶剤を反応溶剤として再使用すると、塩
化シアヌルが加水分解を受けて加水分解物が反応系に混
入し、得られる生成物の純度を低下させ、合成樹脂に添
加した場合に樹脂の物性および難燃性を低下させるとい
う問題があった。However, in the manufacturing method using a hydrophilic solvent, it is difficult to remove the water from the recovered solvent because the water is contained by azeotropic distillation with water during the recovery of the solvent, and therefore the recovered solvent is used as a reaction solvent. When reused, cyanuric chloride undergoes hydrolysis and the hydrolyzate is mixed into the reaction system, which lowers the purity of the product obtained and reduces the physical properties and flame retardancy of the resin when added to synthetic resins. There was a problem.
【０００５】また、非親水性溶剤を使用する製造方法で
は、特開平３−３４９７２号に記載されているように、
高純度、高収率でトリス（トリブロモフェノキシ）−ｓ
−トリアジンが得られるが、反応器の単位容量当たりの
生産量が２５％程度で、経済性の点で問題があった。こ
れは、トリブロモフェノラートは、水中にてトリブロモ
フェノールとアルカリとを、アルカリがトリブロモフェ
ノールのモル数より過剰となるようにして反応させるこ
とにより容易に合成できるが、トリス（トリブロモフェ
ノキシ）−ｓ−トリアジンの生産性、トリブロモフェノ
ラート調製に関する操作性（トリブロモフェノールのポ
リマーの生成しやすさ）およびトリブロモフェノラート
の溶解度を考慮してトリブロモフェノラート水溶液を調
製すると、その濃度は４８重量％が限界であるからであ
る。しかし、トリブロモフェノラート水溶液の濃度が低
いと、塩化シアヌルとの反応において、水の影響により
塩化シアヌルが加水分解を受けて純度の高いトリス（ト
リブロモフェノキシ）−ｓ−トリアジンが得られない。
さらに、塩化シアヌルを溶解させるのに、塩化シアヌル
の溶解度の関係上、多量の非親水性溶剤を必要とし、一
回の製造による生産量が少ないという問題があった。Further, in the production method using a non-hydrophilic solvent, as described in JP-A-3-34972,
Tris (tribromophenoxy) -s with high purity and high yield
-Triazine can be obtained, but the production amount per unit volume of the reactor is about 25%, which is a problem in terms of economy. Tribromophenolate can be easily synthesized by reacting tribromophenol and an alkali in water such that the alkali is in excess of the molar number of tribromophenol, but tris (tribromophenoxy) is used. ) -S-Triazine productivity, operability for preparation of tribromophenolate (ease of formation of polymer of tribromophenol) and solubility of tribromophenolate are taken into consideration when an aqueous solution of tribromophenolate is prepared. This is because the concentration is limited to 48% by weight. However, when the concentration of the aqueous tribromophenolate solution is low, cyanuric chloride is hydrolyzed by the influence of water in the reaction with cyanuric chloride, and high-purity tris (tribromophenoxy) -s-triazine cannot be obtained.
Further, in order to dissolve cyanuric chloride, a large amount of non-hydrophilic solvent is required due to the solubility of cyanuric chloride, and there is a problem that the production amount per production is small.
【０００６】本発明は、このような従来の問題点に着目
してなされたもので、水を減らすことを考える中で、偶
然、トリブロモフェノラート水溶液調製中に塩化シアヌ
ル溶解溶剤である非親水性溶剤を添加したところ、容易
に５０重量％以上の高濃度でトリブロモフェノラートを
溶解させることができることを発見した。そして、水を
極力減らすことにより原料の塩化シアヌルの加水分解を
最小限に抑え、トリブロモフェノラートの高濃度溶解に
より一回の製造による生産量を高めることができる製造
方法を見出したのである。The present invention has been made by paying attention to such conventional problems, and in consideration of reducing water, by chance, during preparation of an aqueous solution of tribromophenolate, a non-hydrophilic solvent which is a cyanuric chloride-dissolving solvent is accidentally prepared. It was discovered that the addition of an organic solvent can easily dissolve tribromophenolate at a high concentration of 50% by weight or more. Then, they have found a production method capable of minimizing the hydrolysis of the raw material cyanuric chloride by reducing water as much as possible, and increasing the production amount in a single production by dissolving tribromophenolate at a high concentration.
【０００７】[0007]
【課題を解決するための手段】本発明は、塩化シアヌル
と、還元剤を含む５０重量％以上の濃度のトリブロモフ
ェノラート水溶液とを、相間移動触媒の存在下で反応さ
せることを特徴とするトリス（トリブロモフェノキシ）
−ｓ−トリアジンの製造方法である。The present invention is characterized by reacting cyanuric chloride with an aqueous solution of tribromophenolate containing a reducing agent at a concentration of 50% by weight or more in the presence of a phase transfer catalyst. Tris (tribromophenoxy)
It is a method for producing -s-triazine.
【０００８】（１）トリブロモフェノラートの調製 トリブロモフェノラートの調製は、あらかじめ水に水酸
化ナトリウムや水酸化カリウム等のアルカリと還元剤を
溶解し、冷却した水溶液に非親水性溶剤を添加し、そこ
へトリブロモフェノールを添加し、加熱するかまたは室
温で完全に溶解させて行なう。非親水性溶剤を添加する
ことにより、５０％（重量％、以下同様）以上の高濃度
のトリブロモフェノラート水溶液を調製することができ
る。また、非親水性溶剤を添加することにより、トリブ
ロモフェノールの酸化重合が抑制される。(1) Preparation of tribromophenolate To prepare tribromophenolate, an alkali such as sodium hydroxide or potassium hydroxide and a reducing agent are previously dissolved in water, and a non-hydrophilic solvent is added to the cooled aqueous solution. Then, tribromophenol is added thereto, and the mixture is heated or completely dissolved at room temperature. By adding a non-hydrophilic solvent, it is possible to prepare an aqueous solution of tribromophenolate having a high concentration of 50% (% by weight, the same applies hereinafter) or higher. Further, the addition of the non-hydrophilic solvent suppresses the oxidative polymerization of tribromophenol.
【０００９】本発明において、トリブロモフェノラート
水溶液の濃度とは、水溶液中のトリブロモフェノラート
をトリブロモフェノールに換算して求めた値である。具
体的には、下式のように、水に対するトリブロモフェノ
ールの濃度として求められる。In the present invention, the concentration of the aqueous tribromophenolate solution is a value obtained by converting the tribromophenolate in the aqueous solution into tribromophenol. Specifically, it is calculated as the concentration of tribromophenol with respect to water as in the following formula.
【数１】 [Equation 1]
【００１０】操作性においては、あらかじめ非親水性溶
剤を添加しておくと、容易にトリブロモフェノラートを
調製できる。さらに、トリブロモフェノラート調製後の
トリブロモフェノラート水溶液は比重が重く、水層と非
親水性溶剤層に容易に分離し、トリブロモフェノラート
は非親水性溶剤に溶解しないため、分離した非親水性溶
剤を抜き取り、新たにトリブロモフェノールを添加して
溶解すると、反応器の容量に対して一度に多量のトリブ
ロモフェノラートを調製できる。抜き取った非親水性溶
剤は反応溶剤としてそのまま使用できる。生産性におい
ても、反応器の容量に対して一度に多量のトリブロモフ
ェノラートを調製できるため、一回の製造による生産量
を高めることができる。また、反応系内に入る水の量が
少ないため、塩化シアヌルの加水分解を最小限に抑える
ことができ、塩化シアヌルを完全に非親水性溶剤に溶解
させる必要なく分散状態で反応ができる。さらに、塩化
シアヌルの取り扱い上、可能であれば、塩化シアヌル粉
末を直接トリブロモフェノラート溶液へ添加して反応さ
せることもできる。In terms of operability, tribromophenolate can be easily prepared by adding a non-hydrophilic solvent in advance. Furthermore, the tribromophenolate aqueous solution after the preparation of tribromophenolate has a high specific gravity and easily separates into an aqueous layer and a non-hydrophilic solvent layer, and tribromophenolate does not dissolve in the non-hydrophilic solvent. If a hydrophilic solvent is taken out and tribromophenol is newly added and dissolved, a large amount of tribromophenolate can be prepared at once with respect to the capacity of the reactor. The extracted non-hydrophilic solvent can be used as it is as a reaction solvent. Also in terms of productivity, a large amount of tribromophenolate can be prepared at once with respect to the capacity of the reactor, so that the production amount in one production can be increased. Further, since the amount of water entering the reaction system is small, the hydrolysis of cyanuric chloride can be minimized, and the reaction can be carried out in a dispersed state without the need to completely dissolve cyanuric chloride in the non-hydrophilic solvent. Furthermore, in handling cyanuric chloride, if possible, it is also possible to add the cyanuric chloride powder directly to the tribromophenolate solution for reaction.
【００１１】本発明に用いるトリブロモフェノラート水
溶液の濃度の上限は８０％である。また、好ましい濃度
は６０〜８０％である。The upper limit of the concentration of the aqueous tribromophenolate solution used in the present invention is 80%. Further, the preferable concentration is 60 to 80%.
【００１２】（２）還元剤 本発明において、還元剤はトリブロモフェノールの酸化
重合を抑制する働きをする。(2) Reducing agent In the present invention, the reducing agent functions to suppress the oxidative polymerization of tribromophenol.
【００１３】本発明に使用される還元剤としては、例え
ば、フェノール、ブロモフェノール、ジブロモフェノー
ル、２，６−ジ−ｔ−ブチル−４−メチルフェノール
（ＢＨＴ）等のフェノール類、亜硫酸アンモニウム、亜
硫酸カリウム、亜硫酸ナトリウム、亜硫酸水素ナトリウ
ム等の亜硫酸塩、硫化ナトリウム、硫化アンモニウム、
硫化カリウム等の硫化物が挙げられる。還元剤の添加量
は、トリブロモフェノール１００重量部に対して０．０
１〜１．０重量部である。添加量が０．０１重量部未満
だと、トリブロモフェノラート水溶液の安定時間が短
く、赤褐色のポリマーが生成する。また、１．０重量部
を超えると、還元剤の水に対する溶解性が劣り、効果の
差は見られない。Examples of the reducing agent used in the present invention include phenols such as phenol, bromophenol, dibromophenol, 2,6-di-t-butyl-4-methylphenol (BHT), ammonium sulfite and sulfite. Sulfites such as potassium, sodium sulfite, sodium hydrogen sulfite, sodium sulfide, ammonium sulfide,
Examples thereof include sulfides such as potassium sulfide. The amount of reducing agent added is 0.0 with respect to 100 parts by weight of tribromophenol.
1 to 1.0 parts by weight. If the amount added is less than 0.01 part by weight, the stabilization time of the aqueous tribromophenolate solution is short and a reddish brown polymer is produced. On the other hand, if it exceeds 1.0 part by weight, the solubility of the reducing agent in water is poor and no difference in effect is observed.
【００１４】（３）塩化シアヌル 本発明に使用される塩化シアヌルは、粉末状のものをそ
のまま反応に使用してもよいし、または非親水性溶剤に
溶解または分散させた塩化シアヌルの溶液または分散液
の状態で反応に使用してもよい。(3) Cyanuric Chloride The cyanuric chloride used in the present invention may be used in the form of powder as it is for the reaction, or a solution or dispersion of cyanuric chloride dissolved or dispersed in a non-hydrophilic solvent. It may be used for the reaction in a liquid state.
【００１５】（４）溶剤 本発明に使用される溶剤は非親水性溶剤であれば特に限
定はないが、例えば塩化メチレン、クロロホルム、四塩
化炭素、トリクロロエチレン、パークロロエチレン、テ
トラクロロエチレン等のハロゲン化炭化水素類、ベンゼ
ン、トルエン、キシレン等の芳香族炭化水素類、ヘキサ
ン等の飽和炭化水素類、クロロベンゼン等のハロゲン置
換芳香族炭化水素類が挙げられる。好ましくは、塩化シ
アヌルの溶解度の高い溶剤、例えばクロロホルム、塩化
メチレン等のハロゲン化炭化水素類である。さらに、塩
化シアヌルを溶解または分散させるのに、これらの溶剤
を２種以上併用することもできる。また、塩化シアヌル
を溶解または分散させるのに使用する溶剤と、トリブロ
モフェノラートを水に高濃度で溶解させるために添加す
る非親水性溶剤とは異なってもよい。トリブロモフェノ
ラートを水に高濃度で溶解させるための非親水性溶剤は
２種以上併用しても差し支えない。蒸留によって回収さ
れた溶剤は、そのまま再使用することができ、必要であ
れば、脱水剤によって水分を除くこともできる。塩化シ
アヌルを溶解または分散させるのに必要な溶剤量は、特
に限定はされないが、塩化シアヌルに対して２．０倍重
量以上であるのが好ましい。それ未満であると、反応操
作が困難となる。トリブロモフェノラート調製のための
溶剤はトリブロモフェノラート調製後に反応器上部より
抜き取ることができるため、その溶剤量は特に限定され
ないが、トリブロモフェノールに対して０．１倍重量以
上であるのが好ましい。それ未満であると、トリブロモ
フェノラートの調製が困難である。(4) Solvent The solvent used in the present invention is not particularly limited as long as it is a non-hydrophilic solvent. For example, halogenated carbonization such as methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, tetrachloroethylene and the like. Examples thereof include hydrogens, aromatic hydrocarbons such as benzene, toluene and xylene, saturated hydrocarbons such as hexane, and halogen-substituted aromatic hydrocarbons such as chlorobenzene. Preferred are solvents having a high solubility for cyanuric chloride, for example, halogenated hydrocarbons such as chloroform and methylene chloride. Furthermore, in order to dissolve or disperse cyanuric chloride, two or more kinds of these solvents can be used together. Further, the solvent used for dissolving or dispersing cyanuric chloride and the non-hydrophilic solvent added for dissolving tribromophenolate in water at a high concentration may be different. Two or more non-hydrophilic solvents for dissolving tribromophenolate in water at a high concentration may be used in combination. The solvent recovered by distillation can be reused as it is, and if necessary, water can be removed by a dehydrating agent. The amount of solvent required to dissolve or disperse cyanuric chloride is not particularly limited, but is preferably 2.0 times or more the weight of cyanuric chloride. If it is less than that, the reaction operation becomes difficult. The solvent for the preparation of tribromophenolate can be withdrawn from the upper part of the reactor after the preparation of tribromophenolate, so the amount of the solvent is not particularly limited, but it is 0.1 times by weight or more relative to tribromophenol. Is preferred. If it is less than that, it is difficult to prepare tribromophenolate.
【００１６】（５）相間移動触媒 本発明に使用される相間移動触媒としては、トリフェニ
ルベンジルホスホニウムクロライド、トリフェニルエチ
ルホスホニウムブロマイド、ブチルトリフェニルホスホ
ニウムクロライド、フェナセチルトリフェニルホスホニ
ウムクロライド、ヘキシルトリフェニルホスホニウムブ
ロマイド、オクチルトリフェニルホスホニウムブロマイ
ド、テトラフェニルホスホニウムブロマイド、２−メチ
ルベンジルトリフェニルホスホニウムブロマイド、メチ
ルトリフェニルホスホニウムアイオダイド、フェナセチ
ルトリフェニルホスホニウムクロライド、アリルトリフ
ェニルホスホニウムブロマイド等の第４級リン化合物の
塩；テトラメチルアンモニウムクロライド、テトラメチ
ルアンモニウムブロマイド、テトラエチルアンモニウム
クロライド、テトラエチルアンモニウムブロマイド、テ
トラプロピルアンモニウムクロライド、テトラプロピル
アンモニウムブロマイド、テトラブチルアンモニウムク
ロライド、テトラブチルアンモニウムブロマイド、トリ
メチルフェニルアンモニウムクロライド、トリメチルフ
ェニルアンモニウムブロマイド、トリエチルフェニルア
ンモニウムクロライド、トリエチルフェニルアンモニウ
ムブロマイド、トリメチルベンジルアンモニウムクロラ
イド、トリメチルベンジルアンモニウムブロマイド、ト
リエチルベンジルアンモニウムクロライド、トリエチル
ベンジルアンモニウムブロマイド、トリブチルベンジル
アンモニウムクロライド、トリブチルベンジルアンモニ
ウムブロマイド、ジメチルベンジルフェニルアンモニウ
ムクロライド、ジメチルベンジルフェニルアンモニウム
ブロマイド、テトラベンジルアンモニウムクロライド、
テトラベンジルアンモニウムブロマイド、トリベンジル
フェニルアンモニウムクロライド、トリベンジルフェニ
ルアンモニウムブロマイド、トリメチルシクロヘキシル
アンモニウムクロライド、トリメチルシクロヘキシルア
ンモニウムブロマイド、トリブチルシクロヘキシルアン
モニウムクロライド、トリブチルシクロヘキシルアンモ
ニウムブロマイド、トリオクチルメチルアンモニウムク
ロライド、トリオクチルメチルアンモニウムブロマイ
ド、トリメチルｎ−ラウリルアンモニウムクロライド、
トリメチルｎ−ラウリルアンモニウムブロマイド、ｎ−
ラウリルピリジニウムクロライド、ｎ−ラウリルピリジ
ニウムブロマイド、ｎ−ステアリルピリジニウムクロラ
イド、ｎ−ステアリルピリジニウムブロマイド等の第４
級窒素化合物の塩；１５−クラウン−５、１８−クラウ
ン−６、ジベンゾ−１８−クラウン−６、ジシクロヘキ
シル−１８−クラウン−６、ジベンゾ−２４−クラウン
−８、ジシクロヘキシル−２４−クラウン−８等のクラ
ウンエーテル等が挙げられる。(5) Phase Transfer Catalyst The phase transfer catalyst used in the present invention includes triphenylbenzylphosphonium chloride, triphenylethylphosphonium bromide, butyltriphenylphosphonium chloride, phenacetyltriphenylphosphonium chloride and hexyltriphenylphosphonium. Salts of quaternary phosphorus compounds such as bromide, octyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, 2-methylbenzyltriphenylphosphonium bromide, methyltriphenylphosphonium iodide, phenacetyltriphenylphosphonium chloride, allyltriphenylphosphonium bromide ; Tetramethylammonium chloride, tetramethylammonium bromide, tetraethyl Lumonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, trimethylphenylammonium chloride, trimethylphenylammonium bromide, triethylphenylammonium chloride, triethylphenylammonium bromide, trimethylbenzyl Ammonium chloride, trimethylbenzylammonium bromide, triethylbenzylammonium chloride, triethylbenzylammonium bromide, tributylbenzylammonium chloride, tributylbenzylammonium bromide, dimethylbenzylphenylammonium Roraido, dimethylbenzyl phenyl ammonium bromide, tetra benzyl ammonium chloride,
Tetrabenzylammonium bromide, tribenzylphenylammonium chloride, tribenzylphenylammonium bromide, trimethylcyclohexylammonium chloride, trimethylcyclohexylammonium bromide, tributylcyclohexylammonium chloride, tributylcyclohexylammonium bromide, trioctylmethylammonium chloride, trioctylmethylammonium bromide, trimethyl n-lauryl ammonium chloride,
Trimethyl n-lauryl ammonium bromide, n-
Fourth such as laurylpyridinium chloride, n-laurylpyridinium bromide, n-stearylpyridinium chloride, n-stearylpyridinium bromide
Salts of secondary nitrogen compounds; 15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexyl-18-crown-6, dibenzo-24-crown-8, dicyclohexyl-24-crown-8 and the like. The crown ether and the like can be mentioned.
【００１７】添加量は、塩化シアヌルに対して０．１〜
１０．０％である。好ましくは、塩化シアヌルに対して
２．０〜５．０％である。The amount of addition is 0.1 to cyanuric chloride.
It is 10.0%. It is preferably 2.0 to 5.0% with respect to cyanuric chloride.
【００１８】相間移動触媒は、あらかじめトリブロモフ
ェノラートの溶液へ添加するか、あるいは塩化シアヌル
の溶液へ添加してもよい。The phase transfer catalyst may be added to the solution of tribromophenolate in advance or to the solution of cyanuric chloride.
【００１９】（６）製造方法 本発明の製造方法においては、非親水性溶剤を使用して
５０％以上の高濃度のトリブロモフェノラート水溶液を
調製し、これを、非親水性溶剤に溶解または分散した塩
化シアヌルと相間移動触媒の溶液へ滴下するか、また
は、この高濃度のトリブロモフェノラート水溶液に、相
間移動触媒と塩化シアヌル粉末を添加する。滴下または
添加した後、必要であれば熟成を行ない、常圧下または
減圧下で非親水性溶剤を反応系より除去することによ
り、高純度のトリス（トリブロモフェノキシ）−ｓ−ト
リアジンが得られる。(6) Manufacturing method In the manufacturing method of the present invention, a non-hydrophilic solvent is used to prepare a high concentration aqueous solution of tribromophenolate of 50% or more, and the tribromophenolate aqueous solution is dissolved in the non-hydrophilic solvent. The phase transfer catalyst and the cyanuric chloride powder are added dropwise to the dispersed solution of cyanuric chloride and the phase transfer catalyst, or to this high-concentration tribromophenolate aqueous solution. After dropping or adding, aging is carried out if necessary, and the non-hydrophilic solvent is removed from the reaction system under normal pressure or reduced pressure to obtain high-purity tris (tribromophenoxy) -s-triazine.
【００２０】反応温度は特に限定されないが、塩化シア
ヌルの溶液または分散液にトリブロモフェノラート水溶
液を滴下する際に回収溶剤を使用した場合は、トリブロ
モフェノラート水溶液の滴下の直前までは塩化シアヌル
の加水分解抑制のために１０℃以下に冷却した方がよ
く、滴下が開始されれば溶剤の沸点まで反応温度を上げ
てもよい。好ましくは、塩化シアヌルの加水分解を極力
抑えるため、低温で滴下した方がよい。The reaction temperature is not particularly limited, but when a recovery solvent is used when the aqueous solution of tribromophenolate is added dropwise to the solution or dispersion of cyanuric chloride, the cyanuric chloride solution is added until just before the addition of the aqueous solution of tribromophenolate. It is better to cool to 10 ° C. or lower in order to suppress the hydrolysis of the above, and the reaction temperature may be raised to the boiling point of the solvent when the dropping is started. Preferably, in order to suppress the hydrolysis of cyanuric chloride as much as possible, it is better to add it dropwise at a low temperature.
【００２１】（７）反応機構 相間移動触媒は、水と非親水性溶剤の不均一系におい
て、非親水性溶剤に溶解した塩化シアヌルと水に溶解し
たトリブロモフェノラートとを反応させることのできる
触媒であり、本発明の反応機構は、水溶性のトリブロモ
フェノラートを相間移動触媒により油溶性のトリブロモ
フェノラートとし、これが非親水性溶剤に移行して塩化
シアヌルと反応する。反応後の相間移動触媒は回収さ
れ、再度水溶性のトリブロモフェノラートを油溶性のト
リブロモフェノラートとするのに使われ、反応は繰り返
される。(7) Reaction Mechanism The phase transfer catalyst is capable of reacting cyanuric chloride dissolved in a non-hydrophilic solvent with tribromophenolate dissolved in water in a heterogeneous system of water and the non-hydrophilic solvent. It is a catalyst, and the reaction mechanism of the present invention is that a water-soluble tribromophenolate is converted into an oil-soluble tribromophenolate by a phase transfer catalyst, which is transferred to a non-hydrophilic solvent to react with cyanuric chloride. After the reaction, the phase transfer catalyst is recovered and used again to convert the water-soluble tribromophenolate into the oil-soluble tribromophenolate, and the reaction is repeated.
【００２２】（８）添加剤 さらに、本発明においては、安定剤、消泡剤等の添加剤
を使用することもできる。(8) Additives Further, in the present invention, additives such as stabilizers and antifoaming agents may be used.
【００２３】[0023]
【実施例】次に、本発明を実施例に基づいて説明する
が、本発明はかかる実施例のみに限定されるものではな
い。EXAMPLES Next, the present invention will be explained based on examples, but the present invention is not limited to such examples.
【００２４】実施例１ 撹拌機、冷却コンデンサー、温度計を有する３００ｍｌ
容量の反応器に、表１に示す量の水、水酸化ナトリウム
６．１ｇ（０．１５モル）および亜硫酸ナトリウム０．
０５ｇを加えて溶解し、冷却した。そこへ表１に示す非
親水性溶剤２５ｇを加えた後、２，４，６−トリブロモ
フェノール５０ｇ（０．１５モル）を加えて溶解させ
た。溶解後に、１０℃以下に冷却した。 Example 1 300 ml with stirrer, cooling condenser, thermometer
In a reactor of capacity, the amount of water shown in Table 1, 6.1 g (0.15 mol) of sodium hydroxide and 0.
05g was added and melt | dissolved, and it cooled. After 25 g of the non-hydrophilic solvent shown in Table 1 was added thereto, 50 g (0.15 mol) of 2,4,6-tribromophenol was added and dissolved. After dissolution, it was cooled to 10 ° C or lower.
【００２５】溶解状態を目視した結果を表１に示す。The results of visual observation of the dissolved state are shown in Table 1.
【００２６】ＴＢＰ（２，４，６−トリブロモフェノー
ル）の濃度は、下式により求めた。The concentration of TBP (2,4,6-tribromophenol) was calculated by the following formula.
【数２】 [Equation 2]
【００２７】比較例１ 撹拌機、冷却コンデンサー、温度計を有する３００ｍｌ
容量の反応器に、表１に示す量の水、水酸化ナトリウム
６．１ｇ（０．１５モル）および亜硫酸ナトリウム０．
０５ｇを加えて溶解し、冷却した。そこへ２，４，６−
トリブロモフェノール５０ｇ（０．１５モル）を加えて
溶解させた。溶解後に、１０℃以下に冷却した。 Comparative Example 1 300 ml equipped with a stirrer, cooling condenser and thermometer
In a reactor of capacity, the amount of water shown in Table 1, 6.1 g (0.15 mol) of sodium hydroxide and 0.
05g was added and melt | dissolved, and it cooled. 2, 4, 6-
50 g (0.15 mol) of tribromophenol was added and dissolved. After dissolution, it was cooled to 10 ° C or lower.
【００２８】溶解状態を目視した結果を表１に示す。The results of visual observation of the dissolved state are shown in Table 1.
【００２９】[0029]
【表１】 [Table 1]
【００３０】実施例２ 撹拌機、冷却コンデンサー、温度計を有する３００ｍｌ
容量の反応器に、表２に示す量の水、水酸化ナトリウム
６．１ｇ（０．１５モル）および亜硫酸ナトリウム０．
０５ｇを加えて溶解し、冷却した。そこへ塩化メチレン
２５ｇを加えた後、２，４，６−トリブロモフェノール
５０ｇ（０．１５モル）を加えて溶解させた。溶解後
に、１０℃以下に冷却し、水層部分の容量を測定した。
その結果を表２に示す。 Example 2 300 ml with stirrer, cooling condenser, thermometer
In a reactor of capacity, the amounts of water shown in Table 2, 6.1 g (0.15 mol) of sodium hydroxide and 0.
05g was added and melt | dissolved, and it cooled. After 25 g of methylene chloride was added thereto, 50 g (0.15 mol) of 2,4,6-tribromophenol was added and dissolved. After dissolution, the mixture was cooled to 10 ° C or lower, and the volume of the water layer portion was measured.
The results are shown in Table 2.
【００３１】[0031]
【表２】 [Table 2]
【００３２】実施例３ 撹拌機、冷却コンデンサー、温度計、滴下ロートを有す
る５００ｍｌ容量の反応器に、塩化メチレン１５０ｇ、
塩化シアヌル５０ｇ（０．２７１モル）を加えて溶解ま
たは分散させた後、トリフェニルエチルホスホニウムブ
ロマイド１．６ｇを加えた。 Example 3 In a 500 ml reactor equipped with a stirrer, cooling condenser, thermometer and dropping funnel, 150 g of methylene chloride,
After 50 g (0.271 mol) of cyanuric chloride was added and dissolved or dispersed, 1.6 g of triphenylethylphosphonium bromide was added.
【００３３】次いで、撹拌機、冷却コンデンサー、温度
計を有する５００ｍｌ容量の他の反応器に、水９６ｇ、
水酸化ナトリウム３４．２ｇ（０．８６モル）、亜硫酸
ナトリウム０．１４ｇを加えて溶解し、１０℃以下に冷
却した。冷却後、反応溶剤の塩化メチレン１３０ｇを加
え、２，４，６−トリブロモフェノール２７２ｇ（０．
８２モル）を添加した。溶解した後、冷却したトリブロ
モフェノラート溶液を、反応温度３〜３０℃で、上述し
た塩化シアヌル溶液に滴下した。滴下終了後、還流下で
３時間熟成した。熟成後、常圧下にて塩化メチレンを留
去した。Then, in another reactor of 500 ml capacity having a stirrer, a cooling condenser and a thermometer, 96 g of water,
34.2 g (0.86 mol) of sodium hydroxide and 0.14 g of sodium sulfite were added and dissolved, and the mixture was cooled to 10 ° C or lower. After cooling, 130 g of methylene chloride as a reaction solvent was added, and 272 g of 2,4,6-tribromophenol (0.
82 mol) was added. After dissolution, the cooled tribromophenolate solution was added dropwise to the above cyanuric chloride solution at a reaction temperature of 3 to 30 ° C. After the dropping was completed, the mixture was aged under reflux for 3 hours. After aging, methylene chloride was distilled off under normal pressure.
【００３４】生成物を濾別乾燥し、白色結晶のトリス
（トリブロモフェノキシ）−ｓ−トリアジンを得た。The product was filtered and dried to obtain white crystals of tris (tribromophenoxy) -s-triazine.
【００３５】結果を表３に示す。The results are shown in Table 3.
【００３６】実施例４ 撹拌機、冷却コンデンサー、温度計を有する５００ｍｌ
容量の反応器に、水９６ｇ、水酸化ナトリウム３４．２
ｇ（０．８６モル）、亜硫酸ナトリウム０．１４ｇを加
えて溶解し、１０℃以下に冷却した。冷却後、反応溶剤
の塩化メチレン１３０ｇを加え、２，４，６−トリブロ
モフェノール２７２ｇ（０．８２モル）を添加した。溶
解した後、冷却してトリフェニルエチルホスホニウムブ
ロマイド１．６ｇおよび塩化メチレン１５０ｇを加え
た。こうして調製したトリブロモフェノラート溶液に、
反応温度３〜３０℃で、塩化シアヌル粉末５０ｇ（０．
２７１モル）を添加した。添加後、還流下で３時間熟成
した。熟成後、常圧下にて塩化メチレンを留去した。 Example 4 500 ml with stirrer, cooling condenser, thermometer
In a capacity reactor, 96 g of water, 34.2 sodium hydroxide
g (0.86 mol) and 0.14 g of sodium sulfite were added and dissolved, and the mixture was cooled to 10 ° C or lower. After cooling, 130 g of methylene chloride as a reaction solvent was added, and 272 g (0.82 mol) of 2,4,6-tribromophenol was added. After dissolution, the mixture was cooled and 1.6 g of triphenylethylphosphonium bromide and 150 g of methylene chloride were added. To the tribromophenolate solution thus prepared,
50 g of cyanuric chloride powder (0.
271 mol) was added. After the addition, the mixture was aged under reflux for 3 hours. After aging, methylene chloride was distilled off under normal pressure.
【００３７】生成物を濾別乾燥し、白色結晶のトリス
（トリブロモフェノキシ）−ｓ−トリアジンを得た。The product was separated by filtration and dried to obtain white crystals of tris (tribromophenoxy) -s-triazine.
【００３８】結果を表３に示す。The results are shown in Table 3.
【００３９】比較例２ 撹拌機、冷却コンデンサー、温度計、滴下ロートを有す
る５００ｍｌ容量の反応器に、塩化メチレン１６０ｇ、
塩化シアヌル２５ｇ（０．１３６モル）を加えて溶解ま
たは分散させた後、トリエチルベンジルアンモニウムク
ロライド０．８ｇを加えた。 Comparative Example 2 In a 500 ml reactor equipped with a stirrer, cooling condenser, thermometer and dropping funnel, 160 g of methylene chloride,
After 25 g (0.136 mol) of cyanuric chloride was added and dissolved or dispersed, 0.8 g of triethylbenzylammonium chloride was added.
【００４０】次いで、撹拌機、冷却コンデンサー、温度
計を有する５００ｍｌ容量の他の反応器に、水１５０
ｇ、水酸化ナトリウム１７．１ｇ（０．４３モル）を加
えて溶解し、１０℃以下に冷却した。冷却後、２，４，
６−トリブロモフェノール１３６ｇ（０．４１モル）を
添加した。溶解した後、冷却したトリブロモフェノラー
ト溶液を、反応温度３〜３０℃で、上述した塩化シアヌ
ル溶液に滴下した。滴下終了後、還流下で３時間熟成し
た。熟成後、常圧下にて塩化メチレンを留去した。Then, another reactor having a capacity of 500 ml equipped with a stirrer, a cooling condenser, and a thermometer is charged with 150 parts of water.
g and 17.1 g (0.43 mol) of sodium hydroxide were added and dissolved, and the mixture was cooled to 10 ° C or lower. After cooling 2, 4,
136 g (0.41 mol) of 6-tribromophenol were added. After dissolution, the cooled tribromophenolate solution was added dropwise to the above cyanuric chloride solution at a reaction temperature of 3 to 30 ° C. After the dropping was completed, the mixture was aged under reflux for 3 hours. After aging, methylene chloride was distilled off under normal pressure.
【００４１】生成物を濾別乾燥し、白色結晶のトリス
（トリブロモフェノキシ）−ｓ−トリアジンを得た。The product was separated by filtration and dried to obtain white crystals of tris (tribromophenoxy) -s-triazine.
【００４２】結果を表３に示す。The results are shown in Table 3.
【００４３】[0043]
【表３】 [Table 3]
【００４４】[0044]
【発明の効果】本発明のトリス（トリブロモフェノキ
シ）−ｓ−トリアジンの製造方法は、公知文献の製造方
法よりも、反応器の単位容量あたりの生産量が高い。ま
た、収率および純度も高い。INDUSTRIAL APPLICABILITY The production method of tris (tribromophenoxy) -s-triazine of the present invention has a higher production amount per unit volume of the reactor than the production methods of known documents. Also, the yield and purity are high.
Claims (2)
％以上の濃度のトリブロモフェノラート水溶液とを、相
間移動触媒の存在下で反応させることを特徴とするトリ
ス（トリブロモフェノキシ）−ｓ−トリアジンの製造方
法。1. Tris (tribromophenoxy) -s characterized by reacting cyanuric chloride with an aqueous solution of tribromophenolate containing a reducing agent at a concentration of 50% by weight or more in the presence of a phase transfer catalyst. -Method for producing triazine.
は分散させた塩化シアヌルの溶液または分散液であるこ
とを特徴とする請求項１記載の製造方法。2. The method according to claim 1, wherein the cyanuric chloride is a solution or dispersion of cyanuric chloride dissolved or dispersed in a non-hydrophilic solvent.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5168833A JP2729346B2 (en) | 1993-07-08 | 1993-07-08 | Method for producing tris (tribromophenoxy) -s-triazine |
| US08/264,385 US5498714A (en) | 1993-07-08 | 1994-06-23 | Process for production of tris(tribromophenoxy)-s-triazine |
| IL11015494A IL110154A (en) | 1993-07-08 | 1994-06-28 | Process for the production of tris(tribromophenoxy)-s-triazine and a tribromophenolate solution for use therein |
| EP94110024A EP0634407B1 (en) | 1993-07-08 | 1994-06-28 | Process for production of tris(tribromophenoxy)-s-triazine |
| DE69428557T DE69428557T2 (en) | 1993-07-08 | 1994-06-28 | Process for the preparation of tris (tribromphenoxy) -s-triazine |
| US08/579,496 US5696302A (en) | 1993-07-08 | 1995-12-27 | Highly concentrated aqueous tribromophenolate solution and a method for preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5168833A JP2729346B2 (en) | 1993-07-08 | 1993-07-08 | Method for producing tris (tribromophenoxy) -s-triazine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0725860A true JPH0725860A (en) | 1995-01-27 |
| JP2729346B2 JP2729346B2 (en) | 1998-03-18 |
Family
ID=15875372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5168833A Expired - Lifetime JP2729346B2 (en) | 1993-07-08 | 1993-07-08 | Method for producing tris (tribromophenoxy) -s-triazine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2729346B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6300415B1 (en) | 1995-11-24 | 2001-10-09 | Chisso Corporation | Propylene composition, process for preparing the same, polypropylene composition, and molded articles |
| US6319991B1 (en) | 1997-05-22 | 2001-11-20 | Chisso Corporation | Propylene polymer blends, processes of producing the same and polypropylene resin compositions |
| CN118530191A (en) * | 2024-07-26 | 2024-08-23 | 山东海王化工股份有限公司 | Full-process continuous green environment-friendly production process of bromotriazine |
-
1993
- 1993-07-08 JP JP5168833A patent/JP2729346B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6300415B1 (en) | 1995-11-24 | 2001-10-09 | Chisso Corporation | Propylene composition, process for preparing the same, polypropylene composition, and molded articles |
| US6319991B1 (en) | 1997-05-22 | 2001-11-20 | Chisso Corporation | Propylene polymer blends, processes of producing the same and polypropylene resin compositions |
| CN118530191A (en) * | 2024-07-26 | 2024-08-23 | 山东海王化工股份有限公司 | Full-process continuous green environment-friendly production process of bromotriazine |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2729346B2 (en) | 1998-03-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5907040A (en) | Process for production of tris(tribromophenoxy)-s-triazine | |
| US3075979A (en) | Preparation of trialkyl isocyanusates | |
| US4196289A (en) | Process for producing triallyl isocyanurate | |
| DE2360709A1 (en) | S-TRIAZINE PRE-POLYMERIZES | |
| JP2729347B2 (en) | Method for producing tris (tribromophenoxy) -s-triazine | |
| JP2729346B2 (en) | Method for producing tris (tribromophenoxy) -s-triazine | |
| US4058570A (en) | Brominated biphenol process | |
| US3408411A (en) | Manufacture of organic compounds containing fluorine | |
| US5498714A (en) | Process for production of tris(tribromophenoxy)-s-triazine | |
| US7468174B2 (en) | Method for producing chlorosulfonyl isocyanate | |
| JP2729348B2 (en) | Method for producing tris (tribromophenoxy) -s-triazine | |
| US4200749A (en) | Preparation of halogenated modified isocyanurates | |
| US2577900A (en) | Process for producing anils | |
| KR20240074708A (en) | Method for preparing bis-resorcinyl triazine | |
| US3576804A (en) | Fluorotriazine compounds | |
| CA2657173A1 (en) | Process for preparing triallyl cyanurate | |
| CA1239418A (en) | Polyphosphazene process | |
| KR840001563B1 (en) | Process for preparing 1-carbymayl-3-(3,5-dichlorophenyl)-hydantoins | |
| US3137694A (en) | Method for isolating tetrameric cyanogen halide from its reaction mixture | |
| KR100484265B1 (en) | Method for preparing 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine | |
| JP3161723B2 (en) | Method for producing chlorosulfonyl isocyanate | |
| US4074052A (en) | Process for preparation of isocyanuric acid triesters | |
| KR930007844B1 (en) | Method for preparing sulfite ester of halogenated neopentyl alcohol | |
| JPS6049170B2 (en) | Method for producing β-alkoxyethoxymethyl halide | |
| US20090192309A1 (en) | Process for preparing triallyl cyanurate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131219 Year of fee payment: 16 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131219 Year of fee payment: 16 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313114 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131219 Year of fee payment: 16 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |