JPH04338344A - Production of hexabromocyclododecane - Google Patents
Production of hexabromocyclododecaneInfo
- Publication number
- JPH04338344A JPH04338344A JP13707891A JP13707891A JPH04338344A JP H04338344 A JPH04338344 A JP H04338344A JP 13707891 A JP13707891 A JP 13707891A JP 13707891 A JP13707891 A JP 13707891A JP H04338344 A JPH04338344 A JP H04338344A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- bromine
- solvent
- cdt
- hbcd
- 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 description 8
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 title abstract description 19
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 46
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 45
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 14
- ZOLLIQAKMYWTBR-RYMQXAEESA-N cyclododecatriene Chemical compound C/1C\C=C\CC\C=C/CC\C=C\1 ZOLLIQAKMYWTBR-RYMQXAEESA-N 0.000 claims abstract description 3
- 239000003960 organic solvent Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 49
- 239000002904 solvent Substances 0.000 abstract description 18
- DEIGXXQKDWULML-MOCCIAMBSA-N (1r,2r,5r,6s,9s,10r)-1,2,5,6,9,10-hexabromocyclododecane Chemical compound Br[C@H]1CC[C@H](Br)[C@H](Br)CC[C@@H](Br)[C@H](Br)CC[C@H]1Br DEIGXXQKDWULML-MOCCIAMBSA-N 0.000 abstract description 13
- 238000000034 method Methods 0.000 description 29
- 235000019441 ethanol Nutrition 0.000 description 19
- 239000000203 mixture Substances 0.000 description 13
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 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 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- DEIGXXQKDWULML-UFVWWTPHSA-N (1r,2r,5s,6r,9s,10r)-1,2,5,6,9,10-hexabromocyclododecane Chemical compound Br[C@H]1CC[C@@H](Br)[C@@H](Br)CC[C@@H](Br)[C@H](Br)CC[C@H]1Br DEIGXXQKDWULML-UFVWWTPHSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000012261 resinous substance Substances 0.000 description 3
- DEIGXXQKDWULML-PQTSNVLCSA-N (1r,2r,5s,6r,9r,10s)-1,2,5,6,9,10-hexabromocyclododecane Chemical compound Br[C@H]1CC[C@@H](Br)[C@H](Br)CC[C@H](Br)[C@H](Br)CC[C@H]1Br DEIGXXQKDWULML-PQTSNVLCSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- WSTVDTWMEQQLAB-UHFFFAOYSA-N 1,2-dibromocyclododeca-1,3-diene Chemical compound BrC1=C(Br)C=CCCCCCCCC1 WSTVDTWMEQQLAB-UHFFFAOYSA-N 0.000 description 1
- SVYOXGBINYWSDQ-UHFFFAOYSA-N 1,4-dioxane;ethanol Chemical compound CCO.C1COCCO1 SVYOXGBINYWSDQ-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007269 dehydrobromination reaction Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- FHHZOYXKOICLGH-UHFFFAOYSA-N dichloromethane;ethanol Chemical compound CCO.ClCCl FHHZOYXKOICLGH-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- -1 etc. Substances 0.000 description 1
- LJQKCYFTNDAAPC-UHFFFAOYSA-N ethanol;ethyl acetate Chemical compound CCO.CCOC(C)=O LJQKCYFTNDAAPC-UHFFFAOYSA-N 0.000 description 1
- ZRSDQBKGDNPFLT-UHFFFAOYSA-N ethanol;oxolane Chemical compound CCO.C1CCOC1 ZRSDQBKGDNPFLT-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- YTZKOQUCBOVLHL-UHFFFAOYSA-N p-methylisopropylbenzene Natural products CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、耐熱性に優れた1,2
,5,6,9,10−ヘキサブロモシクロドデカンを製
造する方法に関する。本発明で得られる1,2,5,6
,9,10−ヘキサブロモシクロドデカンは、高分子化
合物の難燃剤として有用な化合物である。[Industrial Application Field] The present invention is directed to 1, 2 with excellent heat resistance.
, 5,6,9,10-hexabromocyclododecane. 1, 2, 5, 6 obtained by the present invention
,9,10-hexabromocyclododecane is a compound useful as a flame retardant for polymeric compounds.
【0002】0002
【従来の技術】1,2,5,6,9,10−ヘキサブロ
モシクロドデカン(以下HBCDと略記する)はポリス
チレン樹脂等に使用されている難燃剤である。この難燃
剤は、臭素を1,5,9−シス,トランス,トランス−
シクロドデカトリエン(以下CDTと略記する)に付加
させる反応によって合成される。2. Description of the Related Art 1,2,5,6,9,10-hexabromocyclododecane (hereinafter abbreviated as HBCD) is a flame retardant used in polystyrene resins and the like. This flame retardant contains bromine in 1,5,9-cis, trans, trans-
It is synthesized by an addition reaction to cyclododecatriene (hereinafter abbreviated as CDT).
【0003】ODS逆相カラムを装着した高速液体クロ
マトグラフィーを用いて分析すると、HBCDには3種
類の異性体が存在することが知られている。それらはカ
ラムから溶出する順番にα−HBCD、β−HBCD、
γ−HBCDと命名されている[E.R.Larsen
and E.L.Ecker, J.Fire
Sci.,4,261(1986)]。[0003] When analyzed using high performance liquid chromatography equipped with an ODS reverse phase column, it is known that HBCD exists in three types of isomers. They are α-HBCD, β-HBCD,
It has been named γ-HBCD [E. R. Larsen
and E. L. Ecker, J. Fire
Sci. , 4, 261 (1986)].
【0004】本発明者らが、各異性体を単離し、物性値
を測定した結果では、α−、β−、γ−体のそれぞれの
融点は184〜186℃、168〜171℃、196〜
198℃である。また熱重量分析(空気中、昇温速度1
0℃/min)では、5%加熱重量減温度はそれぞれ2
42℃、217℃、245℃で、50%加熱重量減温度
はそれぞれ255℃、232℃、258℃である。従っ
てγ−HBCD、α−HBCD、β−HBCDの順に熱
安定性は高い。難燃剤として用いられるHBCDはγ−
体が主体のものであるが、これらの異性体の存在比の違
いにより、HBCDの品質が大きく左右される。例えば
、融点が低く熱安定性が低いβ−HBCDの存在比が高
くなると、HBCDの融点と耐熱性は低くなる。そのた
め、HBCDの熱分解が比較的低温で起こり始めるため
に、成型加工機の腐蝕が起こったり、樹脂が着色を起こ
す等の問題があった。[0004] The present inventors isolated each isomer and measured their physical properties. According to the results, the melting points of α-, β-, and γ-isomers are 184-186°C, 168-171°C, and 196-196°C.
The temperature is 198°C. In addition, thermogravimetric analysis (in air, heating rate 1
0°C/min), the 5% heating weight loss temperature is 2
At 42°C, 217°C, and 245°C, the 50% heating weight loss temperatures are 255°C, 232°C, and 258°C, respectively. Therefore, the thermal stability is higher in the order of γ-HBCD, α-HBCD, and β-HBCD. HBCD used as a flame retardant is γ-
The quality of HBCD is largely influenced by the difference in the abundance ratio of these isomers. For example, when the abundance ratio of β-HBCD, which has a low melting point and low thermal stability, increases, the melting point and heat resistance of HBCD decrease. Therefore, thermal decomposition of HBCD begins to occur at a relatively low temperature, resulting in problems such as corrosion of the molding machine and coloring of the resin.
【0005】臭素をCDTに付加させる反応によってH
BCDは合成されているが、現在までに以下のようなさ
まざまな反応方法が開示されている。By the reaction of adding bromine to CDT, H
BCD has been synthesized, and various reaction methods such as those described below have been disclosed to date.
【0006】ドイツ特許第1147574号明細書には
、CDTのエチルアルコール溶液へ臭素を滴下して、臭
素付加反応を行うことが記載されてる。しかしこの方法
では、反応途中に不溶の樹脂状物が析出するため、攪拌
が困難になり、スケールアップが困難であった。さらに
このとき生成するHBCDは融点が低く、耐熱性が劣る
といった欠点があった。German Patent No. 1147574 describes that a bromine addition reaction is carried out by dropping bromine into an ethyl alcohol solution of CDT. However, in this method, insoluble resinous substances precipitate during the reaction, making stirring difficult and making scale-up difficult. Furthermore, the HBCD produced at this time has a low melting point and poor heat resistance.
【0007】[0007]
【発明が解決しようとする課題】反応途中に不溶の樹脂
状物が析出する欠点を解決するために、同様の反応方法
でいくつかの混合溶媒系が開示されている。例えば特公
昭49−24474号ではアルコールとベンゼンの混合
溶媒系そして特公昭49−24475号ではアルコール
とエステルの混合溶媒系、USP3833675号では
t−ブチルアルコ−ルとベンゼンの混合溶媒系、特公昭
50−5187号ではアルコ−ルとハロゲン系炭化水素
の混合溶媒系、EP181414号ではアルコ−ルとジ
オキサンの混合溶媒系等である。これらの溶媒で反応を
行うと、反応溶媒の溶解度が高いため反応途中の樹脂状
物の析出はなくなる。しかし生成するHBCDの融点と
耐熱性が低いため、問題が残っていた。Problems to be Solved by the Invention In order to overcome the drawback that insoluble resinous substances precipitate during the reaction, several mixed solvent systems have been disclosed for similar reaction methods. For example, in Japanese Patent Publication No. 49-24474, a mixed solvent system of alcohol and benzene, in Japanese Patent Publication No. 49-24475, a mixed solvent system of alcohol and ester, and in US Pat. No. 3,833,675, a mixed solvent system of t-butyl alcohol and benzene; No. 5187 uses a mixed solvent system of alcohol and a halogenated hydrocarbon, and EP 181414 uses a mixed solvent system of alcohol and dioxane. When the reaction is carried out in these solvents, the solubility of the reaction solvent is high, so there is no precipitation of resinous substances during the reaction. However, problems remained due to the low melting point and low heat resistance of the HBCD produced.
【0008】また、特公昭53−12510号には、反
応器に溶媒を仕込んでおき、CDTと臭素を同時に滴下
して反応する方法が示されている。しかし、生成するH
BCDの耐熱性および融点が低いという問題が残ってい
た。Furthermore, Japanese Patent Publication No. 53-12510 discloses a method in which a solvent is charged in a reactor and CDT and bromine are simultaneously added dropwise to react. However, the H
Problems remained that the heat resistance and melting point of BCD were low.
【0009】上述の反応方法では、耐熱性の高いγ−H
BCDの選択率が低いばかりではなく、臭素付加反応以
外に、アリル位の臭素化、脱臭化水素、または溶媒の臭
素化等のような副反応が起こりやすいため、収率が低下
したり、不純物がHBCDの結晶中に混入するなどの問
題があった。これらの不純物も、成型加工機の腐蝕や、
樹脂の着色の原因になることがわかっている。In the above reaction method, γ-H, which has high heat resistance,
Not only is the selectivity of BCD low, but in addition to the bromine addition reaction, side reactions such as bromination at the allylic position, dehydrobromination, or bromination of the solvent tend to occur, resulting in lower yields and the presence of impurities. There were problems such as mixing into the HBCD crystal. These impurities also cause corrosion of the molding machine,
It is known to cause discoloration of resin.
【0010】そこで、熱安定性の高いγ−HBCDの高
選択的な製造方法が求められていた[0010] Therefore, a highly selective production method of γ-HBCD with high thermal stability was required.
【0011】。[0011].
【課題を解決するための手段】本発明者らは、上記事情
に鑑み、熱安定性の高いγ−HBCDの高選択的な製造
方法について鋭意検討した結果、炭素数1〜4のアルコ
ールまたはそれを含有する有機溶媒中で、臭素とCDT
を反応させHBCDを製造する方法において、ハロゲン
化水素酸を反応溶媒中のアルコールに対して3〜30w
t/vol%加えて反応させると、加えないときに比べ
てγ−HBCDの選択率が著しく向上すること、反応溶
媒との副反応を抑えられること、さらには不純物の生成
量が著しく減少することを見出し本発明に到達した。[Means for Solving the Problems] In view of the above circumstances, the present inventors have conducted intensive studies on a highly selective production method of γ-HBCD with high thermal stability, and have developed an alcohol having 1 to 4 carbon atoms or an alcohol containing γ-HBCD. bromine and CDT in an organic solvent containing
In the method for producing HBCD by reacting, 3 to 30w of hydrohalic acid is added to the alcohol in the reaction solvent.
When t/vol% is added and reacted, the selectivity of γ-HBCD is significantly improved compared to when it is not added, side reactions with the reaction solvent can be suppressed, and the amount of impurities produced is significantly reduced. This discovery led to the present invention.
【0012】すなわち本発明は、臭素を炭素数1〜4の
アルコールまたはそれを含有する有機溶媒中で、CDT
と臭素を反応させ、HBCDを製造する方法において、
CDTと臭素の反応開始前に、ハロゲン化水素酸を反応
溶媒に中のアルコールに対して、3〜30wt/vol
%加えることを特徴とする、HBCDの製造法に関する
。That is, the present invention deals with the treatment of bromine with CDT in an alcohol having 1 to 4 carbon atoms or an organic solvent containing it.
In a method for producing HBCD by reacting with bromine,
Before starting the reaction between CDT and bromine, add 3 to 30 wt/vol of hydrohalic acid to the alcohol in the reaction solvent.
% of HBCD.
【0013】以下本発明を詳細に説明する。The present invention will be explained in detail below.
【0014】本発明の方法で用いられる溶媒は、炭素数
1〜4のアルコールまたはそれを含有する有機溶媒であ
る。炭素数1〜4のアルコールとしては、メタノール、
エタノール、n−プロパノール、イソプロパノール、n
−ブタノール、sec−ブタノール、イソブタノール、
tert−ブタノール、エチレングリコール、ジエチレ
ングリコール、プロピレングリコール等があげられる。
これらのアルコ−ルの中でエタノール、n−プロパノー
ル、tert−ブタノールなどが特に好ましい。アルコ
ールと混合する有機溶媒としては、エーテル系の溶媒、
ハロゲン系炭化水素溶媒、エステル系の溶媒があげられ
る。アルコールと混合するそれぞれの溶媒の混合比率は
特に規定されない。それぞれの溶媒の具体例としては、
エーテル系の溶媒としてはジプロピルエーテル、ジイソ
プロピルエーテル、テトラヒドロフラン(THF)、ジ
オキサン、ジエチレングリコールジメチルエーテル、ジ
エチレングリコールジエチルエーテル等が、ハロゲン系
炭化水素溶媒としては、四塩化炭素、クロロホルム、塩
化メチレン、エチレンジクロライド(EDC)等が、エ
ステル系の溶媒としては酢酸エチル、酢酸メチル、2−
メトキシエチルアセタート等があげられる。混合溶媒と
してはエタノール−酢酸エチル、エタノール−THF、
エタノール−ジオキサン、エタノール−EDC、エタノ
ール−塩化メチレン等が反応成績の面から特に好ましい
ものである。The solvent used in the method of the present invention is an alcohol having 1 to 4 carbon atoms or an organic solvent containing it. Alcohols having 1 to 4 carbon atoms include methanol,
Ethanol, n-propanol, isopropanol, n
-butanol, sec-butanol, isobutanol,
Examples include tert-butanol, ethylene glycol, diethylene glycol, propylene glycol, and the like. Among these alcohols, ethanol, n-propanol, tert-butanol and the like are particularly preferred. Examples of organic solvents that can be mixed with alcohol include ether solvents,
Examples include halogen-based hydrocarbon solvents and ester-based solvents. The mixing ratio of each solvent to be mixed with alcohol is not particularly defined. Specific examples of each solvent include:
Examples of ether solvents include dipropyl ether, diisopropyl ether, tetrahydrofuran (THF), dioxane, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, and examples of halogenated hydrocarbon solvents include carbon tetrachloride, chloroform, methylene chloride, and ethylene dichloride (EDC). ), etc., but examples of ester solvents include ethyl acetate, methyl acetate, 2-
Examples include methoxyethyl acetate. Mixed solvents include ethanol-ethyl acetate, ethanol-THF,
Ethanol-dioxane, ethanol-EDC, ethanol-methylene chloride, etc. are particularly preferred from the viewpoint of reaction results.
【0015】ハロゲン化水素酸の反応溶媒中への溶解方
法は特に限定されない。一例を挙げると、反応溶媒中に
ハロゲン化水素酸ガスを直接吹込む方法や、ハロゲン化
水素酸を含んだ反応溶媒を使用する方法、臭素と反応し
て臭化水素酸を発生するものを反応系中に添加しておく
方法等がある。[0015] The method of dissolving the hydrohalic acid in the reaction solvent is not particularly limited. Examples include a method in which hydrohalic acid gas is directly blown into the reaction solvent, a method in which a reaction solvent containing hydrohalic acid is used, and a method in which a substance that reacts with bromine to generate hydrobromic acid is used. There are methods such as adding it to the system.
【0016】ハロゲン化水素酸の添加時期については、
臭素を反応溶媒に溶解させた中にCDTを滴下して反応
させる場合には、反応溶媒と臭素の副反応を抑制するた
めに反応溶媒へ臭素を溶解する前に、反応溶媒にCDT
を溶解させた中に臭素を滴下して反応させる場合は臭素
の滴下開始前に、臭素とCDTを同時に滴下して反応さ
せる場合には、臭素とCDTを滴下する前にハロゲン化
水素酸を添加すれば良い。Regarding the timing of addition of hydrohalic acid,
When reacting by dropping CDT into bromine dissolved in a reaction solvent, add CDT to the reaction solvent before dissolving bromine in the reaction solvent to suppress side reactions between the reaction solvent and bromine.
When reacting by dropping bromine into a solution of bromine, add hydrohalic acid before dropping bromine, and when reacting by dropping bromine and CDT at the same time, add hydrohalic acid before dropping bromine and CDT. Just do it.
【0017】ハロゲン化水素酸の添加量は、反応溶媒中
のアルコールに対して3〜30wt/vol%(ハロゲ
ン化水素酸/アルコール)好ましくは5〜20wt/v
ol%が選ばれる。3wt/vol%より少ない添加量
では、ハロゲン化水素酸の添加効果が少なく、30wt
/vol%以上加えても添加効果はそれ以上向上せず、
経済的な観点からも好ましくない。The amount of hydrohalic acid added is preferably 3 to 30 wt/vol% (hydrohalic acid/alcohol) relative to the alcohol in the reaction solvent, preferably 5 to 20 wt/v.
ol% is selected. If the addition amount is less than 3wt/vol%, the effect of adding hydrohalic acid is small, and the addition amount is less than 3wt/vol%.
Even if more than /vol% is added, the addition effect does not improve any further,
It is also unfavorable from an economic point of view.
【0018】本反応で使用されるハロゲン化水素酸の種
類は、フッ化水素酸や、塩酸、臭化水素、ヨウ化水素酸
等またはこれらの混合物であり、好ましくは塩酸および
臭化水素酸である。The type of hydrohalic acid used in this reaction is hydrofluoric acid, hydrochloric acid, hydrogen bromide, hydroiodic acid, etc., or a mixture thereof, and preferably hydrochloric acid and hydrobromic acid. be.
【0019】本発明を実施するにあたっての反応方法は
、CDTを反応溶媒に溶解した中に臭素を滴下して反応
させる方法や、臭素を反応溶媒に溶解した中にCDTを
滴下して反応させる方法、反応溶媒中にCDTと臭素を
同時に滴下して反応させる方法などが考えられ何れの方
法でもかまわないが、反応溶媒中にCDTと臭素を同時
に滴下して反応させる方法が耐熱性の高いγ−HBCD
の選択率が高くなるため好ましい。The reaction method for carrying out the present invention is a method in which bromine is added dropwise to a solution of CDT in a reaction solvent, or a method in which CDT is added dropwise to a solution of bromine in a reaction solvent. , a method of simultaneously dropping CDT and bromine into the reaction solvent to cause the reaction is possible, and any method may be used, but a method of simultaneously dropping CDT and bromine into the reaction solvent to cause the reaction is a highly heat-resistant γ- HBCD
This is preferable because the selectivity of
【0020】本発明の方法を実施するにあたってのCD
Tの基質濃度(CDT/反応溶媒=wt/vol%)は
、CDTを溶媒に溶解した中に臭素を滴下して反応させ
る場合や、臭素を溶媒に溶解した中にCDTを滴下して
反応させる方法の場合、特願平2−288453号に開
示されているように、有機溶媒に対して0.1〜20w
t/vol%、好ましくは0.5〜10wt/vol%
が選ばれる。0.1%より低い濃度で反応を行っても、
0.1wt/vol%の時のγ−HBCDの選択率に比
較して、期待されるほどγ−HBCDの選択率は向上せ
ず、また経済的な見地から有用ではない。また20wt
/vol%を越えて反応を行うと、γ−HBCDの選択
率が著しく低下するため選ばれない。また、反応溶媒中
にCDTと臭素を同時に滴下する方法の場合には、有機
溶媒に対して0.1〜50wt/vol%、好ましくは
0.5〜40wt/vol%が選ばれる。0.1%より
低い濃度で反応を行っても、経済的な見地から有用では
なく、40%を越える場合は、スラリー濃度が高くなり
すぎるため好ましくない。CD for carrying out the method of the present invention
The substrate concentration of T (CDT/reaction solvent = wt/vol%) can be determined by adding bromine dropwise into a solution of CDT in a solvent, or dropping CDT into a solution of bromine in a solvent. In the case of the method, as disclosed in Japanese Patent Application No. 2-288453, 0.1 to 20 w of organic solvent is used.
t/vol%, preferably 0.5-10wt/vol%
is selected. Even if the reaction is carried out at a concentration lower than 0.1%,
Compared to the selectivity of γ-HBCD at 0.1 wt/vol%, the selectivity of γ-HBCD is not improved as expected and is not useful from an economic standpoint. Also 20wt
If the reaction is carried out in excess of /vol%, the selectivity of γ-HBCD will decrease significantly, so it is not selected. Furthermore, in the case of a method in which CDT and bromine are simultaneously added dropwise into the reaction solvent, the amount is selected to be 0.1 to 50 wt/vol%, preferably 0.5 to 40 wt/vol%, based on the organic solvent. Even if the reaction is carried out at a concentration lower than 0.1%, it is not useful from an economical point of view, and when it exceeds 40%, the slurry concentration becomes too high, which is not preferable.
【0021】本発明の方法を実施するにあたっての反応
温度は格別の限定はないが、高温で反応をおこなうと、
臭素付加反応以外の置換反応が起こりやすくなるため不
純物が増加したり、反応溶媒と臭素の反応が起こりやす
くなるため、あまり好ましくない。また極端な低温で反
応を行った場合には、溶媒の変性はおさえられるが、反
応速度がおそくなるため反応が完結せず、反応中間体で
止まるため好ましくない。反応温度は通常約−20℃〜
約50℃の範囲である。[0021] There is no particular limitation on the reaction temperature when carrying out the method of the present invention, but if the reaction is carried out at a high temperature,
This is not very preferable because substitution reactions other than bromine addition reactions tend to occur, resulting in an increase in impurities, and reactions between the reaction solvent and bromine tend to occur. Furthermore, when the reaction is carried out at an extremely low temperature, denaturation of the solvent can be suppressed, but the reaction rate is slow and the reaction is not completed and remains as a reaction intermediate, which is not preferable. The reaction temperature is usually about -20℃~
The temperature range is approximately 50°C.
【0022】本発明を実施するにあたっての反応時間は
反応方法や反応温度、仕込み量等により変わりうるが、
CDTを溶媒に溶解した中に臭素を滴下して反応させる
方法の場合、臭素の滴下時間は通常約10分ないし10
時間程度、さらにCDTの滴下が終了してから約0〜3
時間程度反応させることでなしとげられる。臭素を溶媒
に溶解した中にCDTを滴下して反応させる方法の場合
、CDTの滴下時間は通常約10分ないし10時間程度
、さらにCDTの滴下が終了してから約0〜3時間程度
反応させることでなしとげられる。反応溶媒中にCDT
と臭素を同時に滴下する方法の場合は、臭素およびCD
Tの滴下時間は通常約10分ないし20時間程度、さら
にCDTの滴下が終了してから約0〜3時間程度反応さ
せることでなしとげられる。[0022] The reaction time in carrying out the present invention may vary depending on the reaction method, reaction temperature, amount charged, etc.
In the case of a method of reacting by dropping bromine into CDT dissolved in a solvent, the dropping time of bromine is usually about 10 minutes to 10 minutes.
Approximately 0 to 3 hours, and approximately 0 to 3 hours after CDT has finished dropping.
This can be accomplished by reacting for about an hour. In the case of a method of reacting by dropping CDT into a solution of bromine in a solvent, the dropping time of CDT is usually about 10 minutes to 10 hours, and the reaction is continued for about 0 to 3 hours after the dropping of CDT is finished. It can be achieved by doing this. CDT in reaction solvent
In the case of the method of dropping bromine and bromine at the same time, bromine and CD
The time for dropping T is usually about 10 minutes to 20 hours, and the reaction can be completed for about 0 to 3 hours after the dropping of CDT is completed.
【0023】CDTに対する臭素の使用量は、Br2/
CDT(モル比)で3.0以上、好ましくは3.0〜5
.0である。3.0未満では、CDTに対して臭素が不
足しているため、反応が完結しない。5.0を越える場
合では、過剰臭素による副反応が起こりやすくなること
と、経済的な見地からも好ましくない。The amount of bromine used for CDT is Br2/
CDT (molar ratio) of 3.0 or more, preferably 3.0 to 5
.. It is 0. If it is less than 3.0, the reaction will not be completed due to the lack of bromine relative to CDT. If it exceeds 5.0, side reactions due to excess bromine are likely to occur and it is also unfavorable from an economic standpoint.
【0024】反応終了後生成したHBCDは公知の手段
で粉体として単離できる。例えば、析出した結晶をその
まま濾過する方法や反応終了時の反応液を貧溶媒に投入
することで結晶を取り上げる方法、反応終了時の反応液
に貧溶媒を投入する方法などが考えられる。さらにろ液
として回収された溶媒は、新しい溶媒を補充することで
反応溶媒として繰り返し使用することができる。[0024] After the completion of the reaction, the HBCD produced can be isolated as a powder by known means. For example, there may be a method in which the precipitated crystals are directly filtered, a method in which the reaction solution at the end of the reaction is poured into a poor solvent to pick up the crystals, a method in which a poor solvent is introduced into the reaction solution at the end of the reaction, and the like. Furthermore, the solvent recovered as a filtrate can be repeatedly used as a reaction solvent by replenishing it with new solvent.
【0025】[0025]
【発明の効果】本発明の方法を実施することにより、H
BCDのγ−体を高選択率、高収率で製造できるように
なった。また、色相、熱安定性に優れたHBCDを製造
できるようになった。Effect of the invention: By carrying out the method of the present invention, H
It has become possible to produce the γ-form of BCD with high selectivity and high yield. In addition, it has become possible to manufacture HBCD with excellent hue and thermal stability.
【0026】[0026]
【実施例】以下、実施例に従って本発明を更に詳しく説
明するが、本発明はこれらにより限定されるものではな
い。EXAMPLES The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.
【0027】実施例1〜4
還流冷却器、撹拌羽根を装備した丸底フラスコに、表1
に示す組成になるように反応溶媒とHBrを仕込んだ。
その中に表1に示す量のCDTと臭素を15℃で2時間
かけて滴下することで反応させた。滴下終了後、さらに
2時間熟成した。反応終了後の反応スラリー液を高速液
体クロマトグラフィー(カラム TSKゲル−ODS
80TM、溶離液 アセトニトリル/水=80/20
vol%、検出器 UV215nm)で分析しその結
果をまとめて表1に示した。なお同定できない成分につ
いては不明分とした。表1中のDBCD(ジブロモシク
ロドデカジエン)、TBCD(テトラブロモシクロドデ
セン)は、HBCDの反応中間体である。なおTBCD
には異性体が存在するので、高速液体クロマトグラフィ
ーでODS逆相カラムを用いて分析し、カラムから溶出
する順番にα−TBCD、β−TBCDと命名した。Examples 1 to 4 A round-bottomed flask equipped with a reflux condenser and a stirring blade was filled with
The reaction solvent and HBr were charged so as to have the composition shown below. CDT and bromine in the amounts shown in Table 1 were added dropwise thereto at 15° C. over 2 hours to cause a reaction. After the addition was completed, the mixture was further aged for 2 hours. After the reaction, the reaction slurry was subjected to high performance liquid chromatography (column TSK gel-ODS).
80TM, eluent acetonitrile/water = 80/20
vol%, detector UV 215 nm) and the results are summarized in Table 1. In addition, components that could not be identified were classified as unknown. DBCD (dibromocyclododecadiene) and TBCD (tetrabromocyclododecene) in Table 1 are reaction intermediates of HBCD. Furthermore, TBCD
Since there are isomers, they were analyzed by high-performance liquid chromatography using an ODS reverse phase column and named α-TBCD and β-TBCD in the order of elution from the column.
【0028】γ−HBCDの選択率は、γ−HBCDの
生成量をHBCD異性体の合計量で割った値で示した[
γ−HBCD/(α−TBCD+β−TBCD+γ−H
BCD)]。The selectivity of γ-HBCD was expressed as the amount of γ-HBCD produced divided by the total amount of HBCD isomers [
γ-HBCD/(α-TBCD+β-TBCD+γ-H
BCD)].
【0029】反応終了時の反応液をろ過し、得られた結
晶を乾燥させ融点を測定し、その結果をまとめて表1に
示した。[0029] At the end of the reaction, the reaction solution was filtered, the obtained crystals were dried, and the melting point was measured. The results are summarized in Table 1.
【0030】実施例5〜8
還流冷却器、撹拌羽根を装備した丸底フラスコに、表1
に示す組成になるように反応溶媒とHBrと臭素を仕込
んだ。その中に表1に示す量のCDTを15℃で2時間
かけて滴下することで反応させた。滴下終了後、さらに
2時間熟成した。反応終了後、実施例と同様な方法で後
処理と分析を行いその結果をまとめて表1に示した。Examples 5 to 8 Table 1 was added to a round bottom flask equipped with a reflux condenser and a stirring blade.
A reaction solvent, HBr, and bromine were charged so as to have the composition shown below. The amount of CDT shown in Table 1 was added dropwise into the solution at 15° C. over 2 hours to cause a reaction. After the addition was completed, the mixture was further aged for 2 hours. After the reaction was completed, post-treatment and analysis were performed in the same manner as in the examples, and the results are summarized in Table 1.
【0031】実施例9
還流冷却器、撹拌羽根を装備した丸底フラスコに、表1
に示す組成になるように反応溶媒とHBrとCDTを仕
込んだ。その中に表1に示す量の臭素を15℃で2時間
かけて滴下することで反応させた。滴下終了後、さらに
2時間熟成した。反応終了後、実施例と同様な方法で後
処理と分析を行いその結果をまとめて表1に示した。Example 9 In a round bottom flask equipped with a reflux condenser and a stirring blade,
A reaction solvent, HBr, and CDT were charged so as to have the composition shown below. Bromine in the amount shown in Table 1 was added dropwise thereto at 15° C. over 2 hours to cause a reaction. After the addition was completed, the mixture was further aged for 2 hours. After the reaction was completed, post-treatment and analysis were performed in the same manner as in the examples, and the results are summarized in Table 1.
【0032】[0032]
【表1】
比較例1
還流冷却器、撹拌羽根を装備した丸底フラスコに、表2
に示す組成の反応溶媒を仕込んだ。その中に表2に示す
量のCDTと臭素を15℃で2時間かけて滴下すること
で反応させた。滴下終了後、さらに2時間熟成した。反
応終了後、実施例と同様な方法で後処理と分析を行いそ
の結果をまとめて表2に示した。[Table 1] Comparative Example 1 Table 2 was placed in a round bottom flask equipped with a reflux condenser and a stirring blade.
A reaction solvent having the composition shown in was charged. CDT and bromine in the amounts shown in Table 2 were added dropwise thereto at 15° C. over 2 hours to cause a reaction. After the addition was completed, the mixture was further aged for 2 hours. After the reaction was completed, post-treatment and analysis were carried out in the same manner as in the examples, and the results are summarized in Table 2.
【0033】比較例2,3
還流冷却器、撹拌羽根を装備した丸底フラスコに、表2
に示す組成の反応溶媒と臭素を仕込んだ。その中に表2
に示す量のCDTを15℃で2時間かけて滴下すること
で反応させた。滴下終了後、さらに2時間熟成した。反
応終了後、実施例と同様な方法で後処理と分析を行いそ
の結果をまとめて表2に示した。Comparative Examples 2 and 3 Table 2 was placed in a round bottom flask equipped with a reflux condenser and a stirring blade.
A reaction solvent with the composition shown below and bromine were charged. Table 2 in it
The reaction was carried out by adding dropwise the amount of CDT shown in the figure over a period of 2 hours at 15°C. After the addition was completed, the mixture was further aged for 2 hours. After the reaction was completed, post-treatment and analysis were carried out in the same manner as in the examples, and the results are summarized in Table 2.
【0034】比較例4
還流冷却器、撹拌羽根を装備した丸底フラスコに、表2
に示す組成の反応溶媒とCDTを仕込んだ。その中に表
2に示す量の臭素を15℃で2時間かけて滴下すること
で反応させた。滴下終了後、さらに2時間熟成した。反
応終了後、実施例と同様な方法で後処理と分析を行いそ
の結果をまとめて表2に示した。Comparative Example 4 Table 2 was placed in a round bottom flask equipped with a reflux condenser and a stirring blade.
A reaction solvent having the composition shown below and CDT were charged. Bromine in the amount shown in Table 2 was added dropwise thereto at 15° C. over 2 hours to cause a reaction. After the addition was completed, the mixture was further aged for 2 hours. After the reaction was completed, post-treatment and analysis were carried out in the same manner as in the examples, and the results are summarized in Table 2.
【0035】[0035]
【表2】[Table 2]
Claims (1)
有する有機溶媒中で、臭素を1,5,9−シス,トラン
ス,トランス−シクロドデカトリエンと反応させ、1,
2,5,6,9,10−ヘキサブロモシクロドデカンを
製造する方法において、ハロゲン化水素酸を反応溶媒中
のアルコールに対して、3〜30wt/vol%加える
ことを特徴とする、1,2,5,6,9,10−ヘキサ
ブロモシクロドデカンの製造法。Claim 1: Reacting bromine with 1,5,9-cis,trans,trans-cyclododecatriene in an alcohol having 1 to 4 carbon atoms or an organic solvent containing it,
A method for producing 2,5,6,9,10-hexabromocyclododecane, characterized in that 3 to 30 wt/vol% of hydrohalic acid is added to the alcohol in the reaction solvent. , 5,6,9,10-hexabromocyclododecane manufacturing method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3137078A JP3044829B2 (en) | 1991-05-14 | 1991-05-14 | Method for producing hexabromocyclododecane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3137078A JP3044829B2 (en) | 1991-05-14 | 1991-05-14 | Method for producing hexabromocyclododecane |
Publications (2)
Publication Number | Publication Date |
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JPH04338344A true JPH04338344A (en) | 1992-11-25 |
JP3044829B2 JP3044829B2 (en) | 2000-05-22 |
Family
ID=15190385
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3137078A Expired - Fee Related JP3044829B2 (en) | 1991-05-14 | 1991-05-14 | Method for producing hexabromocyclododecane |
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Country | Link |
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JP (1) | JP3044829B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000050368A1 (en) * | 1999-02-22 | 2000-08-31 | Albemarle Corporation | An improved process for producing hexabromocyclododecane |
US6506952B2 (en) | 1999-02-22 | 2003-01-14 | Albemarle Corporation | Production of hexabromocyclododecane of enhanced gamma isomer content |
KR100407857B1 (en) * | 2000-12-22 | 2003-12-01 | 주식회사 상화 | Preparation Method Of Hexabromocyclododecane |
-
1991
- 1991-05-14 JP JP3137078A patent/JP3044829B2/en not_active Expired - Fee Related
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000050368A1 (en) * | 1999-02-22 | 2000-08-31 | Albemarle Corporation | An improved process for producing hexabromocyclododecane |
US6420617B1 (en) | 1999-02-22 | 2002-07-16 | Albemarle Corporation | Process for producing hexabromocyclododecane |
US6506952B2 (en) | 1999-02-22 | 2003-01-14 | Albemarle Corporation | Production of hexabromocyclododecane of enhanced gamma isomer content |
AU779279B2 (en) * | 1999-02-22 | 2005-01-13 | Albemarle Corporation | An improved process for producing hexabromocyclododecane |
KR100407857B1 (en) * | 2000-12-22 | 2003-12-01 | 주식회사 상화 | Preparation Method Of Hexabromocyclododecane |
Also Published As
Publication number | Publication date |
---|---|
JP3044829B2 (en) | 2000-05-22 |
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