JPH0338563A - Production of ethylene oxide adduct to tetrabromobisphenol s - Google Patents
Production of ethylene oxide adduct to tetrabromobisphenol sInfo
- Publication number
- JPH0338563A JPH0338563A JP1173789A JP17378989A JPH0338563A JP H0338563 A JPH0338563 A JP H0338563A JP 1173789 A JP1173789 A JP 1173789A JP 17378989 A JP17378989 A JP 17378989A JP H0338563 A JPH0338563 A JP H0338563A
- Authority
- JP
- Japan
- Prior art keywords
- tetrabromobisphenol
- ethylene oxide
- reaction
- solvent
- alcohol
- 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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 27
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000002904 solvent Substances 0.000 claims abstract description 27
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 8
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 abstract description 6
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 abstract description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 abstract description 4
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 abstract description 4
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007259 addition reaction Methods 0.000 abstract description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 abstract description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 35
- 239000013078 crystal Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 150000002009 diols Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000004040 coloring Methods 0.000 description 5
- -1 polyethylene terephthalate Polymers 0.000 description 5
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- BTANRVKWQNVYAZ-SCSAIBSYSA-N (2R)-butan-2-ol Chemical compound CC[C@@H](C)O BTANRVKWQNVYAZ-SCSAIBSYSA-N 0.000 description 3
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 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 2
- OFBQIWFJRDGFEK-UHFFFAOYSA-N 2-[2,6-dibromo-4-[3,5-dibromo-4-(2-hydroxyethoxy)phenyl]sulfonylphenoxy]ethanol Chemical compound C1=C(Br)C(OCCO)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(OCCO)C(Br)=C1 OFBQIWFJRDGFEK-UHFFFAOYSA-N 0.000 description 2
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical compound CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 2
- 150000001298 alcohols 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
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ASHVGNGFCXYXBN-UHFFFAOYSA-M 1-benzyl-2-methylpyridin-1-ium;chloride Chemical compound [Cl-].CC1=CC=CC=[N+]1CC1=CC=CC=C1 ASHVGNGFCXYXBN-UHFFFAOYSA-M 0.000 description 1
- TVFWSIQTAXZIPC-UHFFFAOYSA-M 1-dodecyl-2-methylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1C TVFWSIQTAXZIPC-UHFFFAOYSA-M 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- 229910052786 argon Inorganic materials 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-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
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-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
- 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
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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はテトラブロモビスフェノールＳのアルキレンオ
キシド付加物の製造方法の改良に関するものである。さ
らに詳しくいえば、本発明は、テトラブロモビスフェノ
ールＳの２個の水酸基それぞれに実質上１モルのエチレ
ンオキシド又はプロピレンオキシドが付加して成る、高
純度で着色の少ないジオール類を効率よく製造する方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an improvement in a method for producing an alkylene oxide adduct of tetrabromobisphenol S. More specifically, the present invention relates to a method for efficiently producing highly pure and less colored diols, which are obtained by adding substantially 1 mole of ethylene oxide or propylene oxide to each of the two hydroxyl groups of tetrabromobisphenol S. It is something.
［従来の技術］
従来、式
で表されるテトラブロモビスフェノールＳに、エチレン
オキシドやプロピレンオキシドなどのアルキレンオキシ
ドを付加させて得られるジオール類は、例えばポリエチ
レンテレフタレートやポリブチレンテレフタレートなど
のポリエステル用の添加型難燃剤及び反応性難燃剤など
として有用であることが知られている。そして、前記ジ
オール類は、このような難燃剤として使用するためには
、アルキレンオキシドの付加していないフェノール性水
酸基が残存している不純物や、アルキレンオキシドがテ
トラブロモビスフェノール５１モルに対し、３モル以上
付加した不純物が少ないなど、純度が高く、かつ着色が
少なくて色相が良好であることが望まれている。[Prior Art] Conventionally, diols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to tetrabromobisphenol S represented by the formula have been used as additive-type diols for polyesters such as polyethylene terephthalate and polybutylene terephthalate. It is known to be useful as a flame retardant and a reactive flame retardant. In order for the diols to be used as such flame retardants, impurities such as residual phenolic hydroxyl groups to which alkylene oxide has not been added, and alkylene oxide containing 3 mol per 51 mol of tetrabromobisphenol are required. It is desired that the purity is high, such as having a small amount of added impurities, and that the coloring is low and the hue is good.
このようなテトラブロモビスフェノールＳにアルキレン
オキシドか付加して成るジオール類の製造方法としては
、これまで種々の方法が提案されている。例えば（１）
溶媒中においてアルカリ性触媒の存在下、ジヒドロキシ
ジフェニルスルホン類を、その水酸基に対して等モル量
以下のアルキレンオキシドと反応させ、次いで溶媒を系
外へ除去しｔ；のち、さらにアルキレンオキシドを加え
て反応させる方法（特開昭５０−１２３６３８号公報）
、（２）極性有機溶媒及び水を含む混合溶媒中において
、塩基性触媒の存在下に、臭素化ビスフェノールＳをア
ルキレンオキシドと反応させる方法（特開昭５２−５１
３５１号公報）、（３）触媒として有機カルボン酸のナ
トリウム又はカリウム塩を用い、ハロゲン化ジフェノー
ル類に、アルキレンオキシドを付加させる方法（特開昭
５２−６２２３２号公報）、（４）ジメチルホルムアミ
ド溶媒中において、トリエチレンジアミン触媒の存在下
、テトラブロモビスフェノールＳをエチレンオキシドと
反応させる方法（特開昭５９−１１２０７３号公報）、
（５）テトラブロモビスフェノールＡ又はテトラブロモ
ビスフェノールＳをアルキレンオキシドによりスラリー
状とし、第三級アミン触媒の存在下に反応させる方法（
特開昭６１−１４８１３号公報）などが開示されている
。Various methods have been proposed so far for producing diols obtained by adding alkylene oxide to tetrabromobisphenol S. For example (1)
In the presence of an alkaline catalyst in a solvent, dihydroxydiphenyl sulfones are reacted with alkylene oxide in an amount equal to or less than the molar amount relative to the hydroxyl group, and then the solvent is removed from the system; after that, further alkylene oxide is added and the reaction is carried out. (Japanese Unexamined Patent Publication No. 123638/1983)
, (2) A method of reacting brominated bisphenol S with an alkylene oxide in a mixed solvent containing a polar organic solvent and water in the presence of a basic catalyst (Japanese Patent Application Laid-Open No. 52-51
351 Publication), (3) A method of adding alkylene oxide to halogenated diphenols using a sodium or potassium salt of an organic carboxylic acid as a catalyst (Japanese Unexamined Patent Publication No. 52-62232), (4) Dimethylformamide A method of reacting tetrabromobisphenol S with ethylene oxide in the presence of a triethylenediamine catalyst in a solvent (Japanese Patent Application Laid-open No. 112073/1983),
(5) A method in which tetrabromobisphenol A or tetrabromobisphenol S is slurried with alkylene oxide and reacted in the presence of a tertiary amine catalyst (
JP-A-61-14813) and the like are disclosed.
しかしながら、（１）の方法においては、反応系の圧力
を加圧、常圧ないし減圧、再び加圧と変化させ、かつ反
応の途中で溶媒を留去するなど、煩雑な操作を必要とす
る上、アルキレンオキシドの消費量も比較的多くなるな
どの欠点があるし、（２）の方法は、混合溶媒を用いる
ため、溶媒を回収、精製し、再使用するには不都合であ
るという欠点を有している。また、（３）の方法におい
ては、生成物の純度に問題があるし、（４）の方法にお
いては、反応終了後、反応混合物を水中に加えて、生成
物を析出させる例が示されているか（実施例１）、この
除虫じるジメチルホルムアミドと水との混合物の処理が
極めて困難であり、さらに（５）の方法においては、生
成物の色相が必ずしも十分に良好ではないという欠点が
ある。However, method (1) requires complicated operations, such as changing the pressure of the reaction system from pressurization, normal pressure to reduced pressure, and pressurization again, and distilling off the solvent during the reaction. However, method (2) has disadvantages such as a relatively large amount of alkylene oxide consumed, and method (2) uses a mixed solvent, which makes it inconvenient to recover, purify, and reuse the solvent. are doing. In addition, in method (3), there is a problem with the purity of the product, and in method (4), an example is shown in which the reaction mixture is added to water after the reaction is completed to precipitate the product. In addition, the method (5) has the disadvantage that the color of the product is not necessarily good enough. be.
このように、従来のテトラブロモビスフェノールＳにア
ルキレンオキシドが付加して成るジオール類の製造につ
いては、必ずしも十分に満足しうる方法が見い出されて
ζ）ないのが実状である。As described above, the reality is that no fully satisfactory method has been found for producing diols formed by adding alkylene oxide to conventional tetrabromobisphenol S.
［発明が解決しようとする課題］
本発明は、このような事情のもとで、テトラブロモビス
フェノールＳの２個の水酸基それぞれに、実質上１モル
のエチレンオキシド又はプロピレンオキシドが付加して
成る、高純度で着色の少ないジオール類を、効率よく工
業的有利に製造する方法を提供することを目的としてな
されたものである。[Problems to be Solved by the Invention] Under these circumstances, the present invention provides a polymer in which substantially 1 mole of ethylene oxide or propylene oxide is added to each of the two hydroxyl groups of tetrabromobisphenol S. The purpose of this invention is to provide an efficient and industrially advantageous method for producing diols with high purity and little coloring.
［課題を解決するだめの手段］
本発明者らは、前記目的を達成するために鋭意研究を重
ねＩ；結果、特定の溶媒及び触媒を用い、テトラブロモ
ビスフェノールＳをエチレンオキシド又はプロピレンオ
キシドと反応させることにより、その目的を達成しうろ
ことを見い出し、この知見に基づいて本発明を完成する
に至った。[Means for Solving the Problems] In order to achieve the above object, the present inventors have conducted extensive research; as a result, tetrabromobisphenol S is reacted with ethylene oxide or propylene oxide using a specific solvent and catalyst. As a result, the inventors discovered that the object could be achieved, and based on this knowledge, they completed the present invention.
すなわち、本発明は、テトラブロモビス７エ７−ｊしＳ
にエチレンオキシド又はプロピレンオキシドを付加させ
て、テトラブロモビスフェノールＳのアルキレンオキシ
ド付加物を製造するに当り、溶媒として炭素数４〜６の
アルコール類を用い、かつ触媒として第四級アンモニウ
ム塩を用いることを特徴とするテトラブロモビスフェノ
ールＳのアルキレンオキシド付加物の製造方法を提供す
るものである。That is, the present invention provides tetrabromobis7E7-j and S
When producing an alkylene oxide adduct of tetrabromobisphenol S by adding ethylene oxide or propylene oxide to it, it is recommended to use an alcohol having 4 to 6 carbon atoms as a solvent and a quaternary ammonium salt as a catalyst. The present invention provides a method for producing a characteristic alkylene oxide adduct of tetrabromobisphenol S.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明方法においては、溶媒として炭素数４〜６のアル
コール類を用いることが必要である。In the method of the present invention, it is necessary to use an alcohol having 4 to 6 carbon atoms as a solvent.
この炭素数４〜６のアルコール類としては、例えばｌ−
ブタノール、２−ブタノール、イソブチルアルコール、
ｔｅｒｔ−ブチルアルコール、ｌ−ペンタノール、２−
ペンタノール、３−ペンタノール、２−メチル−１−ブ
タノール、イソペンチルアルコール、ｔａｒｔ−ペンチ
ルアル１−ル）３−メチル−２−ブタノール、ネオペン
チルアルコール、ｌ−ヘキサノール、２−メチル−１−
ペンタノール、４−メチル−２−ペンタノール、２−エ
チル−１−ブタノール、シクロヘキサノールなどが挙げ
られる。これらのアルコール類は１種用いてもよいし、
２種以上を混合して用いてもよい。Examples of alcohols having 4 to 6 carbon atoms include l-
Butanol, 2-butanol, isobutyl alcohol,
tert-butyl alcohol, l-pentanol, 2-
Pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tart-pentylar) 3-methyl-2-butanol, neopentyl alcohol, l-hexanol, 2-methyl-1-
Examples include pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, and cyclohexanol. One type of these alcohols may be used, or
Two or more types may be mixed and used.
この溶媒として、炭素数３以下のアルコール類、例えば
メタノールやエタノールを用いると反応速度が極めて遅
く、実用的でないし、１−プロパノールや２−プロパノ
ールを用いると反応は進行するものの、反応中に生じた
着色不純物が溶媒中にとどまらず、析出した結晶中に移
行し、着色した生成物を与えるなど好ましくない事態を
招来する。If an alcohol with a carbon number of 3 or less, such as methanol or ethanol, is used as this solvent, the reaction rate will be extremely slow and it is not practical, and if 1-propanol or 2-propanol is used, the reaction will proceed, but no gas will be generated during the reaction. The colored impurities do not stay in the solvent but migrate into the precipitated crystals, resulting in undesirable situations such as giving a colored product.
一方、溶媒として炭素数７以上のアルコール類を用いる
と反応速度が遅くなり実用的でない。また、前記炭素数
４〜６のアルコール類には、本発明の目的を損なわない
範囲で、所望に応じ他の溶媒を添加することもできる。On the other hand, if an alcohol having 7 or more carbon atoms is used as a solvent, the reaction rate becomes slow and is not practical. Further, other solvents may be added to the alcohol having 4 to 6 carbon atoms as desired within a range that does not impair the object of the present invention.
本発明方法における前記溶媒の使用量については特に制
限はないが、通常テトラブロモビスフェノールＳの使用
量の１〜５重量倍、好ましくは１．５〜３重量倍の範囲
で用いられる。この溶媒の量が１重量倍未満では反応終
了後の反応混合物の流動性が不足して、反応器からの取
り出しが困勉となるおそれがあるし、５重量倍を超える
と反応器効率が低下するのみで、特別な利点は得られず
好ましくない。The amount of the solvent used in the method of the present invention is not particularly limited, but it is usually used in an amount of 1 to 5 times, preferably 1.5 to 3 times, the amount of tetrabromobisphenol S used. If the amount of this solvent is less than 1 times by weight, the fluidity of the reaction mixture after the completion of the reaction may be insufficient, making it difficult to take it out from the reactor, while if it exceeds 5 times by weight, the reactor efficiency will decrease. This is not preferable as it does not provide any special benefits.
本発明方法においては、触媒として第四級アンモニウム
塩を用いることが必要である。この第四級アンモニウム
塩としては、例えば塩化テトラメチルアンモニウム、塩
化テトラエチルアンモニウム、塩化テトラブチルアンモ
ニウム、塩化ベンジルトリメチルアンモニウム、塩化ベ
ンジルトリエチルアンモニウム、塩化ベンジルトリブチ
ルアンモニウム、塩化メチルトリオクチルアンモニウム
、塩化−Ｎ−ラウリルピリジニウム、塩化−Ｎ−ラウリ
ルピコリニウム、塩化−Ｎ−ベンジルピコリニウム、臭
化テトラメチルアンモニウム、臭化テトラエチルアンモ
ニウム、臭化テトラブチルアンモニウム、臭化フェニル
トリメチルアンモニウム、臭化ベンジルトリエチルアン
モニウム、ヨウ化テトラメチルアンモニウム、ヨウ化テ
トラブチルアンモニウム、水酸化テトラメチルアンモニ
ウム、テトラブチルアンモニウムハイドロゲンサル７工
一トなどを挙げることができる。In the process of the invention it is necessary to use a quaternary ammonium salt as a catalyst. Examples of the quaternary ammonium salt include tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, methyltrioctylammonium chloride, and -N-lauryl chloride. Pyridinium, N-laurylpicolinium chloride, N-benzylpicolinium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, phenyltrimethylammonium bromide, benzyltriethylammonium bromide, tetraiodide Examples include methylammonium, tetrabutylammonium iodide, tetramethylammonium hydroxide, and tetrabutylammonium hydrogen salt.
これらの第四級アンモニウム塩は、それぞれ単独で用い
てもよいし、２種以上を組み合わせて用いてもよく、ま
た、その使用量はテトラブロモビスフェノールＳに対し
て、通常１〜２０モル％、好ましくは５〜ｌＯモル％の
範囲で選ばれる。この量が１モル％未満では反応速度が
遅く、未反応の７エノール性水酸基が残りやすくなるし
、２０モル％を超えるとその量の割には効果の向上は認
められず、むしろ経済的に不利となり、好ましくない。These quaternary ammonium salts may be used alone or in combination of two or more, and the amount used is usually 1 to 20 mol% based on tetrabromobisphenol S. It is preferably selected within the range of 5 to 10 mol%. If this amount is less than 1 mol%, the reaction rate will be slow and unreacted 7-enol hydroxyl groups will likely remain; if it exceeds 20 mol%, no improvement in effectiveness will be observed for the amount, and rather it will be economically disadvantageous. This is disadvantageous and undesirable.
本発明方法における反応温度は、通常７０〜１５０℃、
好ましくは９０〜１３０℃の範囲で選ばれる。この反応
温度が７０′ｃ未満では反応速度が遅くて実用的でない
し、１５０℃を超えると溶媒のアルコール類へのエチレ
ンオキシド又はプロピレンオキシドの付加が起こるよう
になるので好ましぐない。また、該反応は不活性ガス雰
囲気下、例えば窒素、アルゴン、ヘリウムなどの不活性
ガス雰囲気下で行うことが望ましい。The reaction temperature in the method of the present invention is usually 70 to 150°C,
Preferably, the temperature is selected within the range of 90 to 130°C. If the reaction temperature is less than 70'C, the reaction rate is too slow to be practical, and if it exceeds 150C, ethylene oxide or propylene oxide will be added to the solvent alcohol, which is not preferred. Further, the reaction is desirably carried out under an inert gas atmosphere, for example, an inert gas atmosphere such as nitrogen, argon, helium or the like.
次に、本発明の好適な実施態様の１例について説明する
と、まず、耐圧性の反応器に、それぞれ所要量のテトラ
ブロモビスフェノールＳと炭素ａ４〜６のアルコール類
と第四級アンモニウム塩とを仕込み、反応系内を窒素な
どの不活性ガスで置換したのち、内容物を所定の温度ま
で加熱し、次いで、これにエチレンオキシド又はプロピ
レンオキシドを圧入して、付加反応を起こさせる。エチ
レンオキシド又はプロピレンオキシドの圧入による圧力
増加は０．１〜４ 、０ ｋｇ／ ｃｍ”、好ましくは
０．２−２．０ ｋｇ／ｃｔａ’の範囲ｌ；なるように
制御することが望ましい。エチレンオキシドやプロピレ
ンオキシドの分圧が低すぎると反応速度が遅いし、高す
ぎると反応速度が速くなり、反応熱の制御が困難となる
ので好ましくない。Next, one example of a preferred embodiment of the present invention will be described. First, tetrabromobisphenol S, a4-6 carbon alcohol, and a quaternary ammonium salt are respectively placed in a pressure-resistant reactor in required amounts. After charging and purging the reaction system with an inert gas such as nitrogen, the contents are heated to a predetermined temperature, and then ethylene oxide or propylene oxide is pressurized into the mixture to cause an addition reaction. It is desirable to control the pressure increase due to the injection of ethylene oxide or propylene oxide so that it is in the range of 0.1 to 4.0 kg/cm'', preferably 0.2 to 2.0 kg/cta'. If the partial pressure of propylene oxide is too low, the reaction rate will be slow, and if it is too high, the reaction rate will be too high, making it difficult to control the reaction heat, which is not preferable.
反応が進行するに伴い、反応器の内圧が低下するので、
一定圧力を保持するように、さらにエチレンオキシド又
はプロピレンオキシドを圧入する。As the reaction progresses, the internal pressure of the reactor decreases, so
Further ethylene oxide or propylene oxide is injected to maintain a constant pressure.
反応が終了するとエチレンオキシド又はプロピレンオキ
シドが消費されなくなり、反応系の圧力が変化しなくな
るので、反応混合物を室温まで冷却して取り出しＩ；の
ち、ろ過などの手段によってテトラブロモビスフェノー
ルＳのエチレンオキシド又はプロピレンオキシド付加物
を分離、回収し、次いで適当な溶媒、例えば反応に用い
ｌ；溶媒と同じ溶媒、又は反応に用いた溶媒と相溶性が
あり、かつ第四級アンモニウム塩を溶解しうる溶媒など
で洗浄したのち、乾燥することにより、テトラブロモビ
スフェノールＳの２個の水酸化基それぞれに、実質上１
モルのエチレンオキシド又はプロピレンオキシドが付加
して成る純度が高く、かつ着色のないジオール類が得ら
れる。When the reaction is completed, ethylene oxide or propylene oxide is no longer consumed and the pressure of the reaction system does not change, so the reaction mixture is cooled to room temperature and taken out. The adduct is separated, collected, and then washed with a suitable solvent, such as the same solvent as the solvent used in the reaction, or a solvent that is compatible with the solvent used in the reaction and can dissolve the quaternary ammonium salt. After that, by drying, each of the two hydroxyl groups of tetrabromobisphenol S has substantially 1
Diols with high purity and no coloration are obtained by adding moles of ethylene oxide or propylene oxide.
この反応においては、テトラブロモビスフェノールＳと
炭素数４〜６のアルコール類と第四級アンモニウム塩と
を混合して加熱した状態では、テトラブロモビスフェノ
ールＳは溶媒中に溶解せず、反応系は不均一な分散状態
となっているが、アルキレンオキシドの付加反応が起こ
ると溶解性が大きくなり、反応系は完全な均一な状態又
はかなり透明性の高い状態となる。さらに反応が進むと
、生成物が結晶として析出してきて、反応混合物は再び
不均一な状態となる。まｔ；、反応中に着色しｔ；不純
物が上広するか、反応が終了して、反応混合物を冷却し
た際、着色不純物は溶媒中に溶解しているので、反応混
合物より析出した結晶を、ろ過などの手段により分離、
回収し、適当な溶媒で洗浄すれば、着色のない、色相の
良好なテトラブロモビスフェノールＳのアルキレンオキ
シド付加物が得られる。In this reaction, when tetrabromobisphenol S, an alcohol having 4 to 6 carbon atoms, and a quaternary ammonium salt are mixed and heated, tetrabromobisphenol S does not dissolve in the solvent and the reaction system remains undissolved. Although it is in a uniformly dispersed state, when the alkylene oxide addition reaction occurs, the solubility increases and the reaction system becomes completely homogeneous or highly transparent. As the reaction progresses further, the product precipitates out as crystals, and the reaction mixture becomes heterogeneous again. Either the impurities are colored during the reaction, or when the reaction is completed and the reaction mixture is cooled, the colored impurities are dissolved in the solvent, so the crystals precipitated from the reaction mixture are removed. , separated by means such as filtration,
By collecting and washing with an appropriate solvent, an alkylene oxide adduct of tetrabromobisphenol S with good color and no coloring can be obtained.
〔実施例］
次に、実施例により本発明をさらに詳細に説明するが、
本発明はこれらの例によってなんら限定されるものでは
ない。[Example] Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these examples.
なお、例中の圧力はゲージ圧力を示す。Note that the pressure in the examples indicates gauge pressure.
実施例 １
撹拌装置付耐圧反応器に、テトラブロモビスフェノール
５１００ｇ、ｌ−ブタノール２００ｇ、塩化ベンジルト
リメチルアンモニウム３．０ｇを仕込み、反応器内部を
窒素で置換したのち、内温を１２０℃まで上昇させ、反
応器内の圧力が１ 、３ ｋｇ／ ｃｍ”になるようエ
チレンオキシドを圧入した。内圧が１ 、３ ｋｇ／
ｃｒａ”を保つようエチレンオキシドを圧入しながら、
１２０℃で反応を統けＩ；ところ、５時間後に、もはや
圧力が低下しなくなった。この時点までに圧入したエチ
レンオキシドは１７．５９であった。次いで、反応混合
物を冷却して取り出し、ろ別したところ、着色した成分
はろ液中に溶解しており、エチレンオキシド付加物は白
色の結晶として得られた。この結晶をさらにメタノール
で洗浄したのち乾燥し、ビス（３，５−ジブロモ−４−
β−ヒドロキシエトキシフェニル）スルホン９８．４９
を得た。液体クロマトグラフィーで測定したところ、純
度は９８．２％であった。Example 1 5100 g of tetrabromobisphenol, 200 g of l-butanol, and 3.0 g of benzyltrimethylammonium chloride were charged into a pressure-resistant reactor equipped with a stirring device, and after purging the inside of the reactor with nitrogen, the internal temperature was raised to 120 ° C. Ethylene oxide was pressurized so that the pressure inside the reactor was 1.3 kg/cm.The internal pressure was 1.3 kg/cm.
While pressurizing ethylene oxide to maintain the
The reaction was carried out at 120° C.; however, after 5 hours, the pressure no longer decreased. The amount of ethylene oxide injected up to this point was 17.59. Then, the reaction mixture was cooled, taken out, and filtered. The colored components were dissolved in the filtrate, and the ethylene oxide adduct was obtained as white crystals. The crystals were further washed with methanol, dried, and bis(3,5-dibromo-4-
β-hydroxyethoxyphenyl) sulfone 98.49
I got it. The purity was 98.2% as measured by liquid chromatography.
実施例２
撹拌装置付耐圧反応器に、テトラブロモビスフェノール
５１００９．２−ペンタノール２００ｇ、臭化テトラブ
チルアンモニウム５．７ｇを仕込み、反応器内部を窒素
で置換しｌ；のち、内温を１２０℃まで上昇させ、反応
器内の圧力が１ 、３ ｋｇ／ ｃｒａ”になるようエ
チレンオキシドを圧入した。内圧が１ 、３ ｋｇ／
ｃｍ”を保つようエチレンオキシドを圧入しながら、１
２０℃で反応を続けたところ、４，５時間後にもはや圧
力が低下しなくなり、この時点までに圧入したエチレン
オキシドは１７．５９であった。次いで反応泥倉物を冷
却して取り出し、ろ別したところ、着色した成分はろ液
中に溶解しており、エチレンオキシド付加物は白色の結
晶として得られた。この結晶をさらにメタノールで洗浄
して乾燥し、ビス（３，５−ジブロモ−４−β−ヒドロ
キシエトキシフェニル）スルホン１０４．０９を得た。Example 2 A pressure-resistant reactor equipped with a stirring device was charged with 200 g of tetrabromobisphenol 51009.2-pentanol and 5.7 g of tetrabutylammonium bromide, and the inside of the reactor was replaced with nitrogen; thereafter, the internal temperature was lowered to 120°C. Ethylene oxide was injected into the reactor so that the pressure within the reactor became 1.3 kg/cra.
While pressurizing ethylene oxide to maintain a
When the reaction was continued at 20° C., the pressure no longer decreased after 4 to 5 hours, and the amount of ethylene oxide injected up to this point was 17.59. The reaction slurry was then cooled, taken out, and filtered. The colored components were dissolved in the filtrate, and the ethylene oxide adduct was obtained as white crystals. The crystals were further washed with methanol and dried to obtain bis(3,5-dibromo-4-β-hydroxyethoxyphenyl)sulfone 104.09.
純度は９９．２％でありＩこ 。The purity is 99.2%.
実施例３
撹拌装置付耐圧反応器に、テトラブロモビスフェノール
５１００ｇ、４−メチル−２−ペンタノール２００ｇ、
塩化テトラメチルアンモニウム１．９ｇを仕込み、反応
器内部を窒素で置換したのち、内温を１３０℃まで上昇
させ、反応器内の圧力が１ 、２ ｋｇ／ ｃｌになる
ようプロピレンオキシドを圧入した。内圧が１ 、２
ｋｇ／ ｃ；ｒｔｒ’を保つようプロピレンオキシドを
圧入しながら、１３０℃で反応を続け！こところ、６時
間後にもはや圧力が低下しなくなり、この時点までに圧
入したプロピレンオキシドは２２．５９であった。反応
混合物を冷却して取り出し、ろ別しｔ；ところ、着色し
た成分はろ液中に溶解しており、プロピレンオキシド付
加物は白色の結晶として得られた。この結晶をさらにエ
タノールで洗浄して乾燥し、ビス（３，５−ジブロモ−
４−β−ヒドロキシプロポキシフェニル：スルホン１０
７．１ｇを得た。純度は９８．５％であった。Example 3 In a pressure-resistant reactor equipped with a stirring device, 5100 g of tetrabromobisphenol, 200 g of 4-methyl-2-pentanol,
After charging 1.9 g of tetramethylammonium chloride and purging the inside of the reactor with nitrogen, the internal temperature was raised to 130°C, and propylene oxide was pressurized so that the pressure inside the reactor was 1.2 kg/cl. Internal pressure is 1, 2
Continue the reaction at 130℃ while pressurizing propylene oxide to maintain kg/c; rtr'! However, after 6 hours, the pressure no longer decreased, and the amount of propylene oxide injected up to this point was 22.59. The reaction mixture was cooled, taken out, and filtered; the colored components were dissolved in the filtrate, and the propylene oxide adduct was obtained as white crystals. The crystals were further washed with ethanol, dried, and bis(3,5-dibromo-
4-β-hydroxypropoxyphenyl: sulfone 10
7.1 g was obtained. Purity was 98.5%.
比較例１
反応溶媒として、ｌ−ブタノールの代りに２−プロパノ
ールを用いて、実施例１と同様の操作を行った。Comparative Example 1 The same operation as in Example 1 was performed using 2-propanol instead of l-butanol as the reaction solvent.
撹拌装置付耐圧反応器に、テトラブロモビス７エ／−ル
ＳｌＯｏｇ、２−プロパ／−ル２００ｇ、塩化ベンジル
トリメチルアンモニウム３．０ｐｋ仕込み、反応器内を
窒素で置換したのち、内温を１００°Ｃまで上昇させ、
反応器内の圧力が１．５ｋｙ／ｃＩＲ”を保つようエチ
レンオキシドを圧入しながら反応を続けたところ、６時
間後にもはや圧力が低下しなくなった。この時点までに
圧入したエチレンオキシドは１７．６９であった。A pressure-resistant reactor equipped with a stirring device was charged with tetrabromobis7-el SlOog, 2-propyl-200 g, and benzyltrimethylammonium chloride 3.0 pk, and after purging the inside of the reactor with nitrogen, the internal temperature was raised to 100°. Raise it to C,
When the reaction was continued while injecting ethylene oxide to maintain the pressure inside the reactor at 1.5 ky/cIR, the pressure no longer decreased after 6 hours.The amount of ethylene oxide injected up to this point was 17.69 ky/cIR. Ta.
次いで、反応混合物を冷却して取り出し、ろ加１したと
ころ、ろ液は無色であり、結晶が淡黄褐色に着色してい
た。この結晶の着色は、ｌ−ブタノールで洗浄しても除
くことはできなかった。Next, the reaction mixture was cooled, taken out, and filtered. The filtrate was colorless, and the crystals were colored pale yellowish brown. This coloring of the crystals could not be removed even by washing with l-butanol.
【発明の効果］
本発明の方法によれは、テトラブロモビスフェノールＳ
の２個のフェノール性水酸基それぞれに、アルキレンオ
キシドが１モルずつ付加した、残存フェノール性水酸基
がなく、アルキレンオキシドが、テトラブロモビスフェ
ノールＳ１モルに対し、３モル以上付加した不純物も少
ない、高純度のアルキレンオキシド付加物が得られる。[Effect of the invention] According to the method of the present invention, tetrabromobisphenol S
1 mole of alkylene oxide is added to each of the two phenolic hydroxyl groups in the product.There are no residual phenolic hydroxyl groups, and 3 or more moles of alkylene oxide are added to 1 mole of tetrabromobisphenol S.It is a highly pure product with few impurities. An alkylene oxide adduct is obtained.
また、反応中ｊこ生皮した着色不純物は、反応に用いた
溶媒中に溶解し、析出した結晶中には含有されないので
、着色の少ない、色相の良好な製品が得られる。Further, the colored impurities that are removed during the reaction are dissolved in the solvent used in the reaction and are not contained in the precipitated crystals, so that a product with little coloring and good hue can be obtained.
Claims (1)
又はプロピレンオキシドを付加させて、テトラブロモビ
スフェノールＳのアルキレンオキシド付加物を製造する
に当り、溶媒として炭素数４〜６のアルコール類を用い
、かつ触媒として第四級アンモニウム塩を用いることを
特徴とするテトラブロモビスフェノールＳのアルキレン
オキシド付加物の製造方法。1. In producing an alkylene oxide adduct of tetrabromobisphenol S by adding ethylene oxide or propylene oxide to tetrabromobisphenol S, an alcohol having 4 to 6 carbon atoms is used as a solvent, and quaternary ammonium is used as a catalyst. A method for producing an alkylene oxide adduct of tetrabromobisphenol S, the method comprising using a salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1173789A JP2691618B2 (en) | 1989-07-05 | 1989-07-05 | Method for producing alkylene oxide adduct of tetrabromobisphenol S |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1173789A JP2691618B2 (en) | 1989-07-05 | 1989-07-05 | Method for producing alkylene oxide adduct of tetrabromobisphenol S |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0338563A true JPH0338563A (en) | 1991-02-19 |
| JP2691618B2 JP2691618B2 (en) | 1997-12-17 |
Family
ID=15967182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1173789A Expired - Lifetime JP2691618B2 (en) | 1989-07-05 | 1989-07-05 | Method for producing alkylene oxide adduct of tetrabromobisphenol S |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2691618B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023036868A1 (en) | 2021-09-10 | 2023-03-16 | Reuter Chemische Apparatebau E.K. | (het)aryl substituted bisphenol compounds and thermoplastic resins |
-
1989
- 1989-07-05 JP JP1173789A patent/JP2691618B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023036868A1 (en) | 2021-09-10 | 2023-03-16 | Reuter Chemische Apparatebau E.K. | (het)aryl substituted bisphenol compounds and thermoplastic resins |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2691618B2 (en) | 1997-12-17 |
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