JPS6261204B2 - - Google Patents
Info
- Publication number
- JPS6261204B2 JPS6261204B2 JP58248852A JP24885283A JPS6261204B2 JP S6261204 B2 JPS6261204 B2 JP S6261204B2 JP 58248852 A JP58248852 A JP 58248852A JP 24885283 A JP24885283 A JP 24885283A JP S6261204 B2 JPS6261204 B2 JP S6261204B2
- Authority
- JP
- Japan
- Prior art keywords
- methyl ether
- chloromethyl methyl
- reaction
- hydrogen chloride
- mixture
- 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.)
- Expired
Links
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 59
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 claims description 54
- 229940061627 chloromethyl methyl ether Drugs 0.000 claims description 50
- 229920000642 polymer Polymers 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 26
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 25
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 25
- 238000007265 chloromethylation reaction Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 16
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- -1 chloromethyl methyl Chemical group 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 11
- 238000011084 recovery Methods 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 5
- 206010042674 Swelling Diseases 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 description 1
- CEBRPXLXYCFYGU-UHFFFAOYSA-N 3-methylbut-1-enylbenzene Chemical compound CC(C)C=CC1=CC=CC=C1 CEBRPXLXYCFYGU-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DHGJWSRGFMFRLS-UHFFFAOYSA-N hexa-1,3-dienylbenzene Chemical compound CCC=CC=CC1=CC=CC=C1 DHGJWSRGFMFRLS-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
本願発明は、陰イオン交換樹脂の製造中間体で
あるクロルメチル化されたスチレン系ポリマーの
製造法に関するものである。更に詳しくは、スチ
レン系ポリマーのクロルメチル化反応後に残存し
ている過剰のクロルメチルメチルエーテルおよ
び／またはその分解物を効率よくクロルメチルメ
チルエーテルとして回収する方法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a chloromethylated styrenic polymer, which is an intermediate for producing anion exchange resins. More specifically, the present invention relates to a method for efficiently recovering excess chloromethyl methyl ether and/or its decomposition products remaining after the chloromethylation reaction of a styrene polymer as chloromethyl methyl ether.
従来、スチレン系ポリマーのクロルメチル化反
応は、スチレン系ポリマーを触媒の存在下、過剰
のクロルメチルメチルエーテルと反応させ、反応
終了後、反応混合物に水を加えて触媒を失活させ
ていたが、かゝる方法では残存するクロルメチル
メチルエーテルも同時に加水分解されホルマリ
ン、メタノール、塩酸を含有する希薄水溶液とな
るため、該水溶液は有効な利用法がなく、回収後
廃水処理工程に送られていた。 Conventionally, in the chloromethylation reaction of styrenic polymers, the styrenic polymer was reacted with excess chloromethyl methyl ether in the presence of a catalyst, and after the reaction was completed, water was added to the reaction mixture to deactivate the catalyst. In such a method, the remaining chloromethyl methyl ether is simultaneously hydrolyzed to form a dilute aqueous solution containing formalin, methanol, and hydrochloric acid, so this aqueous solution has no effective use and was sent to a wastewater treatment process after recovery. .
本発明者等は、クロルメチル化反応に使用され
たあと残存する過剰のクロルメチルメチルエーテ
ルの有効な回収法について詳細に検討した結果、
残存する過剰のクロルメチルメチルエーテルを加
水分解することなく、かつ一部分解して生成した
ホルマリン、塩酸、メタノール、メチラール等を
再度クロルメチルメチルエーテルに合成し、クロ
ルメチルメチルエーテルの形で効率的に回収する
方法を見い出し、本発明に到達した。 As a result of detailed study on an effective method for recovering excess chloromethyl methyl ether that remains after being used in the chloromethylation reaction, the present inventors found that
Formalin, hydrochloric acid, methanol, methylal, etc. produced by partially decomposing the remaining excess chloromethyl methyl ether without hydrolyzing it are synthesized again into chloromethyl methyl ether, and it can be efficiently converted into chloromethyl methyl ether in the form of chloromethyl methyl ether. We have found a method to recover them and have arrived at the present invention.
即ち、本発明の要旨は、スチレン系ポリマー粒
子を触媒の存在下、クロルメチルメチルエーテル
と反応させてクロルメチル化ポリマーを製造する
方法において、反応生成混合物に塩化水素を加え
て蒸留することによりクロルメチルメチルエーテ
ルを含有する留出混合物を回収することを特徴と
するクロルメチル化ポリマーの製造法に存する。 That is, the gist of the present invention is a method for producing a chloromethylated polymer by reacting styrenic polymer particles with chloromethyl methyl ether in the presence of a catalyst, by adding hydrogen chloride to the reaction product mixture and distilling it. A method for producing a chloromethylated polymer, characterized in that a distillate mixture containing methyl ether is recovered.
以下、本発明について更に詳細に説明する。 The present invention will be explained in more detail below.
本発明方法におけるスチレン系ポリマー粒子
は、スチレン系架橋共重合体粒子であり、そのス
チレン系モノビニルモノマーは１種又は２種以上
からなる共重合体粒子であつて、スチレン系モノ
ビニルモノマーとしては、スチレン、ａ―メチル
スチレン、ビニルトルエン、イソプロピルスチレ
ン、エチルビニルスチレン、ビニルキシレン等が
挙げられる。 The styrenic polymer particles in the method of the present invention are styrene crosslinked copolymer particles, and the styrenic monovinyl monomers are copolymer particles consisting of one or more types, and the styrene monovinyl monomers include styrene , a-methylstyrene, vinyltoluene, isopropylstyrene, ethylvinylstyrene, vinylxylene and the like.
上記スチレン系ポリマーには、架橋剤として多
官能性ビニルモノマーが少量加えられているの
で、機械的強度及び耐溶剤性に優れたスチレン系
ポリマー粒子である。 Since the styrene polymer contains a small amount of a polyfunctional vinyl monomer as a crosslinking agent, the styrenic polymer particles have excellent mechanical strength and solvent resistance.
多官能性モノマーとしては、ジビニルベンゼ
ン、トリビニルベンゼン、エチレングリコールジ
メタクリレート、テトラエチレングリコールジメ
タクリレート、トリメチロールプロパントリメタ
クリレート、ブタジエンなどが挙げられ、その使
用量は、その用途に応じて適宜選定されるが、通
常、スチレン系モノマー100モルに対して１〜40
モル使用するのが好ましい。 Examples of polyfunctional monomers include divinylbenzene, trivinylbenzene, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, butadiene, and the amount used is appropriately selected depending on the application. However, it is usually 1 to 40% per 100 moles of styrene monomer.
Preference is given to using moles.
スチレン系ポリマー粒子のクロルメチル化反応
は、通常触媒の存在下にスチレン系ポリマー粒子
とクロルメチルメチルエーテルを反応させること
により行なわれる。クロルメチル化反応触媒とし
ては、塩化亜鉛、塩化アルミニウム、塩化スズ等
のルイス酸あるいは酸化亜鉛、酸化アルミニウ
ム、酸化スズ等の金属酸化物が挙げられ、その使
用量はスチレン系ポリマー粒子に対して１〜
500wt％、好ましくは10〜300wt％である。 The chloromethylation reaction of styrenic polymer particles is usually carried out by reacting styrenic polymer particles with chloromethyl methyl ether in the presence of a catalyst. Examples of the chloromethylation reaction catalyst include Lewis acids such as zinc chloride, aluminum chloride, and tin chloride, and metal oxides such as zinc oxide, aluminum oxide, and tin oxide.
500wt%, preferably 10-300wt%.
該クロルメチル化反応は、クロルメチルメチル
エーテルそれ自体を反応溶媒として用いることも
できるが、スチレン系ポリマー粒子の膨潤処理や
クロルメチル化反応の後処理等の便宜のため、有
機溶媒を用いることが好ましい。有機溶媒として
は加水分解されやすいエステルや、ベンゼン、ト
ルエン等のように溶媒自身がクロルメチルメチル
エーテルと反応するような化合物は不適である。 Although chloromethyl methyl ether itself can be used as a reaction solvent in the chloromethylation reaction, it is preferable to use an organic solvent for convenience such as swelling treatment of styrenic polymer particles and post-treatment of the chloromethylation reaction. As the organic solvent, esters that are easily hydrolyzed and compounds such as benzene, toluene, etc., which react with the solvent itself with chloromethyl methyl ether are unsuitable.
好適な有機溶媒としては、ペンタン、ヘキサ
ン、ヘプタン、オクタン、流動パラフイン等の炭
化水素、エチレンジクロライド、ジクロルプロパ
ン、ジクロルメタン、クロロホルム等の脂肪族ハ
ロゲン化水素、ニトロベンゼン、ジニトロベンゼ
ン、ジクロルベンゼン等の置換芳香族炭化水素、
ジエチルエーテル、ジプロピルエーテル、ジブチ
ルエーテル、ジイソアミルエーテル等のエーテル
類が挙げられ、その使用量は、スチレン系ポリマ
ー粒子に対して５重量倍以下、好ましくは0.5〜
３重量倍である。 Suitable organic solvents include hydrocarbons such as pentane, hexane, heptane, octane, and liquid paraffin; aliphatic hydrogen halides such as ethylene dichloride, dichloropropane, dichloromethane, and chloroform; and nitrobenzene, dinitrobenzene, and dichlorobenzene. substituted aromatic hydrocarbons,
Examples include ethers such as diethyl ether, dipropyl ether, dibutyl ether, and diisoamyl ether, and the amount used is 5 times or less, preferably 0.5 to 5 times the weight of the styrene polymer particles.
It is 3 times the weight.
スチレン系ポリマー粒子に対するクロルメチル
メチルエーテルの量は、目的とする陰イオン交換
樹脂の交換容量を考慮して決定されるが、スチレ
ン系ポリマー粒子中のベンゼン環を基準として、
通常0.5〜20モル倍、好ましくは１〜10モル倍、
更に好ましくは1.5〜５モル倍使用される。 The amount of chloromethyl methyl ether relative to the styrenic polymer particles is determined by considering the exchange capacity of the target anion exchange resin, but based on the benzene ring in the styrenic polymer particles,
Usually 0.5 to 20 times the mole, preferably 1 to 10 times the mole,
More preferably, it is used in an amount of 1.5 to 5 moles.
反応温度は20〜150℃、好ましくは30〜100℃で
ある。反応温度が低いと反応が遅くなり、また、
高いと副反応が多くなり好ましくない。反応時間
は１〜20時間である。 The reaction temperature is 20-150°C, preferably 30-100°C. If the reaction temperature is low, the reaction will be slow, and
If it is too high, there will be many side reactions, which is not preferable. Reaction time is 1 to 20 hours.
反応を円滑に進行させるためには、反応に先だ
つてポリマーを膨潤処理しておくのが好ましい。
膨潤処理は、ポリマーを十分乾燥後、室温下で有
機溶媒に浸漬、接触させればよい。有機溶媒とし
ては、クロルメチル化反応の溶媒と同様のものが
好ましい。 In order for the reaction to proceed smoothly, it is preferable to subject the polymer to swelling treatment prior to the reaction.
The swelling treatment may be carried out by sufficiently drying the polymer and then immersing it in an organic solvent at room temperature to bring it into contact with the polymer. The organic solvent is preferably the same as the solvent for the chloromethylation reaction.
反応は、膨潤処理後、所定量のクロルメチルメ
チルエーテル及び触媒を加え、更に昇温した後、
撹拌下、場合により加えられた有機溶媒及びクロ
ルメチルメチルエーテルからなる分散媒中に粒状
ポリマーが懸濁した状態で行なわれる。 The reaction was carried out by adding a predetermined amount of chloromethyl methyl ether and a catalyst after the swelling treatment, and then increasing the temperature.
The granular polymer is suspended in a dispersion medium consisting of an organic solvent and chloromethyl methyl ether, which is optionally added under stirring.
本発明によれば所定時間の反応を行なつた後、
残存している過剰のクロルメチルメチルエーテル
および／またはその分解物を効率よくクロルメチ
ルメチルエーテルとして回収するために、反応生
成混合物に塩化水素を加えることが必要である。
本発明のメカニズムの詳細は十分解明されていな
いが、上記クロルメチル化反応混合物は多数の平
衡系からなりたつており、該反応生成混合物に塩
化水素を加えることにより、たとえば下記平衡反
応に於て、平衡を左辺により移行させ、従つてク
ロルメチルメチルエーテルが効率よく回収できる
ものと考えられる。 According to the present invention, after carrying out the reaction for a predetermined time,
In order to efficiently recover the remaining excess chloromethyl methyl ether and/or its decomposition products as chloromethyl methyl ether, it is necessary to add hydrogen chloride to the reaction product mixture.
Although the details of the mechanism of the present invention have not been fully elucidated, the above chloromethylation reaction mixture consists of many equilibrium systems, and by adding hydrogen chloride to the reaction product mixture, for example, in the equilibrium reaction below, the equilibrium can be maintained. It is thought that chloromethyl methyl ether is transferred more to the left side, and therefore chloromethyl methyl ether can be efficiently recovered.
CH3OCH2Cl＋H2O CH2O＋CH3OH＋HCl
CH3OH＋CH3OCH2Cl CH3OCH2OCH3＋HCl
上記平衡反応から明らかなように、反応生成混
合物の塩化水素濃度は高い方が好ましく、従つて
塩化水素の使用量は、クロルメチル化反応混合物
中に残存しているクロルメチルメチルエーテルに
対して0.5〜10モル倍、好ましくは１〜５モル倍
である。塩化水素の使用量が少なすぎるとクロル
メチルメチルエーテルの回収が不充分となり、又
必要以上に多すぎても回収効率が悪く好ましくな
い。尚、上述の残存しているクロルメチルメチル
エーテルの量は、仕込みのクロルメチルメチルエ
ーテルから、ポリマー中にとり込まれたクロルメ
チルメチルエーテルを差し引いた量であり、従つ
て、そのすべてがクロルメチルメチルエーテルの
形で存在しているとは限らず、クロルメチルメチ
ルエーテル及びその分解物から構成されるもので
ある。 CH 3 OCH 2 Cl+H 2 O CH 2 O+CH 3 OH+HCl CH 3 OH+CH 3 OCH 2 Cl CH 3 OCH 2 OCH 3 +HCl As is clear from the above equilibrium reaction, the higher the hydrogen chloride concentration in the reaction product mixture, the better. The amount of hydrogen chloride used is 0.5 to 10 times, preferably 1 to 5 times by mole, the amount of chloromethyl methyl ether remaining in the chloromethylation reaction mixture. If the amount of hydrogen chloride used is too small, the recovery of chloromethyl methyl ether will be insufficient, and if it is too much than necessary, the recovery efficiency will be poor, which is not preferable. The amount of remaining chloromethyl methyl ether mentioned above is the amount obtained by subtracting the chloromethyl methyl ether incorporated into the polymer from the charged chloromethyl methyl ether, and therefore all of it is chloromethyl methyl ether. It does not necessarily exist in the form of ether, but is composed of chloromethyl methyl ether and its decomposition products.
反応生成混合物に加える塩化水素は、塩酸また
は塩化水素ガスのいずれも使用可能である。塩酸
は、20〜30wt％の濃塩酸及び／又は後述する塩
化水素含有回収水相が使用される。塩化水素とし
て、塩酸を加える場合には、反応生成混合物中の
触媒を失活させるとともに、クロルメチルメチル
エーテルの加水分解を抑制するので好ましい。 As the hydrogen chloride to be added to the reaction product mixture, either hydrochloric acid or hydrogen chloride gas can be used. As the hydrochloric acid, 20 to 30 wt% concentrated hydrochloric acid and/or a recovered aqueous phase containing hydrogen chloride, which will be described later, are used. When hydrochloric acid is added as hydrogen chloride, it is preferable because it deactivates the catalyst in the reaction product mixture and suppresses hydrolysis of chloromethyl methyl ether.
一方、塩化水素ガスも好適に使用されるが、こ
の場合、反応生成混合物中の触媒は失活しないの
で反応終了後、例えば塩基性物質による中和処理
等により触媒を失活させる必要がある。また、塩
化水素として塩酸を使用した場合、蒸留分離によ
りポリマー粒子は水中に懸濁した状態で得られる
が、塩化水素ガスを使用する場合は水がわずかし
か存在しないか、あつてもわずかであるので、蒸
留により留出しない高沸点の有機溶媒をポリマー
粒子を分散させるための分散媒として蒸留に先立
つて、存在させる必要がある。該有機溶媒として
は、前記したクロルメチル化反応溶媒のうち、蒸
留により留出しない高沸点のものが挙げられる。 On the other hand, hydrogen chloride gas is also suitably used, but in this case, since the catalyst in the reaction mixture is not deactivated, it is necessary to deactivate the catalyst by, for example, neutralization treatment with a basic substance after the reaction is completed. In addition, when hydrochloric acid is used as hydrogen chloride, polymer particles are obtained in a suspended state in water by distillation separation, but when hydrogen chloride gas is used, there is little or no water present. Therefore, it is necessary to make a high boiling point organic solvent that cannot be distilled out as a dispersion medium for dispersing the polymer particles prior to distillation. Among the above-mentioned chloromethylation reaction solvents, examples of the organic solvent include those with a high boiling point that are not distilled off.
塩化水素を加えた反応混合物は、蒸留によりク
ロルメチルメチルエーテルを含有する留出混合物
を回収する。蒸留は、常圧または減圧下、クロル
メチルメチルエーテルが留出するが、分散媒であ
る水又は有機溶媒が留出しない温度まで加熱する
ことにより行なわれる。 The reaction mixture to which hydrogen chloride has been added is distilled to recover a distillate mixture containing chloromethyl methyl ether. Distillation is carried out under normal pressure or reduced pressure by heating to a temperature at which chloromethyl methyl ether is distilled out, but water or an organic solvent as a dispersion medium is not distilled out.
塩化水素として塩酸を用いた場合には、回収さ
れた留出混合物はクロルメチルメチルエーテル、
メチラール（ホルムアルデヒドとメタノールの
１：２付加物）並びに水、塩酸、メタノール、ホ
ルマリン等からなり、反応溶媒として有機溶媒を
使用した場合はこれも留出される。また、蒸留残
は、水中にクロルメチル化されたスチレン系ポリ
マー粒子が懸濁している状態である。クロルメチ
ル化されたスチレン系ポリマー粒子は水を分離、
適宜水洗して、あるいは水中に懸濁したままアミ
ノ化工程に供される。一方上記留出混合物は、静
置することにより、多量のクロルメチルメチルエ
ーテル及びメチラール場合により有機溶媒等から
なる油相と水、塩酸、少量のメタノール及びホル
マリン等からなる水相が得られる。該油相は、ク
ロルメチルメチルエーテルを単離する必要はな
く、通常はそのまま次のクロルメチル化反応の原
料として使用される。水相は、濃塩酸水溶液であ
るので、そのままクロルメチル化反応生成混合物
に添加される塩酸として使用することができる。 When hydrochloric acid is used as hydrogen chloride, the recovered distillate mixture is chloromethyl methyl ether,
It consists of methylal (1:2 adduct of formaldehyde and methanol), water, hydrochloric acid, methanol, formalin, etc., and if an organic solvent is used as the reaction solvent, this is also distilled off. Further, the distillation residue is a state in which chloromethylated styrene polymer particles are suspended in water. Chloromethylated styrenic polymer particles separate water,
It is washed with water as appropriate or is subjected to the amination step while suspended in water. On the other hand, by allowing the distillate mixture to stand still, an oil phase consisting of a large amount of chloromethyl methyl ether, methylal, and optionally an organic solvent, and an aqueous phase consisting of water, hydrochloric acid, small amounts of methanol, formalin, etc. are obtained. There is no need to isolate chloromethyl methyl ether from the oil phase, and it is usually used as it is as a raw material for the next chloromethylation reaction. Since the aqueous phase is a concentrated aqueous hydrochloric acid solution, it can be used as it is as hydrochloric acid to be added to the chloromethylation reaction product mixture.
一方、塩化水素として塩化水素ガスを用いた場
合には、回収された留出混合物はクロルメチルメ
チルエーテルを主成分とする油相のみであり、更
にクロルメチル化反応を有機溶媒の存在下で行な
つた場合には、有機溶媒の沸点によつては該有機
溶媒も同時に留出され、油相を形成する。また、
蒸留残は、分散媒である高沸点有機溶媒にクロル
メチル化されたスチレン系ポリマー粒子が懸濁し
ている状態である。クロルメチル化されたスチレ
ン系ポリマー粒子は、通常溶媒を分離することな
く、溶媒中に懸濁したままアミノ化工程に供され
る。一方、油相のみからなる上記留出混合物は、
クロルメチルメチルエーテルを単離する必要はな
く、通常はそのまま次のクロルメチル化反応原料
として使用される。 On the other hand, when hydrogen chloride gas is used as hydrogen chloride, the recovered distillate mixture is only an oil phase mainly composed of chloromethyl methyl ether, and the chloromethylation reaction is further performed in the presence of an organic solvent. In this case, depending on the boiling point of the organic solvent, the organic solvent may also be distilled off at the same time to form an oil phase. Also,
The distillation residue is a state in which chloromethylated styrenic polymer particles are suspended in a high-boiling organic solvent as a dispersion medium. The chloromethylated styrenic polymer particles are usually subjected to the amination step while suspended in the solvent without separating the solvent. On the other hand, the above-mentioned distillate mixture consisting only of the oil phase is
There is no need to isolate chloromethyl methyl ether, and it is usually used as it is as a raw material for the next chloromethylation reaction.
本発明によれば、クロルメチル化反応生成混合
物に塩化水素を加えた後蒸留することにより、ス
チレン系ポリマー粒子のクロルメチル化反応に使
用された過剰のクロルメチルメチルエーテルを加
水分解することなく有効に回収することができ
る。更に、クロルメチルメチルエーテルを含有す
る油相留出物をクロルメチル化反応原料として、
又、場合によつては、留出した濃塩酸をクロルメ
チルメチルエーテル回収操作の塩化水素源として
循環使用することにより、廃水処理操作も軽減さ
れ、かつ工業的有利な反応系を組み立てることが
できる。 According to the present invention, by adding hydrogen chloride to the chloromethylation reaction product mixture and then distilling it, excess chloromethyl methyl ether used in the chloromethylation reaction of styrenic polymer particles can be effectively recovered without hydrolysis. can do. Furthermore, an oil phase distillate containing chloromethyl methyl ether is used as a chloromethylation reaction raw material,
In some cases, by recycling the distilled concentrated hydrochloric acid as a hydrogen chloride source in the chloromethyl methyl ether recovery operation, wastewater treatment operations can be reduced and an industrially advantageous reaction system can be constructed. .
以下、実施例により本発明を更に詳細に説明す
るが、本発明はその要旨を越えない限り以下の実
施例により何等限定されるものではない。 Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples in any way unless it exceeds the gist thereof.
実施例 １
撹拌機および温度調節器を有する１反応器に
スチレン・ジビニルベンゼン共重合体（平均粒径
0.4〜0.5mm粒状品、粒径範囲0.2〜0.8mm、ジビニ
ルベンゼン含有量５重量％）100重量部（以下、
部は重量部を示す）、エチレンジクロライド110部
およびクロルメチルメチルエーテル141部（クロ
ルメチルメチルエーテル／ベンゼン環＝1.9）を
仕込み、30℃で１時間ゆるやかに撹拌下に放置
し、粒状ポリマーの膨潤処理を行なつた。次い
で、反応器に塩化亜塩粉末45部を加え、反応温度
を50℃に保持して、撹拌下15時間クロルメチル化
反応を行なつた。クロルメチル化反応後の混合物
に35％塩酸250部を加えたのち反応器に蒸留装置
をとりつけ、同混合物を、常圧下、98℃まで加熱
して揮発性成分を留去した。留出混合物を静置し
たところ下記の通りの水相および油相が得られ
た。Example 1 Styrene-divinylbenzene copolymer (average particle size
0.4-0.5mm granular product, particle size range 0.2-0.8mm, divinylbenzene content 5% by weight) 100 parts by weight (hereinafter referred to as
(parts indicate parts by weight), 110 parts of ethylene dichloride and 141 parts of chloromethyl methyl ether (chloromethyl methyl ether/benzene ring = 1.9) were charged, and the mixture was left under gentle stirring at 30°C for 1 hour to cause swelling of the granular polymer. I processed it. Next, 45 parts of subsalt chloride powder was added to the reactor, the reaction temperature was maintained at 50°C, and the chloromethylation reaction was carried out with stirring for 15 hours. After adding 250 parts of 35% hydrochloric acid to the mixture after the chloromethylation reaction, a distillation device was attached to the reactor, and the mixture was heated to 98° C. under normal pressure to distill off volatile components. When the distillate mixture was allowed to stand still, an aqueous phase and an oil phase as shown below were obtained.
水 相 水 ８部
塩酸 ９〃
メタノール ６〃その他 ２〃
計 25〃
油 相 エチレンジクロライド 110部
クロルメチルメチルエーテル 44〃
メチラール １〃その他 15〃
計 170〃
蒸留残よりポリマー粒子を取出し、水洗乾燥
後、ポリマー粒子中のクロルメチル基含有量を測
定したところ24％であつた。これはクロルメチル
メチルエーテル55部に相当しており、従つて未反
応で残るクロルメチルメチルエーテルの理論量は
86部と計算される。 Water phase Water 8 parts Hydrochloric acid 9〃 Methanol 6〃Others 2〃Total 25〃 Oil phase Ethylene dichloride 110 parts Chlormethyl methyl ether 44〃 Methyral 1〃Others 15〃Total 170〃 Polymer particles were taken out from the distillation residue, washed with water and dried, The chloromethyl group content in the polymer particles was measured and found to be 24%. This corresponds to 55 parts of chloromethyl methyl ether, so the theoretical amount of chloromethyl methyl ether remaining unreacted is
Calculated at 86 copies.
上記回収された油相にはクロルメチルメチルエ
ーテルが44部含有されていたので、クロルメチル
メチルエーテルの回収率は51％であつた。 Since the recovered oil phase contained 44 parts of chloromethyl methyl ether, the recovery rate of chloromethyl methyl ether was 51%.
なお、ポリマー粒子中のクロルメチル基含有量
は、該ポリマー粒子をジメチルアミンでアミノ化
して陰イオン交換樹脂とし、そのイオン交換容量
より算出したものである。 The content of chloromethyl groups in the polymer particles is calculated from the ion exchange capacity of an anion exchange resin obtained by aminating the polymer particles with dimethylamine.
実施例 ２
スチレン・ジビニルベンゼン共重合体（ジビニ
ルベンゼン含有量３重量％）100部、エチレンジ
クロライド140部およびクロルメチルメチルエー
テル177部（クロルメチルメチルエーテル／ベン
ゼン環＝2.3）および塩化亜鉛粉末40部を用いた
他は、実施例１と同様にして、クロルメチル化反
応およびクロルメチルメチルエーテルの回収を行
ない、下記の通り、水相および油相を得た。Example 2 100 parts of styrene/divinylbenzene copolymer (divinylbenzene content: 3% by weight), 140 parts of ethylene dichloride, 177 parts of chloromethyl methyl ether (chloromethyl methyl ether/benzene ring = 2.3), and 40 parts of zinc chloride powder The chloromethylation reaction and the recovery of chloromethyl methyl ether were carried out in the same manner as in Example 1, except that chloromethyl methyl ether was used, and an aqueous phase and an oil phase were obtained as described below.
水 相 水 ９部
塩酸 14〃
メタノール ９〃
メチラール ６〃その他 ７〃
計 45〃
油 相 エチレンジクロライド 138部
クロルメチルメチルエーテル 78〃
メチラール 19〃その他 24〃
計 259〃
ポリマー中のクロルメチル基含有量を測定した
ところ26％であり、クロルメチルメチルエーテル
の回収率は68％であつた。 Water phase Water 9 parts Hydrochloric acid 14〃 Methanol 9〃 Methyral 6〃Others 7〃Total 45〃 Oil phase Ethylene dichloride 138 parts Chlormethyl methyl ether 78〃 Methyral 19〃Others 24〃Total 259〃 Measurement of the chloromethyl group content in the polymer As a result, the recovery rate of chloromethyl methyl ether was 26%, and the recovery rate of chloromethyl methyl ether was 68%.
Claims (1)
ロルメチルメチルエーテルと反応させてクロルメ
チル化ポリマーを製造する方法において、反応生
成混合物に塩化水素を加えて蒸留することにより
クロルメチルメチルエーテルを含有する留出混合
物を回収することを特徴とするクロルメチル化ポ
リマーの製造法。 ２ 塩化水素が20〜35重量％塩酸である特許請求
の範囲第１項記載の製造法。 ３ 有機溶媒の存在下にクロルメチル化反応を行
なうことを特徴とする特許請求の範囲第１項記載
の製造法。 ４ スチレン系ポリマー粒子が、スチレン―ジビ
ニルベンゼンコポリマーである特許請求の範囲第
１項記載の製造法。 ５ 回収したクロロメチルメチルエーテルをクロ
ルメチル化反応に循環使用することを特徴とする
特許請求の範囲第１項記載の製造法。 ６ 留出混合物を分液して回収された塩化水素を
含有する水相を、反応生成混合物に加えられる塩
化水素として使用することを特徴とする特許請求
の範囲第２項記載の製造法。[Claims] 1. In a method for producing a chloromethylated polymer by reacting styrenic polymer particles with chloromethyl methyl ether in the presence of a catalyst, chloromethyl methyl is produced by adding hydrogen chloride to the reaction product mixture and distilling the mixture. A method for producing a chloromethylated polymer, characterized in that a distillate mixture containing an ether is recovered. 2. The manufacturing method according to claim 1, wherein the hydrogen chloride is 20 to 35% by weight hydrochloric acid. 3. The production method according to claim 1, characterized in that the chloromethylation reaction is carried out in the presence of an organic solvent. 4. The manufacturing method according to claim 1, wherein the styrenic polymer particles are styrene-divinylbenzene copolymer. 5. The production method according to claim 1, characterized in that the recovered chloromethyl methyl ether is recycled to the chloromethylation reaction. 6. The production method according to claim 2, characterized in that the aqueous phase containing hydrogen chloride recovered by separating the distillate mixture is used as hydrogen chloride to be added to the reaction product mixture.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24885283A JPS60137908A (en) | 1983-12-26 | 1983-12-26 | Production of chloromethylated polymer |
| EP84114465A EP0150332A3 (en) | 1983-12-26 | 1984-11-29 | Process for producing a chloromethylated polymer |
| US06/681,102 US4636554A (en) | 1983-12-26 | 1984-12-13 | Process for producing a chloromethylated polymer |
| KR1019840008304A KR850004771A (en) | 1983-12-26 | 1984-12-24 | Method for preparing chloromethylated polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24885283A JPS60137908A (en) | 1983-12-26 | 1983-12-26 | Production of chloromethylated polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60137908A JPS60137908A (en) | 1985-07-22 |
| JPS6261204B2 true JPS6261204B2 (en) | 1987-12-21 |
Family
ID=17184379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24885283A Granted JPS60137908A (en) | 1983-12-26 | 1983-12-26 | Production of chloromethylated polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60137908A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02246924A (en) * | 1989-03-22 | 1990-10-02 | Morito Kk | Arm band for measuring blood pressure |
| EP0776911A2 (en) | 1995-11-28 | 1997-06-04 | Mitsubishi Chemical Industries Limited | Process for preparation of anion exchange resin |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8163138B2 (en) | 2007-05-23 | 2012-04-24 | Dow Global Technologies Llc | Method for processing effluent from chloromethylation of vinyl aromatic polymers |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1049270A (en) * | 1965-10-29 | 1966-11-23 | Wolfen Filmfab Veb | Recovery of monochlorodimethyl ether |
| GB1269986A (en) * | 1969-04-10 | 1972-04-12 | Mitsubishi Chem Ind | Porous cross-linked copolymer and ion-exchange resin |
| US4393145A (en) * | 1979-05-01 | 1983-07-12 | Etablissement Texcontor | Anionic ion exchange resins with cholesterol-decreasing properties |
| JPS58203927A (en) * | 1982-05-24 | 1983-11-28 | Mitsubishi Chem Ind Ltd | Production of chloromethyl alkyl ether |
-
1983
- 1983-12-26 JP JP24885283A patent/JPS60137908A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1049270A (en) * | 1965-10-29 | 1966-11-23 | Wolfen Filmfab Veb | Recovery of monochlorodimethyl ether |
| GB1269986A (en) * | 1969-04-10 | 1972-04-12 | Mitsubishi Chem Ind | Porous cross-linked copolymer and ion-exchange resin |
| US4393145A (en) * | 1979-05-01 | 1983-07-12 | Etablissement Texcontor | Anionic ion exchange resins with cholesterol-decreasing properties |
| JPS58203927A (en) * | 1982-05-24 | 1983-11-28 | Mitsubishi Chem Ind Ltd | Production of chloromethyl alkyl ether |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02246924A (en) * | 1989-03-22 | 1990-10-02 | Morito Kk | Arm band for measuring blood pressure |
| EP0776911A2 (en) | 1995-11-28 | 1997-06-04 | Mitsubishi Chemical Industries Limited | Process for preparation of anion exchange resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60137908A (en) | 1985-07-22 |
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