JPH0242369B2 - - Google Patents
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- Publication number
- JPH0242369B2 JPH0242369B2 JP59100102A JP10010284A JPH0242369B2 JP H0242369 B2 JPH0242369 B2 JP H0242369B2 JP 59100102 A JP59100102 A JP 59100102A JP 10010284 A JP10010284 A JP 10010284A JP H0242369 B2 JPH0242369 B2 JP H0242369B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- carbon atoms
- resin
- epoxy compound
- general formula
- 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 - Lifetime
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- 150000001875 compounds Chemical class 0.000 claims description 42
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 33
- 239000004593 Epoxy Substances 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 description 20
- 238000000034 method Methods 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 11
- 239000000725 suspension Substances 0.000 description 11
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 10
- 239000003456 ion exchange resin Substances 0.000 description 10
- 229920003303 ion-exchange polymer Polymers 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- 230000001588 bifunctional effect Effects 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000002460 imidazoles Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003957 anion exchange resin Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 3
- -1 aliphatic tertiary amines Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000005349 anion exchange Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000009965 odorless effect Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000008159 sesame oil Substances 0.000 description 2
- 235000011803 sesame oil Nutrition 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- MKBBSFGKFMQPPC-UHFFFAOYSA-N 2-propyl-1h-imidazole Chemical compound CCCC1=NC=CN1 MKBBSFGKFMQPPC-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 229940061627 chloromethyl methyl ether Drugs 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- VAUOPRZOGIRSMI-UHFFFAOYSA-N n-(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CNC1=CC=CC=C1 VAUOPRZOGIRSMI-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Epoxy Resins (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
【発明の詳細な説明】
技術分野
本発明は、粒状塩基性イオン交換樹脂の製造法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a method for producing a granular basic ion exchange resin.
本発明の方法によれば陰イオン交換基の形成に
脂肪族第三級アミンを使用しないことによる、樹
脂製造時の環境衛生の著しい改善がなされ、得ら
れた樹脂が優れた耐熱性及びイオン交換能を有す
るものとなる。 According to the method of the present invention, by not using aliphatic tertiary amines to form anion exchange groups, environmental hygiene during resin production is significantly improved, and the resulting resin has excellent heat resistance and ion exchange properties. become capable.
本発明により得られる粒状塩基性イオン交換樹
脂は、水処理、各種薬液の精製、アミノ酸、核酸
等の分離、高分子触媒等に利用することができ
る。 The granular basic ion exchange resin obtained by the present invention can be used for water treatment, purification of various chemical solutions, separation of amino acids, nucleic acids, etc., polymer catalysts, etc.
従来技術との関連における発明の改良点
従来、強塩基性交換樹脂の代表的なものは、イ
オン交換基として第四アンモニウム塩を含むもの
である。この第四アンモニウム塩は、架橋重合体
(付加重合体、重附加重合体、または重縮合重合
体)上に導入されたハロアルキル基(特にクロル
メチル基)に脂肪族第三アミン(特にトリメチル
アミン)を反応させることによつて形成されてい
る。Improvements of the invention in relation to the prior art Conventionally, typical strong basic exchange resins contain quaternary ammonium salts as ion exchange groups. This quaternary ammonium salt reacts an aliphatic tertiary amine (especially trimethylamine) with a haloalkyl group (especially a chloromethyl group) introduced on a crosslinked polymer (addition polymer, polyaddition polymer, or polycondensation polymer). It is formed by
しかし、このような従来の強塩基性交換樹脂の
製造法にはいくつかの欠点がある。 However, such conventional methods for producing strongly basic exchange resins have several drawbacks.
先ず、従来の方法は、一般に製造工程が複雑で
ある。すなわち、最も代表的な強塩基性交換樹脂
は架橋重合体(たとえばジビニルベンゼンで架橋
されたポリスチレン)をクロルメチルメチルエー
テルでクロルメチル化し、それを第四アンモニウ
ム塩化することによつて製造されるが、クロルメ
チル化は適当な溶媒と触媒の存在下に行なう必要
があつて、そのこと自体および反応後の溶媒およ
び触媒の除去の必要の点で工程上煩雑である。ま
た、第四アンモニウム塩化には一般にトリメチル
アミンが使用されるが、このアミンは悪臭物質で
あつてその使用は作業環境上好ましくない。 First, conventional methods generally require complicated manufacturing steps. That is, the most typical strong basic exchange resin is produced by chloromethylating a crosslinked polymer (for example, polystyrene crosslinked with divinylbenzene) with chloromethyl methyl ether and converting it into a quaternary ammonium salt. Chloromethylation must be carried out in the presence of a suitable solvent and catalyst, and is a complicated process in itself and in the necessity of removing the solvent and catalyst after the reaction. Furthermore, trimethylamine is generally used for quaternary ammonium saltation, but this amine is a foul-smelling substance and its use is unfavorable in view of the working environment.
陰イオン交換基の形成に脂肪族第三アミン、特
にトリメチルアミン、を使用するこの種方法のも
う一つの欠点は、製品強塩基性交換樹脂の耐熱性
が低い、ということである。強塩基性交換樹脂の
用途の拡大に伴なつて高温下での使用が求められ
る現状においては耐熱性の不良はその用途に種々
の制限をもたらす。 Another drawback of this kind of process using aliphatic tertiary amines, especially trimethylamine, for the formation of anion exchange groups is that the product strongly basic exchange resin has a low heat resistance. In the current situation where strongly basic exchange resins are required to be used at high temperatures as their applications expand, poor heat resistance brings about various restrictions on their applications.
この様な欠点を解決するために、本発明者らは
陰イオン交換基の形成にイミダゾールを使用する
陰イオン交換樹脂の製造法を発明した(特開昭―
51―151681)。該発明の製造法はハロメチルオキ
シラン化合物をイミダゾール類に反応させ得られ
た変性イミダゾール類(中間体)を多官能性エポ
キシ化合物と反応させて陰イオン交換樹脂を得る
方法である。 In order to solve these drawbacks, the present inventors invented a method for producing anion exchange resins that uses imidazole to form anion exchange groups (Japanese Patent Application Laid-Open No.
51―151681). The production method of the invention is a method in which a halomethyloxirane compound is reacted with an imidazole, and the obtained modified imidazole (intermediate) is reacted with a polyfunctional epoxy compound to obtain an anion exchange resin.
該発明は従来の欠点を克服する方法であるが、
下記の欠点を有する。 Although the invention is a method to overcome the conventional drawbacks,
It has the following drawbacks.
すなわち、上記の変性イミダゾール類は、イミ
ダゾール、イミダゾールとハロメチルオキシラン
化合物の1:1付加体、1:2付加体及びオリゴ
マーとの混合物であるため、得られる陰イオン交
換樹脂は、イミダゾール類に基づく塩基性交換基
のうち、中性塩分解能に寄与するイミダゾリウム
塩基の含有量が少なく、強塩基性交換樹脂として
は、低活性である。 That is, since the above-mentioned modified imidazoles are mixtures of imidazole, 1:1 adducts, 1:2 adducts, and oligomers of imidazole and halomethyloxirane compounds, the obtained anion exchange resin is based on imidazoles. Among the basic exchange groups, the content of imidazolium bases that contribute to neutral salt decomposition ability is small, and the activity as a strong basic exchange resin is low.
発明の要旨
本発明は、ハロメチルオキシラン化合物とイミ
ダゾール類とを反応させて得られる一般式、
(但し、R1は水素原子、炭素数1〜17のアルキ
ル基又は炭素数6〜8のアリール基を、R2は水
素原子又は炭素数1〜3のアルキル基を、Xはハ
ロゲン原子を、nは1以上の整数をそれぞれ表わ
す)で表わされる高分子四級塩と多官能性エポキ
シ化合物を油性媒体中に懸濁させた後これを加熱
し硬化反応せしめることを特徴とする粒状塩基性
イオン交換樹脂の製造法を提供するものである。Summary of the Invention The present invention relates to a general formula obtained by reacting a halomethyloxirane compound and an imidazole, (However, R 1 is a hydrogen atom, an alkyl group with 1 to 17 carbon atoms, or an aryl group with 6 to 8 carbon atoms, R 2 is a hydrogen atom or an alkyl group with 1 to 3 carbon atoms, X is a halogen atom, A particulate basic ion characterized by suspending a polymeric quaternary salt (n is an integer of 1 or more) and a polyfunctional epoxy compound in an oily medium and then heating the suspension to cause a curing reaction. A method for producing a replacement resin is provided.
発明の具体的説明
本発明の方法に用いる高分子四級塩は、ハロメ
チルオキシラン化合物とイミダゾール類とを反応
させて得られる一般式〔〕、
(但し、R1は水素原子、炭素数1〜17のアルキ
ル基又は炭素数6〜8のアリール基を、R2は水
素原子又は炭素数1〜3のアルキル基を、Xはハ
ロゲン基子を、nは1以上の整数をそれぞれ表わ
す)で表わされるものである。Detailed Description of the Invention The polymeric quaternary salt used in the method of the present invention has the general formula [] obtained by reacting a halomethyloxirane compound and an imidazole, (However, R 1 is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or an aryl group having 6 to 8 carbon atoms, R 2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X is a halogen group, n represents an integer of 1 or more).
ここで、ハロメチルオキシラン化合物は、下記
一般式〔〕、
(但し、Xはハロゲン原子、特に塩素、臭素また
はヨウ素である)で示される化合物である。具体
例としては、エピクロルヒドリン、エピブロムヒ
ドリン等が挙げられる。これらは併用することが
できる。 Here, the halomethyloxirane compound has the following general formula [], (wherein X is a halogen atom, especially chlorine, bromine or iodine). Specific examples include epichlorohydrin, epibromohydrin, and the like. These can be used together.
又、イミダゾール類は、下記一般式〔〕、
(但し、R1は水素原子、メチル、エチル、プロ
ピル、ヘキシル、ウンデシル、ヘプタデシル等の
炭素数1〜17のアルキル基;フエニル、トリル、
キシリル等の炭素数6〜8のアリール基;R2は
水素原子またはメチル、エチル、n―プロピル等
の炭素数1〜3のアルキル基を示す)で示される
化合物である。具体的なイミダゾール類として
は、たとえば下記のものがある。イミダゾール、
2―メチルイミダゾール、2―エチルイミダゾー
ル、2―プロピルイミダゾール、2―フエニルイ
ミダゾール、2―ウンデシルイミダゾール、2―
ヘプタデシルイミダゾール、2―エチル―4―メ
チルイミダゾール、2,4―ジメチルイミダゾー
ル、2―フエニル―4―メチルイミダゾール等。
これらは併用することができる。 In addition, imidazoles have the following general formula [], (However, R 1 is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms such as methyl, ethyl, propyl, hexyl, undecyl, heptadecyl; phenyl, tolyl,
It is a compound represented by an aryl group having 6 to 8 carbon atoms such as xylyl; R2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, n-propyl, etc.). Specific examples of imidazoles include the following. imidazole,
2-Methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-
Heptadecylimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, etc.
These can be used together.
高分子四級塩は、上記一般式〔〕で表わされ
るハロメチルオキシラン化合物と、上記一般式
〔〕で表わされるイミダゾール類とを反応させ
ることにより調製される。 The polymer quaternary salt is prepared by reacting a halomethyloxirane compound represented by the above general formula [] with an imidazole represented by the above general formula [].
この反応溶媒としては、前記反応成分に対し不
活性なものであり、かつ後述する多官能性エポキ
シ化合物による樹脂化を妨げないものであればさ
しつかえないが、分子量の大きな高分子四級塩の
調製には特に水が好ましい。 This reaction solvent may be any solvent as long as it is inert to the reaction components and does not interfere with resin formation by the polyfunctional epoxy compound described later, but it is suitable for preparing quaternary salts with large molecular weight polymers. Water is particularly preferred.
反応モル比は、イミダゾール類1モルに対して
ハロメチルオキシラン化合物0.9〜1.5モルが用い
られ、特に1〜1.1モルが好ましい。 As for the reaction molar ratio, 0.9 to 1.5 mol of halomethyloxirane compound is used per 1 mol of imidazole, and 1 to 1.1 mol is particularly preferable.
反応温度は、30〜150℃が用いられるが、特に
50〜120℃が好ましい。30℃未満では反応速度が
遅く、120℃を越えると副反応が起こりやすいの
で好ましくない。 The reaction temperature used is 30 to 150℃, but especially
50-120°C is preferred. If it is less than 30°C, the reaction rate is slow, and if it exceeds 120°C, side reactions are likely to occur, which is not preferable.
また、イミダゾール類にハロメチルオキシラン
化合物を50〜80℃の温度で滴下し、滴下終了後80
〜120℃に昇温することが好ましい。 In addition, a halomethyloxirane compound was added dropwise to imidazoles at a temperature of 50 to 80°C, and after the completion of dropping,
Preferably, the temperature is raised to ~120°C.
反応時間は、2〜30時間が適当である。 A suitable reaction time is 2 to 30 hours.
本発明の方法で用いる多官能性エポキシ化合物
は、オキシラン環を2個以上有する化合物であ
る。 The polyfunctional epoxy compound used in the method of the present invention is a compound having two or more oxirane rings.
本発明で使用するのに適した多官能性エポキシ
化合物の一群は、エポキシ当量100〜3000程度の
いわゆるエポキシ樹脂として知られているもので
ある。具体的には、ビスフエノール系エポキシ樹
脂(たとえば、ビスフエノールAジグリシジルエ
ーテル)、ポリグリコール系エポキシ樹脂(たと
えば、エチレングリコールジグリシジルエーテ
ル、グリセリントリグリシジルエーテル、トリメ
チロールプロパントリグリシジルエーテル)、脂
環系エポキシ樹脂(たとえば、ビニルシクロヘキ
センジエポキサイド)、カルボン酸系エポキシ樹
脂(たとえばフタル酸ジグリシジルエステル)、
アミン系エポキシ樹脂〔たとえば、グリシジルア
ニリン、4,4′―メチレンジアニリンのテトラグ
リシジル化合物、下記一般式〔〕、
(但し、R1、R2は一般式〔〕と同じ、nは0
又は整数である)
で表わされるイミダゾリウム塩基を有するジグリ
シジル化合物〕、ノボラツク系エポキシ樹脂(た
とえば、フエノールノボラツクグリシジルエーテ
ル)などがあり、これらは2種以上を併用するこ
ともできる。 A group of polyfunctional epoxy compounds suitable for use in the present invention are those known as so-called epoxy resins having an epoxy equivalent weight of about 100 to 3000. Specifically, bisphenol-based epoxy resins (e.g., bisphenol A diglycidyl ether), polyglycol-based epoxy resins (e.g., ethylene glycol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether), alicyclic epoxy resins (e.g. vinyl cyclohexene diepoxide), carboxylic acid epoxy resins (e.g. diglycidyl phthalate),
Amine-based epoxy resins [for example, glycidylaniline, tetraglycidyl compounds of 4,4'-methylene dianiline, the following general formula [], (However, R 1 and R 2 are the same as the general formula [], n is 0
or an integer)], novolak-based epoxy resins (for example, phenol novolac glycidyl ether), and two or more of these can also be used in combination.
なお、一般式〔〕で表わされるイミダゾリウ
ム塩基を有するジグリシジル化合物の合成は、前
述の様に調製した一般式〔〕で示される高分子
四級塩に、所定量のハロメチルオキシラン化合物
を反応させた後、アルカリ処理を行なう方法によ
り可能である。 The diglycidyl compound having an imidazolium base represented by the general formula [] is synthesized by reacting a predetermined amount of a halomethyloxirane compound with the polymeric quaternary salt represented by the general formula [] prepared as described above. This can be done by carrying out alkali treatment after treatment.
即ち、反応を概略示すと以下の様である。 That is, the reaction is summarized as follows.
また一般式〔〕においてn=0で表わされ
る、
の合成は、イミダゾール類とハロメチルオキシラ
ン化合物とを1:2のモル比で反応させた後、ア
ルカリ処理を行なう方法により、容易に得ること
ができる。 Also, represented by n=0 in the general formula [], can be easily synthesized by reacting an imidazole and a halomethyloxirane compound at a molar ratio of 1:2, followed by alkali treatment.
本発明の方法に使用する油性媒体としては、上
記高分子四級塩の調製液と多官能性エポキシ化合
物との混合溶液を懸濁状態に保持し、かつ硬化の
ための温度を与える加熱媒体として作用するもの
であれば任意のものが使用可能である。 The oil-based medium used in the method of the present invention is used as a heating medium to maintain the mixed solution of the polymer quaternary salt preparation and the polyfunctional epoxy compound in a suspended state and to provide a temperature for curing. Anything that works can be used.
油性媒体の一つの例は、動植物油、特に植物油
である。具体的には、たとえば、ごま油、えの
油、菜種油、オリーブ油、落花性油等の半乾性油
または不乾性油が適当である。 One example of an oily medium is an animal or vegetable oil, especially a vegetable oil. Specifically, semi-drying oils or non-drying oils such as sesame oil, edible oil, rapeseed oil, olive oil, and peanut oil are suitable.
油性媒体の他の一つの例は、パラフインであ
る。加熱硬化温度で液状のもの(この条件は、上
記の動植物油についてもあてはまる)が使用され
る。 Another example of an oily medium is paraffin. Those that are liquid at the heating curing temperature (this condition also applies to the above-mentioned animal and vegetable oils) are used.
本発明においては、前記高分子四級塩および多
官能性エポキシ化合物を混合してから、上記油性
媒体中に懸濁させるのがふつうである。 In the present invention, the polymer quaternary salt and the polyfunctional epoxy compound are usually mixed and then suspended in the oily medium.
また、多官能性エポキシ化合物として、一般式
()で表わされるイミダゾリウム塩基を有すジ
グリシジル化合物を用いる場合は、前記のように
して調製した高分子四級塩にその一部と反応し得
る所定量のハロメチルオキシラン化合物を反応さ
せた後、アルカリ処理を行なうことにより、上記
のジグリシジル化合物の合成及び高分子四級塩と
の混合が同時にできるので、これを上記油性媒体
中に懸濁させる方法も可能である。 In addition, when using a diglycidyl compound having an imidazolium base represented by the general formula () as a polyfunctional epoxy compound, a portion of the polymer quaternary salt prepared as described above that can react with a portion of the diglycidyl compound may be used. By reacting a fixed amount of a halomethyloxirane compound and then treating it with an alkali, the above-mentioned diglycidyl compound can be synthesized and mixed with the polymeric quaternary salt at the same time, so this is a method of suspending it in the above-mentioned oily medium. is also possible.
懸濁粒子の粒径は、一般に0.1〜1.0mm、好まし
くは0.3〜0.8mmが適当である。 The diameter of the suspended particles is generally 0.1 to 1.0 mm, preferably 0.3 to 0.8 mm.
このような粒径の懸濁液は系を撹拌するだけで
も得られようが、懸濁状態を円滑にするには懸濁
安定剤を使用するのが好ましい。懸濁安定剤を油
性媒体に溶解しておいて、そこへ高分子四級塩、
多官能性エポキシ化合物の混合液を分散懸濁させ
るのがふつうである。 Although a suspension having such a particle size can be obtained simply by stirring the system, it is preferable to use a suspension stabilizer to make the suspension smooth. A suspension stabilizer is dissolved in an oily medium, and a polymer quaternary salt,
Usually, a mixture of polyfunctional epoxy compounds is dispersed and suspended.
本発明の方法に用いられる懸濁液の懸濁状態を
円滑にするための懸濁安定剤としては、一般に、
油性媒体中に親水性物質を分散懸濁させることが
できる公知のいかなる懸濁安定剤物質が使用可で
あるが、代表的なものはたとえば表面活性剤、特
にHLB(親水性―親油性バランス)が12以下の非
イオン性表面活性剤または陰イオン性表面活性剤
である。 Suspension stabilizers for smoothing the suspension state of the suspension used in the method of the present invention generally include:
Any known suspension stabilizer substance capable of dispersing and suspending a hydrophilic substance in an oily medium can be used, but typical examples include surfactants, especially HLB (hydrophilic-lipophilic balance) is a nonionic surfactant or anionic surfactant with 12 or less.
本発明の方法において使用される多官能性エポ
キシ化合物は、高分子四級塩との合計量の5〜70
重量%、好ましくは15〜60重量%の量で使用され
る。 The polyfunctional epoxy compound used in the method of the present invention may contain 5 to 70% of the total amount of the polymeric quaternary salt.
% by weight, preferably from 15 to 60% by weight.
必要に応じて使用される懸濁安定剤の量は、た
とえば表面活性剤(特に非イオン表面活性剤)の
場合は、高分子四級塩と多官能性エポキシ化合物
との合計量に対して1〜40重量%、特に3〜20重
量%であるのがふつうである。 The amount of suspension stabilizer used if necessary is, for example, in the case of a surfactant (especially a nonionic surfactant), 1 to 1% of the total amount of the polymeric quaternary salt and the polyfunctional epoxy compound. ~40% by weight, especially 3-20% by weight is usual.
油性媒体の量は、ビーズ状に硬化する前の懸濁
粒子が過密状態から合一するようなことが生じな
い任意のものでありうる。一般に、硬化すべき懸
濁粒子の重量の1〜10倍量が用いられる。 The amount of oily medium can be any amount that does not cause the suspended particles to coalesce from overcrowding before hardening into beads. Generally, an amount of 1 to 10 times the weight of the suspended particles to be cured is used.
次に、上述の様に高分子四級塩と多官能性エポ
キシ化合物を油性媒体中に懸濁させたものを加熱
し、高分子四級塩と多官能性エポキシ化合物を硬
化反応させる。 Next, as described above, the suspension of the polymeric quaternary salt and the polyfunctional epoxy compound in an oily medium is heated to cause a curing reaction between the polymeric quaternary salt and the polyfunctional epoxy compound.
加熱は、60〜150℃好ましくは80〜110℃で行な
われる。 Heating is carried out at 60-150°C, preferably 80-110°C.
加熱時間は2〜15時間程度である。 Heating time is about 2 to 15 hours.
硬化終了後、ビーズ状樹脂を分離し、脱油を行
ない、水洗すれば、目的の粒状強塩基性イオン交
換樹脂が得られる。 After curing, the beaded resin is separated, deoiled, and washed with water to obtain the desired granular strongly basic ion exchange resin.
発明の効果
本発明の方法で得られる塩基性イオン交換樹脂
は、公知の例えば特開昭52―151681号公報に開示
された陰イオン交換樹脂と比較し、優れたイオン
交換能を有し、また樹脂の着色が少なくかつ低分
子量体の生成も少ないものであり、耐熱性の点で
も優れたものである。Effects of the Invention The basic ion exchange resin obtained by the method of the present invention has superior ion exchange ability compared to the known anion exchange resin disclosed in JP-A-52-151681, and The resin is less colored, less produces low molecular weight substances, and has excellent heat resistance.
本発明の方法により、上述の様な優れた特徴を
有する塩基性イオン交換樹脂の粒状物を簡便な方
法で提供することが可能となつた。 By the method of the present invention, it has become possible to provide basic ion exchange resin granules having the above-mentioned excellent characteristics in a simple manner.
実験例
実施例 1
還流冷却器、温度計、撹拌機を設けた四ツ口フ
ラスコ中に2―メチルイミダゾール72.4g(0.88
モル)を入れ、水100mlを加えて均一溶液にする。
反応温度を50〜55℃に保ち、撹拌しながらエピク
ロルヒドリン81.6g(0.88モル)を約1時間で滴
下し、さらにこの温度で4時間反応させた後、反
応温度を90℃に上昇させ、この温度で14時間にわ
たつて撹拌を続けることにより、高分子四級塩
(中間体Aとする)の調製液を得る。Experimental Examples Example 1 In a four-necked flask equipped with a reflux condenser, a thermometer, and a stirrer, 72.4 g of 2-methylimidazole (0.88
mol) and add 100ml of water to make a homogeneous solution.
While keeping the reaction temperature at 50 to 55°C, 81.6 g (0.88 mol) of epichlorohydrin was added dropwise over about 1 hour while stirring, and after further reacting at this temperature for 4 hours, the reaction temperature was raised to 90°C. By continuing stirring for 14 hours, a prepared solution of a polymeric quaternary salt (referred to as Intermediate A) is obtained.
この中間体A25gと二官能性エポキシ化合物で
ある「エポライト40E」(共栄社油脂化学工業社
製)8.3gとを均一に混合した後、懸濁安定剤
(日本乳化剤社製非イオン性表面活性剤
「Newcol20」HLB=8.1)4gを含むごま油200
g中に撹拌しながら徐々に加える。 After uniformly mixing 25 g of this intermediate A with 8.3 g of the bifunctional epoxy compound "Epolite 40E" (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), Newcol20”HLB=8.1) Sesame oil 200 containing 4g
Gradually add to g while stirring.
80℃で3時間加熱してビーズ状縮合を行なわせ
て硬化させる。 Heat at 80°C for 3 hours to perform bead-like condensation and harden.
冷却後、ビーズ状硬化物を分離し、脱油を行な
つた後、水洗をして目的の強塩基性イオン交換樹
脂を得る。 After cooling, the bead-shaped cured product is separated, deoiled, and then washed with water to obtain the desired strong basic ion exchange resin.
得られた強塩基性イオン交換樹脂は、無色無臭
で、中性塩分解能が4.1meq/g(乾燥物)のビ
ーズ状樹脂(粒径:0.3〜0.7mm)であつた。 The obtained strongly basic ion exchange resin was colorless and odorless, and was a bead-shaped resin (particle size: 0.3 to 0.7 mm) with a neutral salt decomposition ability of 4.1 meq/g (dry material).
実施例 2
実施例1において得られた中間体A25gと二官
能性エポキシ化合物である化合物〔M〕、
6.3gとを均一に混合させた後、実施例1と同
様な方法で加熱及び後処理を行なつた。Example 2 25g of intermediate A obtained in Example 1 and compound [M] which is a bifunctional epoxy compound, After homogeneously mixing 6.3 g of the mixture, heating and post-treatment were performed in the same manner as in Example 1.
得られた強塩基性イオン交換樹脂は、無色無臭
で、中性塩分解能が4.9meq/g(乾燥物)のビ
ーズ状樹脂(粒径:0.3〜0.7mm)であつた。 The obtained strongly basic ion exchange resin was colorless and odorless, and was a bead-shaped resin (particle size: 0.3 to 0.7 mm) with a neutral salt decomposition ability of 4.9 meq/g (dry material).
なお、二官能性エポキシ化合物〔M〕の合成
は、次の様に行つた。 The bifunctional epoxy compound [M] was synthesized as follows.
還流冷却器、温度計、撹拌機を設けた四ツ口フ
ラスコ中に2―メチルイミダゾール24.6g(0.3
モル)を入れ、水60mlを加えて均一溶液にする。
反応温度を25〜30℃に保ち、撹拌しながらエピク
ロルヒドリン55.5g(0.6モル)を1時間で滴下
した後、3時間反応させる。 24.6 g (0.3
mol) and add 60ml of water to make a homogeneous solution.
While maintaining the reaction temperature at 25 to 30°C, 55.5 g (0.6 mol) of epichlorohydrin was added dropwise over 1 hour while stirring, and the mixture was allowed to react for 3 hours.
次いで反応液を冷却し、0〜5℃に保ち、20%
水酸化ナトリウム水溶液60ml(0.3モル)を1時
間で滴下した後3時間撹拌を続けることにより、
二官能性エポキシ化合物〔M〕の調製液を得た。 Then, the reaction solution was cooled and kept at 0 to 5°C, and 20%
By dropping 60 ml (0.3 mol) of sodium hydroxide aqueous solution over 1 hour and continuing stirring for 3 hours,
A prepared solution of bifunctional epoxy compound [M] was obtained.
実施例 3
実施例1において得られた中間体A15gと二官
能性エポキシ化合物である化合物〔N〕、
15gとを均一に混合させた後、実施例1と同様
な方法で加熱及び後処理を行つた。Example 3 15g of intermediate A obtained in Example 1 and compound [N] which is a bifunctional epoxy compound, After homogeneously mixing 15 g of the sample, heating and post-treatment were performed in the same manner as in Example 1.
得られた強塩基性イオン交換樹脂は、無色無臭
で、中性塩分解能が5.1meq/g(乾燥物)のビ
ーズ状樹脂(粒径:0.3〜0.7mm)であつた。 The obtained strongly basic ion exchange resin was colorless and odorless, and was a bead-shaped resin (particle size: 0.3 to 0.7 mm) with a neutral salt decomposition ability of 5.1 meq/g (dry material).
なお、二官能性エポキシ化合物〔N〕の合成
は、実施例1で得られた高分子四級塩(中間体
A)の調製液を50〜55℃に保ち、撹拌しながらエ
ピクロルヒドリン9.3g(0.1モル)を1時間で滴
下した後、3時間反応させる。 In addition, the synthesis of the bifunctional epoxy compound [N] was performed by keeping the prepared solution of the polymer quaternary salt (intermediate A) obtained in Example 1 at 50 to 55°C and adding 9.3 g (0.1 g of epichlorohydrin) with stirring. mol) was added dropwise over 1 hour, and the mixture was allowed to react for 3 hours.
次いで、反応液を冷却し、0〜5℃に保ち、20
%水酸化ナトリウム水溶液20ml(0.1モル)を1
時間で滴下した後、3時間撹拌を続けることによ
り二官能性エポキシ化合物〔N〕の調製液を得
た。 Next, the reaction solution was cooled, kept at 0-5°C, and kept at 20°C.
% sodium hydroxide aqueous solution (20 ml (0.1 mol))
After the dropwise addition for 3 hours, stirring was continued for 3 hours to obtain a prepared solution of bifunctional epoxy compound [N].
参考例
本発明樹脂の耐熱性を調べるため、本発明の樹
脂(実施例1および実施例3で得た樹脂)と市販
強塩基性イオン交換樹脂(三菱化成社製ダイヤイ
オンPA316:スチレン―ジビニルベンゼン系、架
橋度8%、トリメチルアンモニウム塩型、Cl型)
について、示差熱天秤装置(理学電機製、恒温型
示差熱天秤8002H型)を用いて熱減量を次の条件
で測定した。Reference Example In order to investigate the heat resistance of the resin of the present invention, the resin of the present invention (resin obtained in Example 1 and Example 3) and a commercially available strongly basic ion exchange resin (Diaion PA316 manufactured by Mitsubishi Chemical Corporation: styrene-divinylbenzene) type, crosslinking degree 8%, trimethylammonium salt type, Cl type)
The thermal loss was measured using a differential thermal balance device (manufactured by Rigaku Denki, constant temperature differential thermal balance model 8002H) under the following conditions.
雰囲気 :空気中
昇温速度:10℃/min
その結果、本発明樹脂は、260℃迄は何ら重量
減はみられなかつた。一方、市販品の熱減量は、
200℃で13%、260℃で25%であつた。 Atmosphere: In air Temperature increase rate: 10°C/min As a result, the resin of the present invention showed no weight loss at all up to 260°C. On the other hand, the heat loss of commercially available products is
It was 13% at 200°C and 25% at 260°C.
Claims (1)
類とを反応させて得られる一般式、 (但し、R1は水素原子、炭素数1〜17のアルキ
ル基又は炭素数6〜8のアリール基を、R2は水
素原子又は炭素数1〜3のアルキル基を、Xはハ
ロゲン原子を、nは1以上の整数をそれぞれ表わ
す) で表わされる高分子四級塩と多官能性エポキシ化
合物を油性媒体中に懸濁させた後これを加熱し硬
化反応せしめることを特徴とする粒状塩基性イオ
ン交換樹脂の製造法。[Claims] 1. A general formula obtained by reacting a halomethyloxirane compound and an imidazole, (However, R 1 is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or an aryl group having 6 to 8 carbon atoms, R 2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X is a halogen atom, (n represents an integer of 1 or more) and a polyfunctional epoxy compound are suspended in an oily medium and then heated to cause a curing reaction. Method of manufacturing replacement resin.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59100102A JPS60245626A (en) | 1984-05-18 | 1984-05-18 | Production of particulate basic ion-exchange resin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59100102A JPS60245626A (en) | 1984-05-18 | 1984-05-18 | Production of particulate basic ion-exchange resin |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60245626A JPS60245626A (en) | 1985-12-05 |
JPH0242369B2 true JPH0242369B2 (en) | 1990-09-21 |
Family
ID=14265026
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP59100102A Granted JPS60245626A (en) | 1984-05-18 | 1984-05-18 | Production of particulate basic ion-exchange resin |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60245626A (en) |
-
1984
- 1984-05-18 JP JP59100102A patent/JPS60245626A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS60245626A (en) | 1985-12-05 |
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