JPS62281849A - Production of n-alkoxymethyl (meth)acrylamide - Google Patents
Production of n-alkoxymethyl (meth)acrylamideInfo
- Publication number
- JPS62281849A JPS62281849A JP61122221A JP12222186A JPS62281849A JP S62281849 A JPS62281849 A JP S62281849A JP 61122221 A JP61122221 A JP 61122221A JP 12222186 A JP12222186 A JP 12222186A JP S62281849 A JPS62281849 A JP S62281849A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylamide
- reaction
- ion exchange
- 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 3
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 7
- 229920002866 paraformaldehyde Polymers 0.000 claims description 7
- 125000004849 alkoxymethyl group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 37
- 239000003456 ion exchange resin Substances 0.000 abstract description 30
- 229920003303 ion-exchange polymer Polymers 0.000 abstract description 30
- 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 abstract description 29
- 239000003054 catalyst Substances 0.000 abstract description 29
- 230000002378 acidificating effect Effects 0.000 abstract description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 15
- 239000002904 solvent Substances 0.000 abstract description 8
- 229920001429 chelating resin Polymers 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 238000006482 condensation reaction Methods 0.000 abstract description 2
- 239000003973 paint Substances 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 38
- 238000000034 method Methods 0.000 description 20
- 239000003960 organic solvent Substances 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 11
- 230000018044 dehydration Effects 0.000 description 9
- 238000006297 dehydration reaction Methods 0.000 description 9
- 150000003926 acrylamides Chemical class 0.000 description 8
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- LSWADWIFYOAQRZ-UHFFFAOYSA-N n-(ethoxymethyl)prop-2-enamide Chemical compound CCOCNC(=O)C=C LSWADWIFYOAQRZ-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- -1 divinyl compound Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- MSWMMJONWLTTGS-UHFFFAOYSA-N 2-hydroxy-2-oxoacetate;triethylazanium Chemical compound OC(=O)C(O)=O.CCN(CC)CC MSWMMJONWLTTGS-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- YOZHLACIXDCHPV-UHFFFAOYSA-N n-(methoxymethyl)-2-methylprop-2-enamide Chemical compound COCNC(=O)C(C)=C YOZHLACIXDCHPV-UHFFFAOYSA-N 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- BBMHARZCALWXSL-UHFFFAOYSA-M sodium dihydrogenphosphate monohydrate Chemical compound O.[Na+].OP(O)([O-])=O BBMHARZCALWXSL-UHFFFAOYSA-M 0.000 description 1
- JXHZRQHZVYDRGX-UHFFFAOYSA-M sodium;hydrogen sulfate;hydrate Chemical compound [OH-].[Na+].OS(O)(=O)=O JXHZRQHZVYDRGX-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- Catalysts (AREA)
- 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Ｎ−アルコキシメチル（メタ）アクリルアミド
の製造法に関する。さらに具体的には、本発明はＮ−メ
チロール（メタ）アクリルアミドとアルコール類を触媒
の存在下、有機溶媒中で反応してＮ−アルコキシメチル
（メタ）アクリルアミドを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing N-alkoxymethyl (meth)acrylamide. More specifically, the present invention relates to a method for producing N-alkoxymethyl (meth)acrylamide by reacting N-methylol (meth)acrylamide and alcohol in an organic solvent in the presence of a catalyst.
Ｎ−アルコキシメチル（メタ）アクリルアミド類はポリ
マーに架橋官能基を導入する有用な化合物であり、塗料
、接着剤などの分野に広（用いられている。N-alkoxymethyl (meth)acrylamides are useful compounds for introducing crosslinking functional groups into polymers, and are widely used in fields such as paints and adhesives.
Ｎ−アルコキシメチル（メタ）アクリルアミド類の製造
法としては従来から種々の方法が知られている。例えば
、（メタ）アクリルアミド、ホルムアルデヒド、及びア
ルコールを有機溶媒中、酸触媒下で反応して一挙にＮ−
アルコキシメチル（メタ）アクリルアミドを得る方法が
ある（米国特許明細書第３０７９４３４号、特公昭４７
−１０７００号公報、特公開４７−２７４９２号公報）
。この方法は（メタ）アクリルアミドのＮ−メチロール
化反応とそのエーテル化によるＮ−アルコキシメチル化
反応の二段の反応を一挙に行うもので効率がよい反面、
生成物中にメチレンビス（メタ）アクリルアミドなど好
ましくない副生物が比較的多量に混入する欠点がある。Various methods have been known for producing N-alkoxymethyl (meth)acrylamides. For example, (meth)acrylamide, formaldehyde, and alcohol are reacted in an organic solvent under an acid catalyst to produce N-
There is a method for obtaining alkoxymethyl (meth)acrylamide (US Pat. No. 3,079,434, Japanese Patent Publication No. 47
-10700 Publication, Japanese Patent Publication No. 47-27492)
. This method performs two steps of N-methylolation reaction of (meth)acrylamide and N-alkoxymethylation reaction by etherification, and is efficient.
The disadvantage is that relatively large amounts of undesirable by-products such as methylenebis(meth)acrylamide are mixed into the product.
また、（メタ）アクリルアミドとホルムアルデヒドを塩
基触媒下で反応させて得られるＮ−メチロール（メタ）
アクリルアミドを有機溶媒中、酸触媒下でアルコールと
反応させてＮ−アルコキシメチル（メタ）アクリルアミ
ドを得る方法もある。Also, N-methylol (meth) obtained by reacting (meth)acrylamide and formaldehyde under a base catalyst.
There is also a method in which N-alkoxymethyl (meth)acrylamide is obtained by reacting acrylamide with an alcohol in an organic solvent under an acid catalyst.
この方法は種々と検討が試みられており、メチロール化
及びエーテル化の触媒の組み合せとして水酸化ナトリウ
ム−硫酸系（Ｒ，Ｄｏｗｂｅｎｋｏ ｅＬ ａｔ Ｊ、
Ｏｒｇ、 Ｃｈｅｍ、２８３４５Ｂ （１９６３）、水
酸化ナトリウム−リン酸系（米国特許明細書第３２８０
１８９号）、トリエチルアミン−蓚酸系（西独特許明細
書第２３１０５１６号）などがｔａ［されている、これ
らの方法によれば、７０〜９８％程度の取得収率で目的
物が得られるが、未だ副反応防止の点では不充分であり
、副生物及び触媒の除去に繁雑な工程を必要とするとい
う欠点を有す。Various studies have been attempted on this method, including a sodium hydroxide-sulfuric acid system (R, Dowbenko eL at J,
Org, Chem, 28345B (1963), Sodium Hydroxide-Phosphate System (U.S. Patent No. 3280
No. 189), triethylamine-oxalic acid system (West German Patent Specification No. 2310516), etc. have been used. According to these methods, the target product can be obtained with a yield of about 70 to 98%, but there are still It is insufficient in terms of preventing side reactions, and has the disadvantage of requiring complicated steps to remove by-products and catalysts.
一般にＮ−アルコキシメチル（メタ）アクリルアミド類
は一１０〜１０℃付近の低融点、９０〜１００℃１０、
ｌ ＝ ０．０１ ｍｅ Ｈｇ付近の高沸点を持つた
め、再結晶あるいは蒸留などの精製操作が容易には行い
難い。In general, N-alkoxymethyl (meth)acrylamides have a low melting point of around -10~10℃, 90~100℃10,
Since it has a high boiling point around l = 0.01 me Hg, it is difficult to perform purification operations such as recrystallization or distillation.
このように、従来のＮ−アルコキシメチル（メタ）アク
リルアミド類の製法では副反応生成物の抑制が不充分で
あり、また副反応生成物や触媒の製品からの除去にも繁
雑な工程を必要としていたため、副反応の抑制と触媒の
容易な系外への除去が重要な課題となっている。As described above, conventional methods for producing N-alkoxymethyl (meth)acrylamides are insufficient in suppressing side reaction products, and also require complicated steps to remove side reaction products and catalysts from products. Therefore, suppression of side reactions and easy removal of the catalyst from the system have become important issues.
本発明は従来法における問題点を解消すべくなされたも
ので、その目的は工業的に存利に実施することのできる
Ｎ−アルコキシメチル（メタ）アクリルアミド類の製造
法を提供することにあり、さらに具体的にはジビニル化
合物生成等の副反応を抑制し、Ｎ−アルコキシメチル（
メタ）アクリルアミド類を高収率で得ると共に、触媒の
系外への除去の容易なＮ−アルコキシメチル（メタ）ア
クリルアミド類の製造法を提供するものである。The present invention has been made to solve the problems in conventional methods, and its purpose is to provide a method for producing N-alkoxymethyl (meth)acrylamides that can be carried out industrially. More specifically, side reactions such as divinyl compound formation are suppressed, and N-alkoxymethyl (
The object of the present invention is to provide a method for producing N-alkoxymethyl (meth)acrylamides in which meth)acrylamides can be obtained in high yield and the catalyst can be easily removed from the system.
本発明者らは前記目的を達成すべ（鋭意研究の結果、強
酸性イオン交喚閘脂を触媒として用い、有Ｒ溶媒中でＮ
−メチロール（メタ）アクリルアミドとアルコール類、
あるいは（メタ）アクリルアミドとパラホルムアルデヒ
ドを塩基触媒下で、反応させた生成物とアルコール類と
を反応し脱水縮合させることによって、ジビニル化合物
の副生が極めて少なく、高収率でＮ−アルコキシメチル
（メタ）アクリルアミド類が得られること及び反応生成
物からの触媒の分離１桑作が極めて容易であることを見
い出した。本発明はこれらの知見に基づいてなされたも
のである。The present inventors have achieved the above object (as a result of intensive research, we have found that using a strongly acidic ion-exchangeable fat as a catalyst, N
- Methylol (meth)acrylamide and alcohols,
Alternatively, by reacting the product of (meth)acrylamide and paraformaldehyde under a base catalyst with alcohol and dehydration condensation, N-alkoxymethyl (N-alkoxymethyl It has been found that it is extremely easy to obtain meth)acrylamides and to separate the catalyst from the reaction product. The present invention has been made based on these findings.
ｃ問題点を解決するための手段〕
本発明の方決は、
（式中Ｒ１は水素またはメチル基を示す）で表わされる
Ｎ−メチロール（メタ）アクリルアミドと
一般式 Ｒ” ＯＩ＋
（式中Ｒ１はＣ１〜、のアルキル基、アリル基またはベ
ンジル基を示す）
で表わされるアルコール類とを強酸性イオン交換樹脂の
存在下、有機溶媒中で反応させることを特徴とするＮ−
アルコキシメチル（メタ）アクリルアミドの製造法であ
る。Means for Solving Problems c] The solution of the present invention is to combine N-methylol (meth)acrylamide represented by the formula (wherein R1 represents hydrogen or a methyl group) and the general formula R''OI+ (wherein R1 is N-, which is characterized by reacting an alcohol represented by C1 to (representing an alkyl group, allyl group or benzyl group) in an organic solvent in the presence of a strongly acidic ion exchange resin.
This is a method for producing alkoxymethyl (meth)acrylamide.
以下に本発明の実施態様について説明する。Embodiments of the present invention will be described below.
本発明の出発原料であるＮ−メチロール（メタ）アクリ
ルアミドは（メタ）アクリルアミドとホルマリンまたは
パラホルムアルデヒドの反応により合成される。Ｎ−メ
チロール（メタ）アクリルアミドは単離精製したものを
用いてもよいが、（メタ）アクリルアミドとパラホルム
アルデヒドを反応して得られた生成物をそのまま用いる
こともできる。N-methylol (meth)acrylamide, which is the starting material of the present invention, is synthesized by reacting (meth)acrylamide with formalin or paraformaldehyde. Although isolated and purified N-methylol (meth)acrylamide may be used, a product obtained by reacting (meth)acrylamide and paraformaldehyde may also be used as it is.
もう一方の原料であるアルコール類としてはメタノール
、エタノール、プロパツール、イソプロパツール、ブタ
ノール、イソブタノール、アリルアルコール、ヘンシル
アルコールなどを上げることができる０本発明における
脱水縮合反応は、有機溶媒中で、触媒としてイオン交換
樹脂の存在下に行う。Examples of alcohols that are the other raw materials include methanol, ethanol, propatool, isopropanol, butanol, isobutanol, allyl alcohol, and hensyl alcohol.The dehydration condensation reaction in the present invention is carried out in an organic solvent. The reaction is carried out in the presence of an ion exchange resin as a catalyst.
本発明の方法はＮ−メチロール（メタ）アクリルアミド
と前述したアルコール類とを有機溶媒中で強酸性イオン
交換樹脂の存在下に反応させることからなる。この反応
は種々の方法に従って実施することができるが、反応器
中に所定量のＮ−メチロール（メタ）アクリルアミド、
アルコール類、有機溶媒及び強酸性イオン交換樹脂を仕
込み、所定温度で反応を行う方法、または反応器中に所
定量のＮ−メチロール（メタ）アクリルアミド、を機溶
媒及び強酸性イオン交換樹脂を仕込み、所定温度で反応
を行う方法、または反応器中に所定量のＮ−メチロール
（メタ）アクリルアミド、有機溶媒及び強酸性イオン交
換樹脂を仕込み、所定温度に保ち、次いでアルコール類
を徐々に加える方法が操作法、その他を考えると好まし
い。The method of the present invention consists of reacting N-methylol (meth)acrylamide with the alcohols mentioned above in an organic solvent in the presence of a strongly acidic ion exchange resin. This reaction can be carried out according to various methods, but a predetermined amount of N-methylol (meth)acrylamide,
A method in which alcohols, an organic solvent, and a strongly acidic ion exchange resin are charged, and the reaction is carried out at a predetermined temperature, or a method in which a predetermined amount of N-methylol (meth)acrylamide, an organic solvent, and a strongly acidic ion exchange resin are charged in a reactor, A method of carrying out the reaction at a predetermined temperature, or a method of charging a predetermined amount of N-methylol (meth)acrylamide, an organic solvent, and a strong acidic ion exchange resin into a reactor, keeping it at a predetermined temperature, and then gradually adding alcohol is the method of operation. It is preferable considering the law and other factors.
アルコール類はＮ−メチロール（メタ）アクリルアミド
１モルに対し０．８〜２０モルの範囲で用いるのがよく
、好ましくは１．０−１０モルの範囲がよい。The alcohol is preferably used in an amount of 0.8 to 20 mol, preferably 1.0 to 10 mol, per 1 mol of N-methylol(meth)acrylamide.
本発明において用いる有機溶媒の例としてはベンゼン、
トルエンのような芳香族炭化水素類、酢酸メチル、酢酸
エチルのようなエステル類、ジクロルメタン、ジクロル
エタン、クロロホルムのような有機ハルダン化物類、ア
セトン、メチルエチルケトンのようなケトン類、ジメチ
ルホルムアミド、ジメチルアセトアミドのようなアミド
類、ジメチルスルホキシドのようなスルホキシド類など
を上げることができる。Examples of organic solvents used in the present invention include benzene,
Aromatic hydrocarbons such as toluene, esters such as methyl acetate and ethyl acetate, organic haldanides such as dichloromethane, dichloroethane and chloroform, ketones such as acetone and methyl ethyl ketone, dimethylformamide and dimethylacetamide. Amides, sulfoxides such as dimethyl sulfoxide, etc.
また、有機溶媒の使用に代えて、原料のアルコール類を
大過剰に用いることもできる。この方法は化学平衡論的
に生成物Ｎ−アルコキシメチル（メタ）アクリルアミド
の生成を有利にし、また単離精製工程が簡略化させるた
めに特に好ましい。Furthermore, instead of using an organic solvent, a large excess of alcohol as a raw material can also be used. This method is particularly preferred because it favors the production of the product N-alkoxymethyl (meth)acrylamide from a chemical equilibrium perspective and simplifies the isolation and purification steps.
有機溶媒の使用量に特に制限はないが、操作性、経済性
を勘案すると生成物濃度が５〜６０％程度になるように
用いるのが好ましく、１０〜５０％程度が特に好ましい
。There is no particular restriction on the amount of the organic solvent used, but in consideration of operability and economy, it is preferable to use it so that the product concentration is about 5 to 60%, particularly preferably about 10 to 50%.
本発明において触媒として用いる強酸性イオン交換樹脂
としてはスルホン酸基を存する重合体からなるもの、ホ
スホン酸酸基を有する重合体からなるもの、カルボン酸
基を有するフルオロカーボン重合体からなるものなどが
好ましい。通常はスチレンとジビニルへソゼンなどの架
橋性上ツマ−を共重合して得られる樹脂をスルホン化し
たもの、およびフェノールスルホン酸をホルムアルデヒ
ドで縮合した樹脂などのゲル状もしくは多孔質のマクロ
ポーラス状のものなどの市販の強酸性イオン交換樹脂を
用いるのがよい。The strongly acidic ion exchange resin used as a catalyst in the present invention is preferably one made of a polymer having a sulfonic acid group, a polymer having a phosphonic acid group, a fluorocarbon polymer having a carboxylic acid group, etc. . Usually, sulfonated resins obtained by copolymerizing styrene and crosslinkable polymers such as divinyl hesozene, and gel-like or porous macroporous resins such as resins obtained by condensing phenolsulfonic acid with formaldehyde are used. It is preferable to use commercially available strong acidic ion exchange resins such as those available on the market.
市販品の例としては、アンバーライトＩｆｌ−１２０Ｂ
、アンバーライト２００Ｃ、アンバーリスト１５１．ダ
ウエックス５０１ＡＸ８、ダウエックスＭＳＣ−１、ダ
イヤイオン５ＫＩＢ、ダイヤイオンｔｌｃＰ−１５０１
（、ダイヤイオンＩＩＰＫ−５５、ダイヤイオンＰＫ２
１６ 、レバチット５１００．レバチット５Ｐ１２０
、デュオライト Ｃ２０、デュオライト０２６などを挙
げることができる。An example of a commercially available product is Amberlite Ifl-120B.
, Amberlyte 200C, Amberlyst 151. DOWEX 501AX8, DOWEX MSC-1, DIAION 5KIB, DIAION tlcP-1501
(, Diaion IIPK-55, Diaion PK2
16, Revachit 5100. Revachit 5P120
, Duolite C20, Duolite 026, etc.
イオン交換樹脂の使用量は特に制限はされないが、通常
反応液に対して０．０１重量％〜４０重量％の範囲、好
ましくは０．１重量％〜２５重量％の範囲で用いるのが
よい。The amount of the ion exchange resin to be used is not particularly limited, but it is usually in the range of 0.01% to 40% by weight, preferably in the range of 0.1% to 25% by weight based on the reaction solution.
反応温度は、触媒としてのイオン交換樹脂の活性および
熱安定性を考慮すれば室温〜１５０’Ｃの範囲、特に４
０℃〜１２０℃の範囲が好ましい。Considering the activity and thermal stability of the ion exchange resin as a catalyst, the reaction temperature is in the range of room temperature to 150'C, especially 4
A range of 0°C to 120°C is preferred.
反応により生成する脱゛離水が、溶媒またはアルコール
類などとの共沸等により反応系外に除去できる場合は反
応はより促進される。The reaction is further promoted if the deionized water produced by the reaction can be removed from the reaction system by azeotropy with a solvent or alcohol.
反応圧力は、特に制限されるも、のではなく、常圧、加
圧、減圧に亘って広（採用される。反応時間は、原料の
濃度、触媒量、溶剤、反応塩！変などの条件により異な
るが、通常０．５時間から２４時間程度が適当である。The reaction pressure is not particularly limited, but can be widened (adopted) from normal pressure, elevated pressure, and reduced pressure. Although it varies depending on the situation, approximately 0.5 to 24 hours is usually appropriate.
このようにして生成したＮ−アルコキシメチル（メタ）
アクリルアミドは反応混合物からイオン交換樹脂をが別
分離後、溶剤を留去することによって容易に分離取得す
ることができる。更に、精製が必要な場合には公知の方
法に従って再結晶やｇｆｆｌなどを行うことができる。N-alkoxymethyl (meth) produced in this way
Acrylamide can be easily separated and obtained by separating the ion exchange resin from the reaction mixture and then distilling off the solvent. Furthermore, if purification is required, recrystallization, gffl, etc. can be performed according to known methods.
本発明方法において、触媒として使用したイオン交換樹
脂は、反復再使用することが可能であり、触媒活性の持
続または再生するための処理をすることもできる。その
処理としては有機溶剤及び希酸による洗浄処理を行うの
が好ましい。In the method of the present invention, the ion exchange resin used as a catalyst can be repeatedly reused and can also be treated to maintain or regenerate the catalyst activity. As the treatment, it is preferable to perform a cleaning treatment using an organic solvent and a dilute acid.
本発明のもう一つの反応方法は、Ｎ−メチロール（メタ
）アクリルアミドとして、（メタ）アクリルアミドとパ
ラホルムアルデヒドを反応して得られた生成物を用いて
、アルコール類との脱水縮合を行いＮ−アルコキシメチ
ル（メタ）アクリルアミドの製造を行うものであり、脱
水縮合工程は前述の場合と同様に実施される。この場合
、生成するＮ−メチロール（メタ）アクリルアミドは反
応生成物から単離することなく、アルコール類との脱水
縮合工程に移行することができる。Another reaction method of the present invention is to use the product obtained by reacting (meth)acrylamide and paraformaldehyde to produce N-methylol (meth)acrylamide, and conduct dehydration condensation with alcohol to produce N-alkoxy Methyl (meth)acrylamide is produced, and the dehydration condensation step is carried out in the same manner as described above. In this case, the generated N-methylol (meth)acrylamide can be transferred to the dehydration condensation step with the alcohol without being isolated from the reaction product.
Ｎ−メチロール（メタ）アクリルアミドの合成反応は有
機溶媒中で行うのが好ましい、有機溶媒としては前述の
ものが用いられるが、後の脱水縮合工程で用いるアルコ
ール類を用いてもよい。この反応は常法に従って酸触媒
または塩基触媒の存在下で行われる。The synthesis reaction of N-methylol (meth)acrylamide is preferably carried out in an organic solvent. As the organic solvent, those mentioned above are used, but alcohols used in the subsequent dehydration condensation step may also be used. This reaction is carried out in the presence of an acid or base catalyst according to conventional methods.
酸触媒を用いる場合は、後の脱水縮合工程で使用する強
酸性イオン交換樹脂を触媒として用い、アルコール類共
存下で反応を行い、メチロール化とそれに続くアルコキ
シ化を一挙に行う方法が有利である。When using an acid catalyst, it is advantageous to use a strongly acidic ion exchange resin used in the subsequent dehydration condensation step as a catalyst, carry out the reaction in the presence of an alcohol, and perform methylolation and subsequent alkoxylation all at once. .
塩基触媒を用いる場合は、強塩基性あるいは弱塩基性イ
オン交換樹脂、水酸化ナトリウムなどの水酸化アルカリ
、トリエチルアミンなどの第３級アミンを触媒として用
いるのが好ましい。特に塩基性イオン交換樹脂を用いる
方法は触媒の分離回収が容易になり好ましい、水酸化ナ
トリウムまたはトリエチルアミンなどの触媒を用いた場
合は、これらの触媒は後の脱水縮合時の強酸性イオン交
換樹脂触媒に付着させて容易に除去できる。When using a base catalyst, it is preferable to use a strongly basic or weakly basic ion exchange resin, an alkali hydroxide such as sodium hydroxide, or a tertiary amine such as triethylamine as the catalyst. In particular, a method using a basic ion exchange resin is preferred because it facilitates the separation and recovery of the catalyst.If a catalyst such as sodium hydroxide or triethylamine is used, these catalysts are used as strong acid ion exchange resin catalysts during the subsequent dehydration condensation. It can be easily removed by attaching it to the surface.
（メタ）アクリルアミドとパラホルムアルデヒドの反応
は（メタ）アクリルアミドに対し、等モル量ないし１．
５倍モル量のパラホルムアルデヒドを生成物濃度３０重
量％〜９０重量％、好ましくは５０重量％〜８５重量％
の濃度になる量の溶媒あるいはアルコール類中で触媒の
存在下に行う。触媒の使用量は、水酸化アルカリまたは
第３級アミンを用いた場合は（メタ）アクリルアミド１
モルに対し１０−５モル〜１０−１モル、好ましくは１
０−４モル〜１０１モルであり、また塩基性イオン交換
樹脂触媒を用いた場合は反応液に対し、０．０１重量％
〜２０重量％、好ましくは０．１重量％〜１０重量％で
ある。反応温度は室温〜１５０℃、特に４０〜１ｏｏ℃
の範囲が好ましい。反応時間は通常０．５時間から２４
時間程度が適当である。このようにして生成したＮ−メ
チロール（メタ）アクリルアミドは必要により塩基触媒
を分離した後、所定量のアルコール類を加え、更に強酸
性イオン交換樹脂を添加した後、脱水縮合工程に移行す
る。The reaction between (meth)acrylamide and paraformaldehyde is carried out in an equimolar amount to 1.0 molar amount to (meth)acrylamide.
5 times the molar amount of paraformaldehyde at a product concentration of 30% to 90% by weight, preferably 50% to 85% by weight.
It is carried out in the presence of a catalyst in an amount of a solvent or alcohol to give a concentration of . When using alkali hydroxide or tertiary amine, the amount of catalyst used is (meth)acrylamide 1
10-5 mol to 10-1 mol, preferably 1 mol to mol
0-4 mol to 101 mol, and when a basic ion exchange resin catalyst is used, it is 0.01% by weight based on the reaction solution.
-20% by weight, preferably 0.1% - 10% by weight. The reaction temperature is room temperature to 150°C, especially 40 to 100°C.
A range of is preferred. Reaction time is usually 0.5 hours to 24 hours.
An appropriate amount of time is required. After separating the base catalyst from the N-methylol (meth)acrylamide thus produced, if necessary, a predetermined amount of alcohol is added thereto, and a strongly acidic ion exchange resin is further added thereto, followed by a dehydration condensation step.
本発明の方法によれば、副生物の少ないＮ−アルコキン
メチル（メタ）アクリルアミドが高収率で得られる。ま
た本発明は次のような利点も有するものである。According to the method of the present invention, N-alcoquine methyl (meth)acrylamide with few by-products can be obtained in high yield. The present invention also has the following advantages.
Ｉ）目的生成物の収率が高い。I) High yield of target product.
■）副生物が少ないため精製が容易である。■) Purification is easy because there are few by-products.
ＩＩＩ）生成物からの触媒の分離が極めて容易である。III) Separation of the catalyst from the product is extremely easy.
■）触媒の再使用が可能である。■) Catalyst can be reused.
このように、本発明の方法は単に従来文献に未記載の新
製法であるばかりでなく、工業土掻めて有用なＮ−アル
コキシメチル（メタ）アクリルアミドの製法である。As described above, the method of the present invention is not only a new production method that has not been previously described in the literature, but also a method for producing N-alkoxymethyl (meth)acrylamide that is industrially useful.
以下、実施例により本発明の構成および効果をさらに具
体的に説明するが、本発明はこれらの実施例に何ら限定
されるものでない。EXAMPLES Hereinafter, the structure and effects of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.
実施例１
温度計、攪拌機、還流冷却器を付した反応器にＮ−メ千
ロールアクリルアミド５０．６ ｇ （０，５モル）、
エタノール２３０ｇ （５，０モル）、重合禁止剤ハイ
ドロキノンモノメチルエーテル０．０５ ｇ 、及び強
酸性イオン交換樹脂アンバーライトＩＲ−１２０Ｂ １
．０ｇを仕込み、攪拌下で８０℃、６時間反応させた。Example 1 In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 50.6 g (0.5 mol) of N-methylol acrylamide was added.
230 g (5.0 mol) of ethanol, 0.05 g of polymerization inhibitor hydroquinone monomethyl ether, and strong acidic ion exchange resin Amberlite IR-120B 1
．． 0 g was charged and reacted at 80° C. for 6 hours with stirring.
反応終了後、室温まで冷却し、イオン交換樹脂を１戸別
した。反応液を高速液体クロマトグラフ分析したところ
９４．７％の反応収率でＮ−エトキシメチルアクリルア
ミドが生成していた。反応液を減圧下で溶媒留去したと
ころ無色透明液体のＮ−エトキシメチルアクリルアミド
６１．５ ｇを取得した。取得収率は９５．２％であっ
た。After the reaction was completed, it was cooled to room temperature, and the ion exchange resin was separated from each other. High performance liquid chromatography analysis of the reaction solution revealed that N-ethoxymethylacrylamide was produced with a reaction yield of 94.7%. The solvent of the reaction solution was distilled off under reduced pressure to obtain 61.5 g of N-ethoxymethylacrylamide as a colorless transparent liquid. The obtained yield was 95.2%.
実施例２〜５
実施例１と同様の方法でＮ−メチロールアクリルアミド
０．５モルと各種アルコール５．０モルを重合禁止剤ハ
イドロキノンモノメチルエーテル及び強酸性イオン交換
樹脂の共存下で反応させて、対応するＮ−アルコキシメ
チルアクリルアミドを得た。各実施例により得られたＮ
−アルコキシメチルアクリルアミドの反応収率（反応液
の高速液クロ分析）、取得量および取得収率を、それぞ
れの原料及び反応条件と共にまとめて表１に示した。Examples 2 to 5 In the same manner as in Example 1, 0.5 mol of N-methylolacrylamide and 5.0 mol of various alcohols were reacted in the coexistence of a polymerization inhibitor hydroquinone monomethyl ether and a strongly acidic ion exchange resin. N-alkoxymethylacrylamide was obtained. N obtained in each example
The reaction yield (high-performance liquid chromatography analysis of the reaction solution), the amount obtained, and the obtained yield of -alkoxymethylacrylamide are summarized in Table 1 together with the respective raw materials and reaction conditions.
表−１
実施例６
温度計、攪拌機、滴下ロート、蒸留装置を付した反応器
にＮ−メチロールアクリルアミド５０．６ ｇ（０，５
モル）、エタノール９２ｇ（２０モル）−重合禁止剤ハ
イドロキノンモノメチルエーテル０．１ｇ及び強酸性イ
オン交換樹脂アンバーリスト１５．０．５ｇを仕込み、
還流下（約８１℃）で３時間反応させる。この時、反応
器に付した蒸留装置からエタノールと水の共沸物を留出
させ、留出分に相当する工・タノールを滴下ロートから
反応器に補った。Table 1 Example 6 50.6 g of N-methylolacrylamide (0.5
mol), 92 g (20 mol) of ethanol, 0.1 g of polymerization inhibitor hydroquinone monomethyl ether, and 15.0.5 g of strongly acidic ion exchange resin Amberlyst.
React for 3 hours under reflux (approximately 81° C.). At this time, an azeotrope of ethanol and water was distilled out from a distillation device attached to the reactor, and ethanol and tanol corresponding to the distillate were added to the reactor from the dropping funnel.
反応終了後こ室温まで冷却し、イオン交１負樹脂を７１
別した。反応液を分析したところ、９７．９％の反応収
率でＮ−エトキシメチルアクリルアミドが生成していた
°。反応液を減圧下で溶媒留去したところ無色透明液体
のＮ−エトキシメチルアクリルアミド６３．５ ｇを取
得した。取得収率は９８．３％であづた。After the reaction was completed, the mixture was cooled to room temperature, and 71% of the ion exchanger 1 negative resin was added.
Separated. Analysis of the reaction solution revealed that N-ethoxymethylacrylamide was produced with a reaction yield of 97.9%. The solvent of the reaction solution was distilled off under reduced pressure to obtain 63.5 g of N-ethoxymethylacrylamide as a colorless transparent liquid. The obtained yield was 98.3%.
実施例７
実施例６と同様の反応器にＮ−メチロールメタアクリル
アミド５７．６ｇ（０，５モル）、メタノール１００ｇ
（３，１モル）、ベンゼン１００ｇ （１，３モル）
、重合禁止剤ハイドロキノン０．１ ｇ及び強酸性イオ
ン交換樹脂アンパリス）１５０．５ｇを仕込み、還流下
（約７０℃）で５時間反応させる。この時、反応器に付
した蒸留装置から、メタノール、ベンゼン及び水の混合
物を留出させ、留出分に相当するメタノールとベンゼン
の等量混合物を滴下コートから反応器に補った。反応終
了後、室温まで冷却し、イオン交換樹脂をが刑した。反
応液を分析したところ９３．７％の反応収率でＮ−メト
キンメチルメタアクリルアミドが生成していた。反応液
を減圧下で溶媒留去したところ無色透明液体のＮ−メト
キシメチルメタアクリルアミド６０．Ｏｇを取得した。Example 7 In a reactor similar to Example 6, 57.6 g (0.5 mol) of N-methylolmethacrylamide and 100 g of methanol were added.
(3,1 mol), benzene 100g (1,3 mol)
, 0.1 g of a polymerization inhibitor hydroquinone, and 150.5 g of a strongly acidic ion exchange resin Amparis), and the mixture was reacted under reflux (about 70° C.) for 5 hours. At this time, a mixture of methanol, benzene, and water was distilled out from a distillation device attached to the reactor, and an equal amount of a mixture of methanol and benzene corresponding to the distillate was added to the reactor from the drop coat. After the reaction was completed, it was cooled to room temperature and the ion exchange resin was boiled. Analysis of the reaction solution revealed that N-methynemethylmethacrylamide was produced with a reaction yield of 93.7%. When the solvent of the reaction solution was distilled off under reduced pressure, N-methoxymethylmethacrylamide was obtained as a colorless transparent liquid (60%). Obtained Og.
取得収率は９２．９％であった。The obtained yield was 92.9%.
実施例日
実施例６と同様の反応器にアクリルアミド３３５ｇ （
０，５モル）、エタノール２０ ｇ （０，４モル）、
９４％バラホルムアルデヒド１９．２ｇ（０，６モル）
、重合禁止剤ハイドロキノンモノメチルエーテル０．１
ｇ及び強塩基性イオン交換樹脂アンバーライ） ＩＲＩ
Ｉ−４００、０、２ ｇを仕込み、６０℃で７時間、攪
拌下で反応した。反応終了後、室温まで冷却し、イオン
交換樹脂を決別した。Example day: 335 g of acrylamide (
0.5 mol), 20 g ethanol (0.4 mol),
94% rose formaldehyde 19.2g (0.6 mol)
, polymerization inhibitor hydroquinone monomethyl ether 0.1
g and strong basic ion exchange resin Amberly) IRI
0.2 g of I-400 was charged and reacted at 60°C for 7 hours with stirring. After the reaction was completed, it was cooled to room temperature and the ion exchange resin was separated.
次いで、強酸性イオン交換樹脂アンバーライトＩＲ−１
２０Ｂ １．ｏｇ及びエタノール９５ｇ（２，１モル）
を追添加した後、還流下（約８１℃）で６時間反応させ
る。この時、反応器に付した蒸留装置からエタノールと
水の共沸物を留出させ、留出分に相当するエタノールを
滴下ロートから反応器に補った。Next, strongly acidic ion exchange resin Amberlite IR-1
20B 1. og and ethanol 95g (2.1 mol)
After additionally adding , the mixture is allowed to react under reflux (approximately 81°C) for 6 hours. At this time, an azeotrope of ethanol and water was distilled out from a distillation device attached to the reactor, and ethanol corresponding to the distillate was supplemented into the reactor from the dropping funnel.
反応終了後、室温まで冷却し、イオン交換樹脂を１戸別
した。反応液を分析したところ、９１．０％の反応収率
でＮ−エトキシメチルアクリルアミドが生成していた。After the reaction was completed, it was cooled to room temperature, and the ion exchange resin was separated from each other. Analysis of the reaction solution revealed that N-ethoxymethylacrylamide was produced with a reaction yield of 91.0%.
反応液を減圧下で溶媒留去したところ無色透明液体のＮ
−エトキンメチルアクリルアミド６０．５ ｇを取得し
た。取得収率は９３．７％であった。When the solvent was distilled off from the reaction solution under reduced pressure, N was a colorless and transparent liquid.
-Etquin 60.5 g of methylacrylamide were obtained. The obtained yield was 93.7%.
Claims (2)
Ｎ−メチロール（メタ）アクリルアミドと 一般式Ｒ＾２ＯＨ （式中Ｒ＾２はＣ＿１〜＿４のアルキル基、アリル基ま
たはベンジル基を示す） で表わされるアルコール類とを強酸性イオン交換樹脂の
存在下、有機溶媒中で反応させることを特徴とするＮ−
アルコキシメチル（メタ）アクリルアミドの製造法。(1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 represents hydrogen or a methyl group) ^2 represents an alkyl group, allyl group or benzyl group of C_1 to_4) N-
A method for producing alkoxymethyl (meth)acrylamide.
メタ）アクリルアミドとパラホルムアルデヒドを反応し
て得られた生成物を用いる特許請求の範囲第１項記載の
製造法。(2) As N-methylol (meth)acrylamide (
2. The manufacturing method according to claim 1, which uses a product obtained by reacting meth)acrylamide and paraformaldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61122221A JPH0610176B2 (en) | 1986-05-29 | 1986-05-29 | Process for producing N-alkoxymethyl (meth) acrylamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61122221A JPH0610176B2 (en) | 1986-05-29 | 1986-05-29 | Process for producing N-alkoxymethyl (meth) acrylamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62281849A true JPS62281849A (en) | 1987-12-07 |
| JPH0610176B2 JPH0610176B2 (en) | 1994-02-09 |
Family
ID=14830550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61122221A Expired - Fee Related JPH0610176B2 (en) | 1986-05-29 | 1986-05-29 | Process for producing N-alkoxymethyl (meth) acrylamide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0610176B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08198833A (en) * | 1995-01-30 | 1996-08-06 | Dainippon Ink & Chem Inc | Production of n-butoxymethyl (meth)acrylamides |
| CN114315625A (en) * | 2021-12-28 | 2022-04-12 | 徐州博康信息化学品有限公司 | Preparation method of acid diffusion inhibitor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6168453A (en) * | 1984-09-11 | 1986-04-08 | Mitsui Toatsu Chem Inc | Production of n-alkoxymethyl(meth)acrylamide |
-
1986
- 1986-05-29 JP JP61122221A patent/JPH0610176B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6168453A (en) * | 1984-09-11 | 1986-04-08 | Mitsui Toatsu Chem Inc | Production of n-alkoxymethyl(meth)acrylamide |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08198833A (en) * | 1995-01-30 | 1996-08-06 | Dainippon Ink & Chem Inc | Production of n-butoxymethyl (meth)acrylamides |
| CN114315625A (en) * | 2021-12-28 | 2022-04-12 | 徐州博康信息化学品有限公司 | Preparation method of acid diffusion inhibitor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0610176B2 (en) | 1994-02-09 |
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