JPH04321658A - Production of n-methylolacrylamide - Google Patents
Production of n-methylolacrylamideInfo
- Publication number
- JPH04321658A JPH04321658A JP3116666A JP11666691A JPH04321658A JP H04321658 A JPH04321658 A JP H04321658A JP 3116666 A JP3116666 A JP 3116666A JP 11666691 A JP11666691 A JP 11666691A JP H04321658 A JPH04321658 A JP H04321658A
- Authority
- JP
- Japan
- Prior art keywords
- methylolacrylamide
- acrylamide
- reaction
- present
- formaldehyde
- 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.)
- Pending
Links
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 11
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 10
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 10
- 239000003125 aqueous solvent Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 abstract description 12
- 239000006227 byproduct Substances 0.000 abstract description 11
- 239000012452 mother liquor Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- -1 ammonium hydroxide compound Chemical class 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 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 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 229940027983 antiseptic and disinfectant quaternary ammonium compound Drugs 0.000 description 1
- LAUPTJWHHKNSCT-UHFFFAOYSA-M benzyl-hexadecyl-dimethylazanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 LAUPTJWHHKNSCT-UHFFFAOYSA-M 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical compound CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 description 1
- 229960004830 cetylpyridinium Drugs 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- VCAVAURZPNANDQ-UHFFFAOYSA-N ethyl-hexadecyl-dimethylazanium Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CC VCAVAURZPNANDQ-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical compound CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、アクリルアミドとホル
ムアルデヒドまたはパラホルムアルデヒドとを反応せし
めることによってＮ−メチロールアクリルアミドを製造
する方法に関するものである。Ｎ−メチロールアクリル
アミドは、繊維処理、感光性樹脂、接着剤、塗料などに
広く用いられる架橋性モノマーである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing N-methylolacrylamide by reacting acrylamide with formaldehyde or paraformaldehyde. N-methylol acrylamide is a crosslinking monomer widely used in fiber treatments, photosensitive resins, adhesives, paints, etc.
【０００２】0002
【従来の技術】Ｎ−メチロールアクリルアミドの製造法
については、従来から種々の方法が知られている。例え
ば、アクリルアミドとホルムアルデヒドとを水性溶媒中
で水酸化ナトリウムを触媒として、アクリルアミド濃度
６０から９７％で反応させる方法（特公昭３８−１５３
５８号公報）、アクリルアミドとホルムアルデヒドとを
無溶媒で、トリエチルアミンやトリエタノ−ルアミンの
ような三級アミン類を触媒として用いて反応させる方法
（特公昭３５−４２０８号公報）、無溶媒または水もし
くは有機溶媒中で塩基性陰イオン交換樹脂を触媒とする
方法（特開昭４９−１４４１８号公報、特開昭４９−３
６６１５号公報および特開昭４９−１２７９１２号公報
）、等が提案されている。BACKGROUND OF THE INVENTION Various methods have been known for producing N-methylolacrylamide. For example, a method in which acrylamide and formaldehyde are reacted in an aqueous solvent using sodium hydroxide as a catalyst at an acrylamide concentration of 60 to 97% (Japanese Patent Publication No. 38-153
58), a method of reacting acrylamide and formaldehyde without a solvent using tertiary amines such as triethylamine or triethanolamine as a catalyst (Japanese Patent Publication No. 35-4208), a method of reacting acrylamide and formaldehyde without a solvent, using water or organic A method using a basic anion exchange resin as a catalyst in a solvent (JP-A-49-14418, JP-A-49-3
No. 6615 and Japanese Unexamined Patent Publication No. 127912/1983), etc. have been proposed.
【０００３】しかしながら、従来のＮ−メチロールアク
リルアミド製造法では副反応生成物の抑制が十分でなく
、反応液中に副生成物が蓄積され、Ｎ−メチロールアク
リルアミドの収率が低下するのみならず、高純度のＮ−
メチロールアクリルアミドを得るには煩雑な精製工程を
必要としなければならないこと、触媒の使用量が多いこ
と、あるいは触媒が比較的高価なものであることなど、
工業的に実施する方法としては改善すべき問題があった
。However, in the conventional method for producing N-methylolacrylamide, side reaction products are not sufficiently suppressed, and byproducts accumulate in the reaction solution, resulting in not only a decrease in the yield of N-methylolacrylamide, but also High purity N-
Obtaining methylol acrylamide requires a complicated purification process, requires a large amount of catalyst, or is relatively expensive.
There were problems that needed to be improved as a method for industrial implementation.
【０００４】0004
【発明が解決しようとする課題】本発明は、従来法にお
ける問題点を解決すべくなされたもので、その目的は工
業的に有利に実施することのできるＮ−メチロールアク
リルアミドの製造方法を提供することにある。さらに具
体的には、反応選択率を向上させ、副反応生成物の生成
を抑制することにより、高純度のＮ−メチロールアクリ
ルアミドを高収率で得ることのできるＮ−メチロールア
クリルアミドの製造方法を提供することにある。OBJECTS OF THE INVENTION The present invention has been made to solve the problems in conventional methods, and its purpose is to provide a method for producing N-methylolacrylamide that can be carried out industrially advantageously. There is a particular thing. More specifically, it provides a method for producing N-methylolacrylamide that can obtain high-purity N-methylolacrylamide in high yield by improving reaction selectivity and suppressing the production of side reaction products. It's about doing.
【０００５】[0005]
【課題を解決するための手段】本発明者らは前記目的を
達成すべく鋭意研究の結果、Ｎ−メチロールアクリルア
ミドを製造する際に水酸化四級アンモニウム化合物の存
在下で反応を行なうと副生物の生成が抑制され、高選択
率で反応が進行することを見出して本発明に到達した。[Means for Solving the Problem] As a result of intensive research to achieve the above object, the present inventors have found that when the reaction is carried out in the presence of a quaternary ammonium hydroxide compound when producing N-methylol acrylamide, by-products are produced. The present invention was achieved by discovering that the formation of is suppressed and the reaction proceeds with high selectivity.
【０００６】本発明は、水性溶媒中、アクリルアミドと
ホルムアルデヒドまたはパラホルムアルデヒドを反応さ
せ、Ｎ−メチロールアクリルアミドを製造する方法にお
いて、該反応を水酸化四級アンモニウム化合物の存在下
で行なうことを特徴とするＮ−メチロールアクリルアミ
ドの製造方法に関するものである。The present invention is a method for producing N-methylolacrylamide by reacting acrylamide with formaldehyde or paraformaldehyde in an aqueous solvent, characterized in that the reaction is carried out in the presence of a quaternary ammonium hydroxide compound. The present invention relates to a method for producing N-methylol acrylamide.
【０００７】以下に本発明の実施態様について説明する
。本発明の方法は、出発原料であるアクリルアミドとホ
ルムアルデヒドまたはパラホルムアルデヒドとを、水性
溶媒中、水酸化四級アンモニウム化合物を触媒として用
いて反応を行なうことからなる。[0007] Embodiments of the present invention will be explained below. The method of the present invention consists of reacting starting materials acrylamide and formaldehyde or paraformaldehyde in an aqueous solvent using a quaternary ammonium hydroxide compound as a catalyst.
【０００８】本発明に用いる出発原料であるアクリルア
ミドは、水溶液あるいは結晶のいずれのものでもよい。
また、ホルムアルデヒドは水溶液が好ましく、市販の３
７％ホルマリンを用いることができる。パラホルムアル
デヒドも市販の純度７０から９５％のものでよい。[0008] Acrylamide, which is a starting material used in the present invention, may be in the form of an aqueous solution or a crystal. Further, formaldehyde is preferably an aqueous solution, and commercially available 3
7% formalin can be used. Paraformaldehyde may also be commercially available with a purity of 70 to 95%.
【０００９】本発明におけるアクリルアミドとホルムア
ルデヒドあるいはパラホルムアルデヒドとの使用割合は
、アクリルアミド１モルに対しホルムアルデヒドあるい
はパラホルムアルデヒド（ホルムアルデヒド換算）は０
．５から２モル、好ましくは０．８から１．５モルの範
囲がよい。[0009] The ratio of acrylamide and formaldehyde or paraformaldehyde used in the present invention is such that formaldehyde or paraformaldehyde (in terms of formaldehyde) is 0 per mole of acrylamide.
．． The amount ranges from 5 to 2 mol, preferably from 0.8 to 1.5 mol.
【００１０】本発明に用いる溶媒は、水または水とこれ
に可溶な有機溶媒との混合溶媒であればよく、有機溶媒
としてはメタノール、エタノール、アセトンなどを挙げ
ることができる。混合溶媒を用いる場合の水の割合は５
０重量％以上が好ましい。The solvent used in the present invention may be water or a mixed solvent of water and an organic solvent soluble therein. Examples of the organic solvent include methanol, ethanol, and acetone. When using a mixed solvent, the proportion of water is 5
It is preferably 0% by weight or more.
【００１１】本発明に用いることのできる水酸化四級ア
ンモニウム化合物としては、水酸化テトラメチルアンモ
ニウム、水酸化テトラエチルアンモニウム、水酸化テト
ラプロピルアンモニウム、水酸化テトラブチルアンモニ
ウム、水酸化トリメチルベンジルアンモニウム、水酸化
セチルエチルジメチルアンモニウム、水酸化セチルジメ
チルベンジルアンモニウム、水酸化ヘキサデシルトリメ
チルアンモニウム、水酸化トリオクチルメチルアンモニ
ウムおよび水酸化セチルピリジニウムなどを挙げること
ができる。また、反応系内で四級アンモニウム塩と水酸
化ナトリウムなどの強アルカリとにより水酸化四級アン
モニウム化合物を生成させて用いてもよい。しかし、イ
オン交換樹脂のような高分子量の四級アンモニウム化合
物は、その使用量が多く、副生物の生成量も多いため不
適当である。Examples of quaternary ammonium hydroxide compounds that can be used in the present invention include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, and tetramethylammonium hydroxide. Examples include cetyl ethyldimethylammonium, cetyldimethylbenzylammonium hydroxide, hexadecyltrimethylammonium hydroxide, trioctylmethylammonium hydroxide, and cetylpyridinium hydroxide. Alternatively, a quaternary ammonium hydroxide compound may be generated by using a quaternary ammonium salt and a strong alkali such as sodium hydroxide in the reaction system. However, high molecular weight quaternary ammonium compounds such as ion exchange resins are unsuitable because they are used in large amounts and produce large amounts of by-products.
【００１２】本発明において用いる水酸化四級アンモニ
ウム化合物の使用量は、アクリルアミド１モルに対して
０．００１から１０モル％、好ましくは０．０１から５
モル％の範囲の中から選ばれる。The amount of the quaternary ammonium hydroxide compound used in the present invention is 0.001 to 10 mol %, preferably 0.01 to 5 mol %, based on 1 mol of acrylamide.
Selected from a range of mol%.
【００１３】また、前記水酸化四級アンモニウム化合物
は、従来、触媒として知られているアルカリ金属化合物
または三級アミン類と一緒に用いることができる。アル
カリ金属化合物としては、水酸化リチウム、水酸化ナト
リウム、水酸化カリウム、リン酸三ナトリウム、リン酸
二ナトリウム、ピロリン酸ナトリウム、リン酸三カリウ
ム、リン酸二カリウムおよびホウ酸ナトリウムなど、三
級アミン類としては、トリメチルアミン、トリエチルア
ミン、トリエタノ−ルアミンおよびＮ−エチルモルホリ
ンなどを、それぞれ挙げることができる。Further, the quaternary ammonium hydroxide compound can be used together with an alkali metal compound or tertiary amines conventionally known as catalysts. Alkali metal compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, sodium pyrophosphate, tripotassium phosphate, dipotassium phosphate, and sodium borate, and tertiary amines. As examples, trimethylamine, triethylamine, triethanolamine and N-ethylmorpholine can be mentioned.
【００１４】この場合、水酸化四級アンモニウム化合物
は、全使用量の５０モル％以上になるように用いるのが
よい。In this case, the quaternary ammonium hydroxide compound is preferably used in an amount of 50 mol % or more of the total amount used.
【００１５】反応は、反応温度が２０から８０℃、好ま
しくは３０から６０℃の範囲、反応溶液のｐＨが７以上
、好ましくは８から１２の範囲で実施するのがよい。The reaction is preferably carried out at a reaction temperature of 20 to 80°C, preferably 30 to 60°C, and a pH of the reaction solution of 7 or more, preferably 8 to 12.
【００１６】本発明の方法によれば、副生物の少ないＮ
−メチロールアクリルアミドが水溶液として得られる。
結晶のＮ−メチロールアクリルアミドを得る場合は、反
応溶液から該アミドを晶析、分離することにより容易に
高純度のものが得られる。According to the method of the present invention, N
- Methylolacrylamide is obtained as an aqueous solution. When obtaining crystalline N-methylolacrylamide, highly pure one can be easily obtained by crystallizing and separating the amide from the reaction solution.
【００１７】また、Ｎ−メチロールアクリルアミドは溶
解性がよく、反応溶液からＮ−メチロールアクリルアミ
ドを分離した後の分離母液には未反応原料と共に生成物
のＮ−メチロールアクリルアミドも含まれている。本発
明の方法では副生物の生成が極めて少ないため、従来の
方法とは異なりこの分離母液をリサイクル使用すること
が容易である。Furthermore, N-methylolacrylamide has good solubility, and the separated mother liquor after separating N-methylolacrylamide from the reaction solution contains the product N-methylolacrylamide as well as unreacted raw materials. Since the method of the present invention produces very few by-products, it is easy to recycle the separated mother liquor, unlike conventional methods.
【００１８】また、本発明の方法で得られるＮ−メチロ
ールアクリルアミド含有溶液は、該アミドを単離するこ
となくそのまま水溶液として、たとえばＮ−ブトキシメ
チルアクリルアミド、Ｎ−ジメチルアミノメチルアクリ
ルアミドなどのＮ−メチロールアクリルアミド誘導体の
合成に用いることができる。Further, the N-methylol acrylamide-containing solution obtained by the method of the present invention can be used as an aqueous solution as it is without isolating the amide. It can be used to synthesize acrylamide derivatives.
【００１９】[0019]
【実施例】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はない。
実施例１
攪拌機、温度計、ｐＨ計を備えた２００ｃｃ反応器に、
６０ｇの結晶アクリルアミド、１４ｇの水を投入し、内
温を５０℃にしてアクリルアミドを溶解する。ついで、
触媒として１０％水酸化テトラエチルアンモニウム水溶
液を加え、溶液のｐＨを１０に調整する。ついで、９５
％パラホルムアルデヒド２７．２ｇを加え、前記触媒水
溶液を用いて反応溶液のｐＨを１０に保ちながら反応さ
せる。なお、反応に要した触媒の使用量は０．０９モル
％（対アクリルアミド）であった。反応液を高速液体ク
ロマトグラフで分析したところ、反応開始１時間後、反
応溶液中のＮ−メチロールアクリルアミドの生成率は９
３．２％、副生物は０．２％であった。EXAMPLES The structure and effects of the present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples in any way. Example 1 A 200cc reactor equipped with a stirrer, a thermometer, and a pH meter was
Add 60 g of crystalline acrylamide and 14 g of water, and raise the internal temperature to 50°C to dissolve the acrylamide. Then,
A 10% aqueous tetraethylammonium hydroxide solution is added as a catalyst, and the pH of the solution is adjusted to 10. Then, 95
% paraformaldehyde is added, and the reaction is carried out while maintaining the pH of the reaction solution at 10 using the aqueous catalyst solution. The amount of catalyst required for the reaction was 0.09 mol% (based on acrylamide). When the reaction solution was analyzed by high-performance liquid chromatography, the production rate of N-methylolacrylamide in the reaction solution was 9 after 1 hour from the start of the reaction.
3.2%, and by-products were 0.2%.
【００２０】実施例２〜５
表１に示した触媒および反応条件を用いて、実施例１と
同様の方法でアクリルアミドとホルムアルデヒドあるい
はパラホルムアルデヒドとの反応を行なった。Examples 2 to 5 Acrylamide and formaldehyde or paraformaldehyde were reacted in the same manner as in Example 1 using the catalyst and reaction conditions shown in Table 1.
【００２１】比較例１〜３
触媒に水酸化ナトリウム、トリエチルアミンまたは強塩
基性イオン交換樹脂アンバーリストＡ２６を用いた以外
は実施例１と同様の方法で反応を行った。Comparative Examples 1 to 3 Reactions were conducted in the same manner as in Example 1 except that sodium hydroxide, triethylamine, or a strongly basic ion exchange resin Amberlyst A26 was used as the catalyst.
【００２２】上述の実施例および比較例における反応結
果を表１に示す。Table 1 shows the reaction results in the above-mentioned Examples and Comparative Examples.
【００２３】[0023]
【表１】[Table 1]
【００２４】[0024]
【発明の効果】本発明の方法によれば、副生物の少ない
Ｎ−メチロールアクリルアミドが高い収率で得られる。
また本発明は次のような利点も有する。
（１）副生物が少なく、精製が容易である。
（２）副生物が少ないため、結晶Ｎ−メチロールアクリ
ルアミドを取得した後の分離母液のリサイクル使用が容
易である。
（３）反応速度が向上し、反応時間が短縮する。According to the method of the present invention, N-methylolacrylamide with few by-products can be obtained in high yield. The present invention also has the following advantages. (1) There are few by-products and purification is easy. (2) Since there are few byproducts, it is easy to recycle the separated mother liquor after obtaining crystalline N-methylolacrylamide. (3) The reaction rate is improved and the reaction time is shortened.
Claims (1)
アルデヒドまたはパラホルムアルデヒドを反応させ、Ｎ
−メチロールアクリルアミドを製造する方法において、
該反応を水酸化四級アンモニウム化合物の存在下で行な
うことを特徴とするＮ−メチロールアクリルアミドの製
造方法。Claim 1: By reacting acrylamide with formaldehyde or paraformaldehyde in an aqueous solvent, N
- A method for producing methylol acrylamide,
A method for producing N-methylolacrylamide, characterized in that the reaction is carried out in the presence of a quaternary ammonium hydroxide compound.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3116666A JPH04321658A (en) | 1991-04-22 | 1991-04-22 | Production of n-methylolacrylamide |
| TW081102481A TW226364B (en) | 1991-04-12 | 1992-04-01 | |
| US07/865,270 US5220065A (en) | 1991-04-12 | 1992-04-08 | Method for producing n-methylolacrylamide |
| EP92106245A EP0508455B1 (en) | 1991-04-12 | 1992-04-10 | Method for producing N-methylolacrylamide |
| DE69206307T DE69206307T2 (en) | 1991-04-12 | 1992-04-10 | Process for the preparation of N-methylolacrylamide. |
| KR1019920006067A KR100215228B1 (en) | 1991-04-12 | 1992-04-11 | Method for producing n-methylolacrylamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3116666A JPH04321658A (en) | 1991-04-22 | 1991-04-22 | Production of n-methylolacrylamide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04321658A true JPH04321658A (en) | 1992-11-11 |
Family
ID=14692891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3116666A Pending JPH04321658A (en) | 1991-04-12 | 1991-04-22 | Production of n-methylolacrylamide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04321658A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4605312B1 (en) * | 1996-02-28 | 2011-01-05 | パナソニック株式会社 | High resolution and stereoscopic image recording optical disc, optical disc playback device, optical disc recording device |
-
1991
- 1991-04-22 JP JP3116666A patent/JPH04321658A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4605312B1 (en) * | 1996-02-28 | 2011-01-05 | パナソニック株式会社 | High resolution and stereoscopic image recording optical disc, optical disc playback device, optical disc recording device |
| JP2011010302A (en) * | 1996-02-28 | 2011-01-13 | Panasonic Corp | Optical disk for recording high-resolution and three-dimensional image, optical disk reproducing apparatus and optical disk recording apparatus |
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