JPH0474159A - Production of 2-acrylamido-2-methylpropanesulfonic acid - Google Patents
Production of 2-acrylamido-2-methylpropanesulfonic acidInfo
- Publication number
- JPH0474159A JPH0474159A JP18445990A JP18445990A JPH0474159A JP H0474159 A JPH0474159 A JP H0474159A JP 18445990 A JP18445990 A JP 18445990A JP 18445990 A JP18445990 A JP 18445990A JP H0474159 A JPH0474159 A JP H0474159A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- acrylonitrile
- amps
- organic carboxylic
- sulfuric acid
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 title claims description 6
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 title claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 57
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 12
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 24
- 235000011054 acetic acid Nutrition 0.000 abstract description 8
- 238000004040 coloring Methods 0.000 abstract description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract description 2
- 229920002972 Acrylic fiber Polymers 0.000 abstract description 2
- 150000008064 anhydrides Chemical class 0.000 abstract description 2
- 235000019253 formic acid Nutrition 0.000 abstract description 2
- 235000006408 oxalic acid Nutrition 0.000 abstract description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract 1
- 229910017604 nitric acid Inorganic materials 0.000 abstract 1
- 229920000867 polyelectrolyte Polymers 0.000 abstract 1
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 35
- 239000013078 crystal Substances 0.000 description 32
- -1 aliphatic monocarboxylic acids Chemical class 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 3
- 241001550224 Apha Species 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 101100278642 Mus musculus Dtl gene Proteins 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 238000006434 Ritter amidation reaction Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/13—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/14—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton
- C07C309/15—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton containing amino groups bound to the carbon skeleton the nitrogen atom of at least one of the amino groups being part of any of the groups, X being a hetero atom, Y being any atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/08—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with halogenosulfonic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）発明の目的
［産業上の利用分野］
本発明は２−アクリルアミド−２−メチルプロパンスル
ホン酸を、高品質かつ高収率で製造する方法に関するも
のである。Detailed Description of the Invention (a) Object of the Invention [Industrial Application Field] The present invention relates to a method for producing 2-acrylamido-2-methylpropanesulfonic acid with high quality and high yield.
［従来の技術］
２−アクリルアミド−２−メチルプロパンスルホン酸（
以下ｒＡＭＰｓ」と略す）は、一般に反応溶媒を兼ねる
過剰のアクリロニトリル中に、所定量の硫酸又は発煙硫
酸を全量添加混合後、イソブチレンを添加し、反応混合
物より析出する結晶として得られるＡＭＰＳを分離する
ことにより製造される（特公昭５Ｏ−３００５９）。[Prior art] 2-acrylamido-2-methylpropanesulfonic acid (
rAMPs) is generally produced by adding and mixing a predetermined amount of sulfuric acid or fuming sulfuric acid to excess acrylonitrile, which also serves as a reaction solvent, and then adding isobutylene to separate AMPS, which is obtained as crystals that precipitate from the reaction mixture. (Japanese Patent Publication No. 5O-30059).
［発明が解決しようとする課題］
ＡＭＰＳは、重合により単独重合体及び共重合体を形成
し、高分子電解質としてアクリル繊維の染色性改善剤、
抄紙用分散剤、凝集側等に利用されるが、これらのいく
つかでは低着色かつ高純度のＡＭＰＳが要求されている
。[Problems to be Solved by the Invention] AMPS forms homopolymers and copolymers through polymerization, and is used as a polymer electrolyte to improve the dyeability of acrylic fibers.
It is used as a dispersant for papermaking, aggregation, etc., but some of these require AMPS with low coloration and high purity.
しかし、本発明者らが前記特公昭５０−３００５９号公
報に記載された方法を追試した結果、濃度９５％以上の
硫酸を用いて合成した場合には、目的物が９０％以上の
高収率で得られるものの、ＡＭＰＳ結晶に着色が生じ、
濃度９５％未満の硫酸を用いると、着色は抑制されるも
のの、ＡＭＰＳの収率は低下することが判明した。However, as a result of repeating the method described in Japanese Patent Publication No. 50-30059, the present inventors found that when sulfuric acid with a concentration of 95% or more was used, the desired product was synthesized in a high yield of 90% or more. However, coloration occurs in the AMPS crystal,
It has been found that when sulfuric acid with a concentration of less than 95% is used, although coloring is suppressed, the yield of AMPS is reduced.
一方、特公昭５６−５３３０６号公報等では、反応混合
物より得られたＡＭＰＳ結晶を含水酢酸で再結晶するこ
とにより、精製する方法が捉案されている。On the other hand, Japanese Patent Publication No. 56-53306 and the like propose a method of purifying AMPS crystals obtained from a reaction mixture by recrystallizing them with hydrous acetic acid.
しかし、このような再結晶の実施は設備費、労務費及び
原料単位等の増加をもたらし、経済的に好ましくない。However, implementation of such recrystallization results in increases in equipment costs, labor costs, raw material units, etc., and is economically unfavorable.
従って、特別な精製方法を用いることなく、着色の抑制
されたＡＭＰＳ結晶を、合成反応のみで高収率で製造す
る方法が望まれていた。Therefore, there has been a desire for a method for producing AMPS crystals with suppressed coloration in high yield through only synthetic reactions without using any special purification methods.
本発明は、ＡＭＰＳ結晶を高収率で得ることができ、か
つＡＭＰＳ結晶の着色度を小さくすることができる経済
的なＡＭＰＳの製造方法を提供することを課題とする。An object of the present invention is to provide an economical method for producing AMPS that can obtain AMPS crystals in high yield and reduce the degree of coloration of the AMPS crystals.
（ロ）発明の構成
［課題を解決するための手段１
本発明者らはかかる問題点について鋭意検討した結果、
アクリロニトリルとイソブチレン及び硫酸を反応させる
際に、有機カルボン酸又は有機カルボン酸無水物を存在
させると、得られるＡＭＰＳ結晶の着色を改善できるこ
とを見出し本発明に至った。(b) Structure of the invention [Means for solving the problem 1 As a result of the inventors' intensive study on such problems,
The inventors have discovered that the presence of an organic carboxylic acid or an organic carboxylic acid anhydride during the reaction of acrylonitrile with isobutylene and sulfuric acid can improve the coloring of the resulting AMPS crystals, leading to the present invention.
すなわち本発明は、アクリロニトリル、濃度９５％以上
のｇ酸及びイソブチレンを反応させて２−アクリルアミ
ド−２−メチルプロパンスルホン酸を製造する方法にお
いて、有機カルボン酸又は有機カルボン酸無水物の存在
下で、反応させることを特徴とする２−アクリルアミド
−２−メチル１０パンスルホン酸の製造方法である。That is, the present invention provides a method for producing 2-acrylamido-2-methylpropanesulfonic acid by reacting acrylonitrile, g acid at a concentration of 95% or more, and isobutylene, in the presence of an organic carboxylic acid or an organic carboxylic acid anhydride, This is a method for producing 2-acrylamido-2-methyl 10-panesulfonic acid, which is characterized by carrying out a reaction.
以下、本発明の製造方法に使用する各成分及びそれらの
反応条件等について説明する。Hereinafter, each component used in the production method of the present invention, their reaction conditions, etc. will be explained.
く有機カルボン酸又は、その無水物〉
本発明で用いる有機カルボン酸又は有機カルボン酸無水
物（以下、有機カルボン酸等という）は、分子中にカル
ボキシル基又は酸無水物基（−Ｃｏ−ＯＣＯ−）を有す
る化合物であれば特に制限はなく、具体的には、脂肪族
モノカルボン酸であるギ酸、酢酸、プロピオン酸、酪酸
など、脂肪族ジカルボン酸であるシュウ酸、マロン酸、
コハク酸、アジピン酸など、あるいは不飽和カルボン酸
であるアクリル酸、メタクリル酸、マレイン酸、フマル
酸など、さらには芳香族のカルボン酸である安、セ、香
酸、フタル酸などがあげられる。Organic carboxylic acid or anhydride thereof> The organic carboxylic acid or organic carboxylic anhydride (hereinafter referred to as organic carboxylic acid, etc.) used in the present invention has a carboxyl group or an acid anhydride group (-Co-OCO- ) is not particularly limited as long as the compound has the following: specifically, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, and
Examples include succinic acid, adipic acid, etc., unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, etc., and aromatic carboxylic acids such as ammonium, seric acid, aromatic acid, and phthalic acid.
また、有機カルボン酸無水物としては無水酢酸、無水マ
レイン酸、無水フタル酸などがある。Examples of organic carboxylic anhydrides include acetic anhydride, maleic anhydride, and phthalic anhydride.
有機カルボン酸等の好ましい添加割合は、アクリロニト
リルの１００重量部（以下単に部という）当たり０．０
１〜５．０部であり、より好ましくは０゜０５〜０．５
部である。添加割合が、０．０１部未満では、着色を抑
制する効果が十分でないことがあり、添加割合が５．０
部を越えると、ＡＭＰＳ結晶を高収率で得られないこと
がある。The preferred addition ratio of organic carboxylic acid, etc. is 0.0 parts by weight (hereinafter simply referred to as parts) of acrylonitrile.
1 to 5.0 parts, more preferably 0.05 to 0.5 parts.
Department. If the addition ratio is less than 0.01 part, the effect of suppressing coloring may not be sufficient, and the addition ratio is 5.0 parts.
If the amount is exceeded, AMPS crystals may not be obtained in high yield.
有機カルボン酸等は、その全量を予めアクリロニトリル
に添加してもよいし、又反応中、例えばイソブチレンの
添加と同時に連続的に添加してもよい。The entire amount of the organic carboxylic acid etc. may be added to the acrylonitrile in advance, or may be added continuously during the reaction, for example at the same time as the addition of isobutylene.
〈アクリロニトリル〉
本発明に用いるアクリロニトリルは、一般に市販されて
いる工業品でよいが、含水量が０．２重量％以下、より
好ましくは０．０５重量％以下のアクリロニトリルを用
いて反応させると、硫酸エステル等の副生を抑制し、Ａ
ＭＰＳの収率を高めることができるため、含水量が０．
２重量％以下に脱水されたものを使用することが好まし
い。<Acrylonitrile> The acrylonitrile used in the present invention may be a generally commercially available industrial product, but if the reaction is performed using acrylonitrile with a water content of 0.2% by weight or less, more preferably 0.05% by weight or less, sulfuric acid By suppressing by-products such as esters, A
Since the yield of MPS can be increased, the water content is 0.
It is preferable to use one that has been dehydrated to 2% by weight or less.
アクリロニトリルの脱水は、モレキュラーシーブ、脱水
樹脂及び五酸化リン等の脱水剤を用いてもよいし、又は
シクロヘキサン、ノルマルヘキサン及びヘンゼン等の適
当な溶媒との蒸留で共沸除去してもよい。Acrylonitrile may be dehydrated using a dehydrating agent such as a molecular sieve, a dehydrating resin, and phosphorus pentoxide, or may be azeotropically removed by distillation with a suitable solvent such as cyclohexane, n-hexane, and Hensen.
本発明における反応は、アクリロニトリルと硫酸が等モ
ル量でも進行するが、反応の進行にともなってスラリー
濃度が増大し、撹拌が困難になる恐れがあるため、アク
リロニトリルに反応溶媒としての機能を兼備させ、硫酸
１モルに対し、アクリロニトリルを４．０モル以上用い
ることが好ましい。The reaction in the present invention proceeds even with equimolar amounts of acrylonitrile and sulfuric acid, but as the reaction progresses, the slurry concentration increases and stirring may become difficult. It is preferable to use 4.0 mol or more of acrylonitrile per 1 mol of sulfuric acid.
〈硫酸〉
反応に用いる硫酸の濃度は９５％以上であることが必要
であり、より好ましくは９８〜１０２％である。<Sulfuric acid> The concentration of sulfuric acid used in the reaction needs to be 95% or more, more preferably 98 to 102%.
硫酸濃度が９５％未満では硫酸エステル等の副生により
ＡＭＰＳの収率が低下し、硫酸濃度が１０２％より高い
とイソブチレンのスルホン化物が副生し、またＡＭＰＳ
結晶が着色する恐れがある９硫酸濃度は濃硫酸、発煙硫
酸、無水硫酸及び水を任意の割合で混合することにより
調整することができる。When the sulfuric acid concentration is less than 95%, the yield of AMPS decreases due to by-products such as sulfuric esters, and when the sulfuric acid concentration is higher than 102%, isobutylene sulfonated products are produced as by-products, and AMPS
9 The concentration of sulfuric acid, which may cause coloration of the crystals, can be adjusted by mixing concentrated sulfuric acid, fuming sulfuric acid, sulfuric anhydride, and water in arbitrary proportions.
また、発煙硫酸又は無水硫酸を添加することにより、ア
クリロニトリル中の水分を硫酸に変換することも可能で
ある。この場合、添加した発煙硫酸又は無水硫酸の添加
量は、反応に用いる硫酸の添加量として加算される。It is also possible to convert the moisture in acrylonitrile into sulfuric acid by adding fuming sulfuric acid or sulfuric anhydride. In this case, the amount of added fuming sulfuric acid or sulfuric anhydride is added as the amount of sulfuric acid used in the reaction.
〈イソブチレン〉
イソブチレンの好ましい添加割合は、硫酸１モル当たり
０．８〜１．２モル、より好ましくは０．８〜１．０モ
ルである。<Isobutylene> The preferred addition ratio of isobutylene is 0.8 to 1.2 mol, more preferably 0.8 to 1.0 mol, per 1 mol of sulfuric acid.
イソブチレンの添加割合が、硫酸１モル当たり０．８モ
ルより少ないと、ＡＭＰＳ結晶が着色することがあり、
一方硫酸１モル当たり１．２モルより多くしても、リッ
ター反応生成物であるｔｅｒｔ−フチルアクリルアミド
を副生成物として生ずるのみであり、経済的に好ましく
ない。If the addition ratio of isobutylene is less than 0.8 mol per 1 mol of sulfuric acid, AMPS crystals may be colored.
On the other hand, if the amount is more than 1.2 mol per mol of sulfuric acid, only tert-phthylacrylamide, which is a Ritter reaction product, will be produced as a by-product, which is not economically preferable.
なお、ＡＭＰＳ結晶の着色及びｔｅｒｔ−ブチルアクリ
ルアミド等の副生を、より効率的に抑制し、高純度のＡ
ＭＰＳを高収率で得るには、硫酸に対するイソブチレン
のモル比を０．８〜１．２に維持しつつ、両者をアクリ
ロニトリル中に、連続的及び／又は断続的に添加するこ
とが好ましい。In addition, coloring of AMPS crystals and by-products such as tert-butylacrylamide can be suppressed more efficiently, and highly purified A
In order to obtain MPS in a high yield, it is preferable to maintain the molar ratio of isobutylene to sulfuric acid at 0.8 to 1.2 and add both to acrylonitrile continuously and/or intermittently.
もしアクリロニトリル中に硫酸のみを添加混合した後イ
ソブチレンを添加混合すると、アクリロニトリルと硫酸
とが反応するのに充分長い時間接触するため、アクリロ
ニトリルの加水分解生成物であるアクリルアミド及びア
クリル酸等がＡＭＰＳの結晶中に混入したり、反応混合
物中において、硫酸がイソブチレンに対し大過剰に存在
するため、イソブチレンのスルホン化物が析出し、ＡＭ
ＰＳの結晶中に混入する恐れがある。If only sulfuric acid is added and mixed into acrylonitrile and then isobutylene is added and mixed, the acrylonitrile and sulfuric acid will be in contact for a long enough time to react, so that acrylamide, acrylic acid, etc., which are hydrolysis products of acrylonitrile, will become AMPS crystals. Because sulfuric acid is present in large excess relative to isobutylene in the reaction mixture, sulfonated isobutylene precipitates, and AM
There is a possibility that it may be mixed into the PS crystal.
〈反応条件〉
好ましい反応温度は一１０〜７０’Ｃ１より好ましくは
３０〜５０゛Ｃである。反応温度が７０°Ｃより高いと
ＡＭＰＳの結晶が着色する傾向にあり、逆に反応温度が
一１０°Ｃより低いと硫酸エステルが副生ずるため、収
率が低下する傾向にある。<Reaction Conditions> The preferred reaction temperature is -10 to 70'C1, more preferably 30 to 50'C. If the reaction temperature is higher than 70°C, AMPS crystals tend to be colored, whereas if the reaction temperature is lower than 110°C, sulfuric acid ester is produced as a by-product, which tends to lower the yield.
く反応後の処理〉
本発明の方法に従い反応させると、その進行にともなっ
てＡＭＰＳの結晶が析出する。析出した結晶の分離は、
例えば濾過や遠心分離など通常の分離方法によって可能
である。かくして分離した結晶は、必要に応して溶媒洗
浄後、真空乾燥等により乾燥する。Treatment after Reaction> When the reaction is carried out according to the method of the present invention, AMPS crystals are precipitated as the reaction progresses. Separation of precipitated crystals is
For example, this can be done by conventional separation methods such as filtration and centrifugation. The thus separated crystals are washed with a solvent, if necessary, and then dried by vacuum drying or the like.
なお、結晶を分離した後のアクリロニトリルは、蒸留し
て再利用することも可能である。Note that the acrylonitrile after the crystals have been separated can be distilled and reused.
［作用］
有機カルボン酸等がＡＭＰＳの結晶着色を抑制する機構
について、詳細は不明であるが、着色に関与する過剰の
ＳＯｌと有機カルボン酸等との次のようなスルホン化反
応によるものと推定される。[Effect] Although the details of the mechanism by which organic carboxylic acids, etc. suppress AMPS crystal coloring are unknown, it is presumed to be due to the following sulfonation reaction between excess SOI and organic carboxylic acids, etc., which are involved in coloring. be done.
Ｓｏ、＋Ｒ−ＣＯＯＨ−ＲＣＯＯ３ＯｉＨ［実施例］ 以下実施例にて本発明を具体的に説明する。So, +R-COOH-RCOO3OiH [Example] The present invention will be specifically explained below with reference to Examples.
なお、以下の実施例における百分率は重量百分率を表す
。Note that the percentages in the following examples represent weight percentages.
実施例及び比較例において得られたＡＭＰＳの純度は、
高速液体クロマトグラフＬ−６０００（日立製作新製）
を用いて測定した値であり、ＡＰＨＡはＡＭＰＳ結晶の
２５％水溶液１＝ツイｚＪＩＳ−に−１５５１に準して
測定した値であり、大きな値である程ＡＭＰＳ結晶の２
５％水溶液が強く着色していることを示す指標である。The purity of AMPS obtained in Examples and Comparative Examples is
High performance liquid chromatograph L-6000 (newly manufactured by Hitachi)
APHA is a value measured according to 25% aqueous solution of AMPS crystal 1 = Twiz JIS-1551, and the larger the value, the 25% aqueous solution of AMPS crystal.
This is an indicator showing that the 5% aqueous solution is strongly colored.
実施例１
撹拌機、滴下ロート及びガス吹き込み管を備えた１１力
゛ラス反応器に、アクリロニトリル３７５ｇ（８，７２
モル）と酢酸０．４ ｇ （アクリロニトリルに対して
０．１％）を仕込み、０゛ｃ以下に冷却した後、１００
％硫酸９８ｇを滴下した。直ちに３０°Ｃまで昇温し、
゛イソブチレン５６ｇを攪拌しながら５２分間にわたっ
て導入した。室温で１時間熟成後、反応混合物を濾過し
、アクリロニトリル１５０ｇで洗浄後、５０℃で３時間
減圧乾燥し、ＡＭＰＳ結晶１８６ｇ （理論量）９０．
０％）を得た。Example 1 375 g of acrylonitrile (8,72
mol) and acetic acid 0.4 g (0.1% based on acrylonitrile), cooled to below 0°C,
% sulfuric acid was added dropwise. Immediately raise the temperature to 30°C,
56 g of isobutylene were introduced over a period of 52 minutes with stirring. After aging at room temperature for 1 hour, the reaction mixture was filtered, washed with 150 g of acrylonitrile, and dried under reduced pressure at 50° C. for 3 hours to obtain 186 g (theoretical amount) of AMPS crystals.
0%) was obtained.
ＡＭＰＳ結晶の純度は９８．９％であり、この結晶のＡ
Ｐ ＨＡは２０であった。The purity of AMPS crystal is 98.9%, and the A
PHA was 20.
実施例２
イソブチレンの導入中、酢酸０．４ｇを５２分間にわた
って連続的に添加した他は実施例１と同様にして、ＡＭ
ＰＳ結晶１９１ｇ （理論量の９２．０％）を得た。Example 2 AM
191 g (92.0% of theoretical amount) of PS crystals were obtained.
ＡＭＰＳ結晶の純度は９８．２％であり、この結晶のＡ
ＰＨＡは３０であった。The purity of the AMPS crystal is 98.2%, and the A
PHA was 30.
実施例３〜実施例８
有機カルボン酸等の種類や量を変更した以外は実施例１
と同様にして反応を行った場合の結果を実施例９
撹拌機、滴下ロート及びガス吹き込み管を備えたＩＬガ
ラス反応器に、モレキュラーシーブ４Ａによって含水量
０．０５％に脱水したアクリロニトリル３７５ｇ （
８，７２モル）と酢酸０．７５ｇ（アクリロニトリルに
対して０．２％）を仕込み、これを撹拌しながら、イソ
ブチレンガス５６ｇ（１モル）と１００％硫酸１０３ｇ
（１，０５モル）を一定の添加速度で同時に５２分間に
わたって添加した。Examples 3 to 8 Example 1 except that the type and amount of organic carboxylic acid etc. were changed.
Example 9 The results were obtained when the reaction was carried out in the same manner as in Example 9. Into an IL glass reactor equipped with a stirrer, a dropping funnel, and a gas blowing tube, 375 g of acrylonitrile dehydrated to a water content of 0.05% with Molecular Sieve 4A (
8.72 mol) and acetic acid 0.75 g (0.2% based on acrylonitrile), and while stirring, add 56 g (1 mol) of isobutylene gas and 103 g of 100% sulfuric acid.
(1.05 mol) were added simultaneously at a constant addition rate over 52 minutes.
このとき、最初１５°Ｃであった反応液の温度は、反応
が進行するにつれて昇温しだが、冷却により４５°Ｃ以
下に保持しながら反応をおこなった。At this time, the temperature of the reaction solution, which was initially 15°C, rose as the reaction proceeded, but the reaction was carried out while being maintained at 45°C or lower by cooling.
室温で１時間熟成後、反応混合物を濾過し、アクリロニ
トリル１５０ｇで洗浄後、５０°Ｃで３時間真空乾燥し
、ＡＭＰＳの結晶−１８９ｇ（０，９１モル）を得た。After aging at room temperature for 1 hour, the reaction mixture was filtered, washed with 150 g of acrylonitrile, and vacuum dried at 50°C for 3 hours to obtain 189 g (0.91 mol) of AMPS crystals.
ＡＭＰＳの純度は９９．３％であり、この結晶のＡＰＨ
Ａは１５であった。The purity of AMPS is 99.3%, and the APH of this crystal is
A was 15.
実施例１０
酢酸０．７５ ｇの代わりに無水マレイン酸０．３７５
ｇを仕込んだこと以外は実施例９と同様にして反応を行
った。Example 10 0.375 maleic anhydride instead of 0.75 g acetic acid
The reaction was carried out in the same manner as in Example 9 except that g was charged.
得られたＡＭＰＳの純度は９９．２％であり、ＡＰＨＡ
は２５であった。The purity of the obtained AMPS was 99.2%, and the purity of APHA
was 25.
比較例１
酢酸を添加しない他は全て実施例１と同様の操作を行い
、ＡＭＰＳ結晶１９４ｇ （理論量の９３゜６％）を得
た。Comparative Example 1 The same operations as in Example 1 were carried out except that acetic acid was not added, and 194 g of AMPS crystals (93.6% of the theoretical amount) were obtained.
このＡＭＰＳ結晶の純度は、９２，１％であり、ＡＰＨ
Ａは２００であった。The purity of this AMPS crystal is 92.1%, and the APH
A was 200.
比較例２
実施例１において、酢酸を添加せず、９０％硫酸を用い
た以外は全て同様の操作を行い、ＡＭＰＳ結晶１４５ｇ
（理論量の７０．０％）を得た。Comparative Example 2 The same operations as in Example 1 were performed except that 90% sulfuric acid was used without adding acetic acid, and 145 g of AMPS crystals were obtained.
(70.0% of theory).
このＡＭＰＳ結晶の純度は、９９．０％であり、ＡＰＨ
Ａは１０であった。The purity of this AMPS crystal is 99.0%, and the APH
A was 10.
（ハ）発明の効果
本発明により、着色のない高品質のＡＭＰＳ結晶を高収
率かつ容易に製造することが可能となり、ＡＭＰＳの経
済的な新製法として斯界にもたらす影響は計り知れない
ものがある。(c) Effects of the invention The present invention makes it possible to easily produce uncolored, high-quality AMPS crystals in high yield, and the impact it will have on the industry as an economical new method for producing AMPS will be immeasurable. be.
手 続 補 正 書hand Continued Supplementary Positive book
Claims (1)
ブチレンを反応させて２−アクリルアミド−２−メチル
プロパンスルホン酸を製造する方法において、有機カル
ボン酸又は有機カルボン酸無水物の存在下で、反応させ
ることを特徴とする２−アクリルアミド−２−メチルプ
ロパンスルホン酸の製造方法。1. In a method for producing 2-acrylamido-2-methylpropanesulfonic acid by reacting acrylonitrile, sulfuric acid with a concentration of 95% or more, and isobutylene, the reaction is performed in the presence of an organic carboxylic acid or an organic carboxylic acid anhydride. A characterized method for producing 2-acrylamido-2-methylpropanesulfonic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2184459A JP2551209B2 (en) | 1990-07-12 | 1990-07-12 | Method for producing 2-acrylamido-2-methylpropanesulfonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2184459A JP2551209B2 (en) | 1990-07-12 | 1990-07-12 | Method for producing 2-acrylamido-2-methylpropanesulfonic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0474159A true JPH0474159A (en) | 1992-03-09 |
| JP2551209B2 JP2551209B2 (en) | 1996-11-06 |
Family
ID=16153524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2184459A Expired - Lifetime JP2551209B2 (en) | 1990-07-12 | 1990-07-12 | Method for producing 2-acrylamido-2-methylpropanesulfonic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2551209B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952052A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Synthesis method of 2-acrylamide-2-methylpropanesulfonic acid (AMPS) |
| CN104230764A (en) * | 2014-09-03 | 2014-12-24 | 巨野县中海化工有限公司 | Preparation method of 2-acrylamide-2-methyl propanesulfonic acid |
| CN105461599A (en) * | 2014-09-03 | 2016-04-06 | 中国石油化工股份有限公司 | Acrylamide monomer and preparation method therefor |
| CN105601546A (en) * | 2016-01-29 | 2016-05-25 | 寿光市荣晟新材料有限公司 | Synthesizing method of 2-acrylamide-2-methylpropane sulfonic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54163524A (en) * | 1978-06-12 | 1979-12-26 | Nitto Chem Ind Co Ltd | Production of high-purity 2-acrylamide-2- methylpropanesulfonic acid |
| JPS6147458A (en) * | 1984-07-27 | 1986-03-07 | アライド・コロイズ・リミテツド | Manufacture of sulfonic acid |
-
1990
- 1990-07-12 JP JP2184459A patent/JP2551209B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54163524A (en) * | 1978-06-12 | 1979-12-26 | Nitto Chem Ind Co Ltd | Production of high-purity 2-acrylamide-2- methylpropanesulfonic acid |
| JPS6147458A (en) * | 1984-07-27 | 1986-03-07 | アライド・コロイズ・リミテツド | Manufacture of sulfonic acid |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952052A (en) * | 2011-08-30 | 2013-03-06 | 中国石油化工股份有限公司 | Synthesis method of 2-acrylamide-2-methylpropanesulfonic acid (AMPS) |
| CN104230764A (en) * | 2014-09-03 | 2014-12-24 | 巨野县中海化工有限公司 | Preparation method of 2-acrylamide-2-methyl propanesulfonic acid |
| CN105461599A (en) * | 2014-09-03 | 2016-04-06 | 中国石油化工股份有限公司 | Acrylamide monomer and preparation method therefor |
| CN105461599B (en) * | 2014-09-03 | 2017-11-07 | 中国石油化工股份有限公司 | A kind of acrylamide monomer and preparation method thereof |
| CN105601546A (en) * | 2016-01-29 | 2016-05-25 | 寿光市荣晟新材料有限公司 | Synthesizing method of 2-acrylamide-2-methylpropane sulfonic acid |
| CN105601546B (en) * | 2016-01-29 | 2017-10-24 | 寿光市荣晟新材料有限公司 | A kind of synthetic method of the methyl propane sulfonic acid of 2 acrylamido 2 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2551209B2 (en) | 1996-11-06 |
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