JP2915132B2 - Method for producing isocyanuric acid - Google Patents
Method for producing isocyanuric acidInfo
- Publication number
- JP2915132B2 JP2915132B2 JP30699990A JP30699990A JP2915132B2 JP 2915132 B2 JP2915132 B2 JP 2915132B2 JP 30699990 A JP30699990 A JP 30699990A JP 30699990 A JP30699990 A JP 30699990A JP 2915132 B2 JP2915132 B2 JP 2915132B2
- Authority
- JP
- Japan
- Prior art keywords
- isocyanuric acid
- alkali metal
- reaction
- urea
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- -1 alkali metal amidate Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 3
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 3
- 229940059260 amidate Drugs 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 5
- 150000001339 alkali metal compounds Chemical class 0.000 description 5
- 229910000104 sodium hydride Inorganic materials 0.000 description 4
- 239000012312 sodium hydride Substances 0.000 description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BCNBMSZKALBQEF-UHFFFAOYSA-N 1,3-dimethylpyrrolidin-2-one Chemical compound CC1CCN(C)C1=O BCNBMSZKALBQEF-UHFFFAOYSA-N 0.000 description 1
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 150000005218 dimethyl ethers Chemical class 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical class [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 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
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- WNVQBUHCOYRLPA-UHFFFAOYSA-N triuret Chemical compound NC(=O)NC(=O)NC(N)=O WNVQBUHCOYRLPA-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は尿素を原料としてイソシアヌル酸（以下、CA
と略記する。）を製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention uses urea as a raw material and isocyanuric acid (hereinafter referred to as CA).
Abbreviated. ).
CAは工業的に有用な中間原料である。例えば、CAを塩
素化した塩素化イソシアヌルは、粒状で簡便かつ活性が
高いプール殺菌剤として広く用いられており、又、アリ
ル化したアリルイソシアヌレートは樹脂改質剤や架橋助
剤として好適に用いられている。CA is an industrially useful intermediate material. For example, chlorinated isocyanuric acid obtained by chlorinating CA is widely used as a simple, highly active, and highly active pool fungicide, and allylated allyl isocyanurate is preferably used as a resin modifier or a crosslinking aid. Have been.
このような工業的には有用なCAは、一般に有機溶媒中
で尿素を加熱することにより製造される。その反応を示
せば下記式（１）のとおりである。Such industrially useful CA is generally produced by heating urea in an organic solvent. The reaction is as shown in the following formula (1).
しかし、アンモニアガス発生雰囲気下、高温で長時間
溶媒を加熱すると溶媒が一部劣化する。そこで溶媒の寿
命を長くするには反応温度を低下させることが好ましい
が、（１）式で示される反応を短時間で完全に進行させ
るには200℃以上の温度が必要であるとされている。し
かし、温度を上げすぎると生成したCAがアンモニアと反
応し、却ってCAの収率が低下する。 However, when the solvent is heated at a high temperature for a long time in an ammonia gas generating atmosphere, the solvent partially deteriorates. Therefore, it is preferable to lower the reaction temperature in order to prolong the life of the solvent, but it is said that a temperature of 200 ° C. or more is required to completely advance the reaction represented by the formula (1) in a short time. . However, if the temperature is too high, the generated CA reacts with ammonia, and on the contrary the CA yield decreases.
そこで本発明者らは、上記の方法において反応温度を
従来より低下させる方法について鋭意研究した。その結
果、特定の化合物を存在させることにより反応温度を従
来より低くしても、CAが短時間でほぼ定量的に得られ、
かつCAとアンモニアとの反応もほとんど生じないことを
見出し、本発明を完成した。Therefore, the present inventors have diligently studied a method for lowering the reaction temperature in the above-mentioned method than before. As a result, even if the reaction temperature is lowered by the presence of a specific compound, CA can be obtained almost quantitatively in a short time,
In addition, they have found that the reaction between CA and ammonia hardly occurs, and completed the present invention.
即ち、本発明は、尿素を有機溶媒中でアルカリ金属水
素化物、アルカリ金属アミド化物又はイソシアヌル酸の
アルカリ金属塩（以下、これらを単にアルカリ金属化合
物ともいう。）の存在下に加熱することを特徴とするイ
ソシアヌル酸の製造法である。That is, the present invention is characterized in that urea is heated in an organic solvent in the presence of an alkali metal hydride, an alkali metal amidate or an isocyanuric acid alkali metal salt (hereinafter, these are also simply referred to as alkali metal compounds). Is a method for producing isocyanuric acid.
本発明において用いられる有機溶媒は、イソシアヌル
酸の製造反応温度、一般には100℃以上で液体であり、
アルカリ金属化合物の１種類もしくは２種類以上を溶解
させ、かつ、それ自身が反応しないものであれば公知の
ものが何ら制限されずに使用し得る。有機溶媒として好
適な化合物としては例えば、エチレングリコールジメチ
ルエーテル、ジエチレングリコールジメチルエーテル、
トリエチレングリコールジメチルエーテル、テトラエチ
レングリコールジメチルエーテルなどのポリエチレング
リコールジメチルエーテル類;2−メチルピロリドン、2,
4−ジメチルピロリドン、2,2,4−トリメチルピロリド
ン、２−シクロヘキシルピロリドン、２−シクロヘキシ
ル−４−メチルピロリドン、２−シクロヘキシル−4,4
−ジメチルピロリドンなどのピロリドン誘導体類；ジメ
チルスルホキシド、N,N−ジメチルホルムアミドなどが
ある。The organic solvent used in the present invention is a liquid at a production reaction temperature of isocyanuric acid, generally 100 ° C. or higher,
Known ones can be used without any limitation as long as they dissolve one or more kinds of alkali metal compounds and do not react themselves. Compounds suitable as organic solvents include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether,
Polyethylene glycol dimethyl ethers such as triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether; 2-methylpyrrolidone, 2,
4-dimethylpyrrolidone, 2,2,4-trimethylpyrrolidone, 2-cyclohexylpyrrolidone, 2-cyclohexyl-4-methylpyrrolidone, 2-cyclohexyl-4,4
-Pyrrolidone derivatives such as dimethylpyrrolidone; dimethylsulfoxide, N, N-dimethylformamide and the like.
上記の有機溶媒の使用量は、特に制限されないが、得
られるCAの収率を勘案すると、尿素の濃度が１〜90重量
％の範囲となるように選ぶことが好ましい。The amount of the organic solvent used is not particularly limited, but is preferably selected so that the concentration of urea is in the range of 1 to 90% by weight in consideration of the yield of the obtained CA.
次に、アルカリ金属水素化物は、水素化リチウム、水
素化ナトリウム、水素化カリウムが挙げられ、アルカリ
金属アミド化物は、リチウムアミド、ナトリウムアミ
ド、カリウムアミドが挙げられ、イソシアヌル酸のアル
カリ金属塩は、イソシアヌル酸のモノリチウム塩、ジリ
チウム塩、トリリチウム塩、モノナトリウム塩、ジナト
リウム塩、トリナトリウム塩、モノカリウム塩、ジカリ
ウム塩、トリカリウム塩等が挙げられる。これらの中で
もCAの収率を高くするためには、ナトリウム化合物を用
いることが好ましい。Next, alkali metal hydrides include lithium hydride, sodium hydride, and potassium hydride, and alkali metal amidates include lithium amide, sodium amide, and potassium amide, and an alkali metal salt of isocyanuric acid is Monolithium salt, dilithium salt, trilithium salt, monosodium salt, disodium salt, trisodium salt, monopotassium salt, dipotassium salt, tripotassium salt and the like of isocyanuric acid are exemplified. Among them, in order to increase the yield of CA, it is preferable to use a sodium compound.
これらのアルカリ金属化合物の使用量は、CAを高収率
で得るためには尿素に対してモル比で1/1〜1/1000の範
囲であることが好ましく、更には1/10〜1/40であること
がより好ましい。有機溶媒、尿素、及びアルカリ金属化
合物の導入順序は特に限定されない。反応温度は、前記
（１）式の反応を進行させて、且つ生成するCAの分解を
防止するためには好ましくは100℃〜300℃の範囲で、更
に好ましくは150℃〜200℃である。反応時間は好ましく
は10分間以上で、更に好ましくは１時間以上である。The use amount of these alkali metal compounds is preferably in the range of 1/1 to 1/1000 in molar ratio to urea in order to obtain CA in high yield, and more preferably 1/10 to 1/1000. More preferably, it is 40. The order of introducing the organic solvent, urea, and the alkali metal compound is not particularly limited. The reaction temperature is preferably in the range of 100 ° C. to 300 ° C., and more preferably 150 ° C. to 200 ° C., in order to allow the reaction of the formula (1) to proceed and to prevent the decomposition of generated CA. The reaction time is preferably at least 10 minutes, more preferably at least 1 hour.
（効果） 本発明の方法によれば、従来法より反応温度を50℃以
上下げることができる。これにより、エネルギーコスト
を低減させることができ、また、溶媒の寿命を延ばすこ
とができる。(Effect) According to the method of the present invention, the reaction temperature can be lowered by 50 ° C. or more than the conventional method. As a result, energy costs can be reduced, and the life of the solvent can be extended.
（実施例） 実施例１ 容量300mlの三っ口フラスコに溶媒としてテトラエチ
レングリコールジメチルエーテルを100g入れ、150℃に
加熱し、撹拌しながら、尿素10g及び尿素に対し1/40モ
ル量の水素化ナトリウムを添加した。５時間150℃で撹
拌を続けた。その後、室温まで冷却し生じた沈殿物を濾
取した。また、濾液から溶媒を留去すると固体が得られ
た。この沈殿物と濾液から得られた固体はそれぞれ6.10
g及び1.00gであった。元素分析、赤外線吸収スペクトル
及び質量分析からどちらもCAと同定した。また収率は両
者あわせて99％であった。(Example) Example 1 100 g of tetraethylene glycol dimethyl ether as a solvent was placed in a 300 ml three-necked flask, heated to 150 ° C., and stirred, while stirring, 10 g of urea and 1/40 mole of sodium hydride based on urea. Was added. Stirring was continued at 150 ° C. for 5 hours. Thereafter, the mixture was cooled to room temperature and the resulting precipitate was collected by filtration. The solvent was distilled off from the filtrate to obtain a solid. The solid obtained from this precipitate and the filtrate was 6.10 each.
g and 1.00 g. All were identified as CA from elemental analysis, infrared absorption spectrum and mass spectrometry. The yield was 99% in both cases.
比較例１ 水素化ナトリウムを加えないこと以外実施例１と同様
に反応を行った結果、沈殿物と濾液から得られた固体は
それぞれ3.50g及び4.55gであった。実施例１と同様にし
てこれらの分析を行った結果、尿素、ビウレット、トリ
ウレットの混合物で、まったくCAは含まれていなかっ
た。Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that sodium hydride was not added. As a result, the precipitate and the solid obtained from the filtrate were 3.50 g and 4.55 g, respectively. As a result of performing these analyzes in the same manner as in Example 1, it was found that the mixture of urea, biuret, and triuret contained no CA.
比較例２ 水素化ナトリウムを用いず、温度を200℃にして反応
を行なったこと以外は実施例１と同様にして反応を行な
った。その結果、尿素の転化率は96％であり、CAの選択
率は99％であった。Comparative Example 2 A reaction was carried out in the same manner as in Example 1 except that the reaction was carried out at a temperature of 200 ° C. without using sodium hydride. As a result, the conversion of urea was 96%, and the selectivity of CA was 99%.
実施例２ 溶媒に２−シクロヘキシルピロリドンを用いること以
外は実施例１と同様に反応を行なった。尿素の転化率は
97％でCAの選択率は99％であった。Example 2 A reaction was carried out in the same manner as in Example 1 except that 2-cyclohexylpyrrolidone was used as a solvent. The conversion of urea is
At 97%, the selectivity of CA was 99%.
実施例３ 表１で示したアルカリ金属化合物を用いること以外は
実施例１と同様に反応を行なった。結果は表１の通りで
あった。Example 3 A reaction was carried out in the same manner as in Example 1 except that the alkali metal compound shown in Table 1 was used. The results were as shown in Table 1.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C07D 251/32 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. 6 , DB name) C07D 251/32 CA (STN) REGISTRY (STN)
Claims (1)
物、アルカリ金属アミド化物又はイソシアヌル酸のアル
カリ金属塩の存在下に加熱することを特徴とするイソシ
アヌル酸の製造法。1. A process for producing isocyanuric acid, comprising heating urea in an organic solvent in the presence of an alkali metal hydride, an alkali metal amidate or an alkali metal salt of isocyanuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30699990A JP2915132B2 (en) | 1990-11-15 | 1990-11-15 | Method for producing isocyanuric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30699990A JP2915132B2 (en) | 1990-11-15 | 1990-11-15 | Method for producing isocyanuric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04364173A JPH04364173A (en) | 1992-12-16 |
| JP2915132B2 true JP2915132B2 (en) | 1999-07-05 |
Family
ID=17963798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30699990A Expired - Fee Related JP2915132B2 (en) | 1990-11-15 | 1990-11-15 | Method for producing isocyanuric acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2915132B2 (en) |
-
1990
- 1990-11-15 JP JP30699990A patent/JP2915132B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04364173A (en) | 1992-12-16 |
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