JPH0812688A - New nitrogen-containing organic phosphorus compound and its production - Google Patents
New nitrogen-containing organic phosphorus compound and its productionInfo
- Publication number
- JPH0812688A JPH0812688A JP14156894A JP14156894A JPH0812688A JP H0812688 A JPH0812688 A JP H0812688A JP 14156894 A JP14156894 A JP 14156894A JP 14156894 A JP14156894 A JP 14156894A JP H0812688 A JPH0812688 A JP H0812688A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- chlorophosphate
- nitrogen
- dichlorophosphate
- containing organic
- 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.)
- Withdrawn
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、主に難燃剤などの樹脂
添加剤として有用な、新規な含窒素有機燐化合物とその
製造方法に関わり、さらに詳しくはハロ燐酸ジエステル
及び／またはジハロ燐酸エステルと、分子内に２つのア
ミノ基を有する化合物の、脱ハロゲン化水素反応にて生
成する、燐及び窒素の含有率が高くかつ熱安定性の良
い、含窒素有機燐化合物とその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel nitrogen-containing organic phosphorus compound which is mainly useful as a resin additive such as a flame retardant and a method for producing the same, more specifically, a halophosphoric acid diester and / or a dihalophosphoric acid ester. And a nitrogen-containing organic phosphorus compound having a high phosphorus and nitrogen content and good thermal stability, which is produced by a dehydrohalogenation reaction of a compound having two amino groups in the molecule, and a method for producing the same.
【０００２】[0002]
【従来の技術】有機燐化合物、特に燐酸エステルは、樹
脂の可塑剤及び難燃剤として広く使用されおり、特に酸
素原子を含む樹脂に対して優れた難燃作用を示す事が知
られている。代表的な燐酸エステルとしては、トリフェ
ニルホスフェートやトリクレジルホスフェートが挙げら
れる。しかし、これらのエステルは揮発し易い欠点があ
り、樹脂との押出し・成形時の作業環境の汚染やモール
ドデポジット、成形品表面へのしみ出しなどの問題を起
こしている。これに対応して、低揮発性のポリ燐酸エス
テルが開発されている。例えば、特公昭５１−１９８５
８号や特公平２−１８３３６号等には一般式（５）の化
合物が示されている。2. Description of the Related Art Organophosphorus compounds, especially phosphoric acid esters, are widely used as plasticizers and flame retardants for resins, and are known to exhibit excellent flame retardant action especially for resins containing oxygen atoms. Typical phosphoric acid esters include triphenyl phosphate and tricresyl phosphate. However, these esters have a drawback that they are liable to volatilize, causing problems such as contamination of the working environment during extrusion / molding with resin, mold deposit, and exudation on the surface of the molded product. In response to this, low-volatile polyphosphate esters have been developed. For example, Japanese Patent Publication No. Sho 51-1985.
No. 8 and Japanese Examined Patent Publication No. 2-18336 show compounds of the general formula (5).
【０００３】[0003]
【化６】 [Chemical 6]
【０００４】［ここでｎは０または１〜２０の整数であ
り、Ｒ1，Ｒ2，Ｒ3，Ｒ4は独立にフェニル基、ヒドロキ
シフェニル基、またはアルキル基が１〜３個置換したア
リール基を示し、Ｒ5は多価フェノール残基である。］ 一方、難燃剤としての燐と窒素が相乗効果を示す事も周
知であり、例えば「ポリマーの難燃化＝その化学と実際
技術＝」（平成４年、大成社刊）などに記載されてい
る。特に樹脂との相溶性が良く組成物の物性を損なわな
い含窒素有機燐化合物は樹脂添加剤として期待されてい
る。[Wherein n is 0 or an integer of 1 to 20, and R 1 , R 2 , R 3 and R 4 are independently a phenyl group, a hydroxyphenyl group or an aryl group having 1 to 3 alkyl groups substituted. represents a group, R 5 is a polyhydric phenol residue. On the other hand, it is well known that phosphorus and nitrogen as flame retardants have a synergistic effect, and is described in, for example, “Polymer Flame Retardancy = Its Chemistry and Actual Technology =” (1992, published by Taiseisha). There is. In particular, nitrogen-containing organic phosphorus compounds, which have good compatibility with resins and do not impair the physical properties of the composition, are expected as resin additives.
【０００５】燐と窒素を共に含む有機化合物として、例
えば特開平２−１８０９５９号や特開平５−１９４４３
８号に燐酸素酸とトリアジン化合物の塩が、特公昭５８
−５５１５３号や特開昭６３−７５０８８号には、９，
１０−ジヒドロ−９−オキサ−１０−ホスファフェナン
トレン−１０−オキシド及びそのベンゼン核置換体の１
０位にメチレン基を介してアミン類の結合した化合物
が、特開昭６３−２３５３６３号にはモノ燐酸エステル
アミドが、又特開昭５４−１１９５４４号や特開平４−
１４５０９０号にはオルガノホスファゼン化合物が示さ
れている。しかしこれらの化合物は、有効元素である燐
と窒素の濃度を上げる事が困難であったり、熱安定性に
問題があったり、あるいは合成が困難で製品が高価とな
るなど、問題が多い。As an organic compound containing both phosphorus and nitrogen, for example, JP-A-2-180959 and JP-A-5-19443.
No. 8 is a salt of phosphoric acid and a triazine compound.
-55153 and JP-A-63-75088 describe 9,
1- of 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and its benzene nucleus substitution product
Compounds in which amines are bound to the 0-position through a methylene group, monophosphoric acid ester amides are disclosed in JP-A-63-235363, JP-A-54-119544 and JP-A-4-194544.
No. 145090 discloses organophosphazene compounds. However, these compounds have many problems such that it is difficult to increase the concentrations of phosphorus and nitrogen which are effective elements, there is a problem in thermal stability, or synthesis is difficult and the product is expensive.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、燐と窒素の
含有率が高く、かつ熱安定性の良い含窒素有機燐化合物
とその製造方法を提供する事を目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a nitrogen-containing organic phosphorus compound having a high phosphorus and nitrogen content and good thermal stability, and a method for producing the same.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、前記目標
を達成すべく鋭意研究した結果、ハロ燐酸ジエステル及
び／またはジハロ燐酸エステルと、２つのアミノ基を持
つ化合物を、脱ハロゲン化水素反応させる事により、燐
・窒素を共に含みかつ熱安定性の良い化合物が得られる
事を見いだし、本発明を完成するに至った。DISCLOSURE OF THE INVENTION As a result of intensive studies to achieve the above-mentioned object, the inventors of the present invention dehalogenated halophosphoric acid diester and / or dihalophosphoric acid ester and a compound having two amino groups. It was found that a compound containing both phosphorus and nitrogen and having good thermal stability was obtained by the reaction, and the present invention was completed.
【０００８】すなわち本発明は、一般式（２）及び／ま
たは（３）で示される、単一または異種混合物であるハ
ロ燐酸ジエステル及び／またはジハロ燐酸エステルと、
一般式（４）で示される、分子内に２つのアミノ基を有
する化合物を、脱ハロゲン化水素反応で得られる一般式
（１）で示される化合物とその製造方法に関する。That is, the present invention relates to a halophosphoric acid diester and / or a dihalophosphoric acid ester represented by the general formulas (2) and / or (3), which are single or heterogeneous mixtures.
The present invention relates to a compound represented by the general formula (1), which is obtained by a dehydrohalogenation reaction of a compound having two amino groups in the molecule, and a method for producing the same.
【０００９】[0009]
【化７】 [Chemical 7]
【００１０】[0010]
【化８】 Embedded image
【００１１】（ＸはＣｌまたはＢｒ、Ｒ1，Ｒ2は独立
に、Ｃ1〜Ｃ10のアルキル基、アルケニル基、シクロア
ルキル基、または(X is Cl or Br, R 1 and R 2 are independently C 1 to C 10 alkyl group, alkenyl group, cycloalkyl group, or
【００１２】[0012]
【化９】 [Chemical 9]
【００１３】（ここで、Ｒ3はＣ1〜Ｃ4のアルキル基を
示し、ｌは０〜３の整数を示す）で表されるアリール基
を示す。）(Wherein R 3 represents a C 1 to C 4 alkyl group, and l represents an integer of 0 to 3). )
【００１４】[0014]
【化１０】 [Chemical 10]
【００１５】[0015]
【化１１】 [Chemical 11]
【００１６】本発明の原料である上記一般式（２）のハ
ロ燐酸ジエステルとしては、例えばクロロ燐酸ジメチ
ル、クロロ燐酸ジエチル、クロロ燐酸メチルエチル、ク
ロロ燐酸ジプロピル、クロロ燐酸ジイソプロピル、クロ
ロ燐酸ジ−ｎ−ブチル、クロロ燐酸ジイソブチル、クロ
ロ燐酸ジ−ｔ−ブチル、クロロ燐酸メチルブチル、クロ
ロ燐酸ジ−ｎ−ペンチル、クロロ燐酸ジネオペンチル、
クロロ燐酸ジ−ｎ−ヘキシル、クロロ燐酸ジ−ｎ−オク
チル、クロロ燐酸ジ−２−エチルヘキシル、クロロ燐酸
ジ−ｎ−デシル、クロロ燐酸ジアリル、クロロ燐酸ジブ
テニル、クロロ燐酸ジシクロヘキシル、クロロ燐酸ジフ
ェニル、クロロ燐酸ジクレジル、クロロ燐酸ジキシリ
ル、クロロ燐酸ジ（トリメチルフェニル）、クロロ燐酸
ジ（エチルフェニル）、クロロ燐酸ジ（プロピルフェニ
ル）、クロロ燐酸ジ（イソプロピルフェニル）、クロロ
燐酸ジ（ブチルフェニル）、クロロ燐酸フェニルクレジ
ル、クロロ燐酸フェニルキシリル、ブロモ燐酸ジメチ
ル、ブロモ燐酸ジエチル、ブロモ燐酸メチルエチル、ブ
ロモ燐酸ジプロピル、ブロモ燐酸ジイソプロピル、ブロ
モ燐酸ジ−ｎ−ブチル、ブロモ燐酸ジ−２−エチルヘキ
シル、ブロモ燐酸ジ−ｎ−デシル、ブロモ燐酸ジアリ
ル、ブロモ燐酸ジブテニル、ブロモ燐酸ジシクロヘキシ
ル、ブロモ燐酸ジフェニル、ブロモ燐酸ジクレジル、ブ
ロモ燐酸ジキシリル、ブロモ燐酸ジ（トリメチルフェニ
ル）等が挙げられる。又、上記一般式（３）のジハロ燐
酸エステルとしては、例えばジクロロ燐酸メチル、ジク
ロロ燐酸エチル、ジクロロ燐酸プロピル、ジクロロ燐酸
イソプロピル、ジクロロ燐酸ｎ−ブチル、ジクロロ燐酸
イソブチル、ジクロロ燐酸ｔ−ブチル、ジクロロ燐酸ｎ
−ペンチル、ジクロロ燐酸ネオペンチル、ジクロロ燐酸
ｎ−ヘキシル、ジクロロ燐酸ｎ−オクチル、ジクロロ燐
酸２−エチルヘキシル、ジクロロ燐酸ｎ−デシル、ジク
ロロ燐酸アリル、ジクロロ燐酸ブテニル、ジクロロ燐酸
シクロヘキシル、ジクロロ燐酸フェニル、ジクロロ燐酸
クレジル、ジクロロ燐酸キシリル、ジクロロ燐酸トリメ
チルフェニル、ジクロロ燐酸エチルフェニル、ジクロロ
燐酸プロピルフェニル、ジクロロ燐酸イソプロピルフェ
ニル、ジクロロ燐酸ブチルフェニル、ジブロモ燐酸メチ
ル、ジブロモ燐酸エチル、ジブロモ燐酸プロピル、ジブ
ロモ燐酸イソプロピル、ジブロモ燐酸ｎ−ブチル、ジブ
ロモ燐酸２−エチルヘキシル、ジブロモ燐酸ｎ−デシ
ル、ジブロモ燐酸アリル、ジブロモ燐酸ブテニル、ジブ
ロモ燐酸シクロヘキシル、ジブロモ燐酸フェニル、ジブ
ロモ燐酸クレジル、ジブロモ燐酸キシリル、ジブロモ燐
酸トリメチルフェニル等が挙げられる。特に好ましい物
として、クロロ燐酸ジフェニル、クロロ燐酸ジクレジ
ル、クロロ燐酸ジキシリルがある。これらのハロ燐酸ジ
エステル及び／またはジハロ燐酸エステルは、例えばル
イス酸触媒のもとで、オキシハロゲン化燐に対し、１〜
２倍モルの該当するアルコール類及び／またはフェノー
ル類を加え、脱ハロゲン化水素反応する事で合成でき
る。Examples of the halophosphoric acid diester of the above-mentioned general formula (2), which is a raw material of the present invention, include dimethyl chlorophosphate, diethyl chlorophosphate, methylethyl chlorophosphate, dipropyl chlorophosphate, diisopropyl chlorophosphate and di-n-chlorophosphate. Butyl, diisobutyl chlorophosphate, di-t-butyl chlorophosphate, methylbutyl chlorophosphate, di-n-pentyl chlorophosphate, dineopentyl chlorophosphate,
Di-n-hexyl chlorophosphate, di-n-octyl chlorophosphate, di-2-ethylhexyl chlorophosphate, di-n-decyl chlorophosphate, diallyl chlorophosphate, dibutenyl chlorophosphate, dicyclohexyl chlorophosphate, diphenyl chlorophosphate, chlorophosphate Dicresyl, dixylyl chlorophosphate, di (trimethylphenyl) chlorophosphate, di (ethylphenyl) chlorophosphate, di (propylphenyl) chlorophosphate, di (isopropylphenyl) chlorophosphate, di (butylphenyl) chlorophosphate, phenyl chlorophosphate Zil, phenyl xylyl chlorophosphate, dimethyl bromophosphate, diethyl bromophosphate, methylethyl bromophosphate, dipropyl bromophosphate, diisopropyl bromophosphate, di-n-butyl bromophosphate, di-2-ethylhexyl bromophosphate, di-bromophosphate - decyl, bromo acid diallyl, bromo phosphate Jibuteniru, bromo acid dicyclohexyl, bromo diphenyl phosphate, bromo phosphate dicresyl, bromo phosphoric dixylyl, etc. bromo phosphate di (trimethylphenyl) and the like. Examples of the dihalophosphate ester represented by the general formula (3) include methyl dichlorophosphate, ethyl dichlorophosphate, propyl dichlorophosphate, isopropyl dichlorophosphate, n-butyl dichlorophosphate, isobutyl dichlorophosphate, t-butyl dichlorophosphate, dichlorophosphate. n
-Pentyl, neopentyl dichlorophosphate, n-hexyl dichlorophosphate, n-octyl dichlorophosphate, 2-ethylhexyl dichlorophosphate, n-decyl dichlorophosphate, allyl dichlorophosphate, butenyl dichlorophosphate, cyclohexyl dichlorophosphate, phenyl dichlorophosphate, cresyl dichlorophosphate. , Xylyl dichlorophosphate, trimethylphenyl dichlorophosphate, ethylphenyl dichlorophosphate, propylphenyl dichlorophosphate, isopropylphenyl dichlorophosphate, butylphenyl dichlorophosphate, methyl dibromophosphate, ethyl dibromophosphate, propyl dibromophosphate, isopropyl dibromophosphate, n-dibromophosphate Butyl, 2-ethylhexyl dibromophosphate, n-decyl dibromophosphate, allyl dibromophosphate, butenyl dibromophosphate, cyclohexyl dibromophosphate Le, dibromo acid phenyl, dibromo acid cresyl, dibromo acid xylyl include dibromo phosphate trimethylphenyl like. Particularly preferred are diphenyl chlorophosphate, dicresyl chlorophosphate, and dixylyl chlorophosphate. These halophosphoric acid diesters and / or dihalophosphoric acid esters can be used, for example, in the presence of a Lewis acid catalyst to give 1 to 1 to phosphorus oxyhalide.
It can be synthesized by adding twice the molar amount of the corresponding alcohols and / or phenols and conducting a dehydrohalogenation reaction.
【００１７】本発明のもう一方の原料である上記一般式
（４）の二つのアミノ基を持つ化合物としては、例えば
エチレンジアミン、ブチレンジアミン、ヘキサメチレン
ジアミン、フェニレンジアミン、尿素、メチル尿素、
Ｎ，Ｎ’ジメチル尿素、Ｎ，Ｎ’ジエチル尿素、しゅう
酸ジアミド、グアニジン、アミノグアニジン、ビウレッ
ト、グアニル尿素、グアニルチオ尿素、グアナミン、メ
チルグアナミン、フェニルグアナミン等が挙げられる
が、得に好ましい物として、尿素、Ｎ，Ｎ’ジメチル尿
素、グアニジンがある。The compound having two amino groups of the above-mentioned general formula (4) which is the other raw material of the present invention includes, for example, ethylenediamine, butylenediamine, hexamethylenediamine, phenylenediamine, urea, methylurea,
N, N ′ dimethylurea, N, N ′ diethylurea, oxalic acid diamide, guanidine, aminoguanidine, biuret, guanylurea, guanylthiourea, guanamine, methylguanamine, phenylguanamine, and the like are preferable. There are urea, N, N ′ dimethylurea and guanidine.
【００１８】一般式（２）及び／または（３）の化合物
と、一般式（４）の化合物の脱ハロゲン化水素反応は、
通常無水条件下に０〜１５０℃の温度で行い、２時間な
いし１０時間程度でほぼ完結する。脱離したハロゲン化
水素は、一般式（４）の化合物及び／またはその分解物
と反応して塩を形成するため、一般式（２）及び／また
は（３）の化合物に対する、一般式（４）の化合物の仕
込量は、通常等モル（２倍当量）以上とし、等モル〜２
倍モルの範囲が望ましい。反応の進行と共に反応物の粘
度が上昇するので、必要に応じて反応温度を上げて反応
を完結させる。The dehydrohalogenation reaction of the compound of the general formula (2) and / or (3) with the compound of the general formula (4) is
Usually, the reaction is performed under anhydrous conditions at a temperature of 0 to 150 ° C., and is completed in about 2 to 10 hours. The eliminated hydrogen halide reacts with the compound of the general formula (4) and / or a decomposition product thereof to form a salt, so that the compound of the general formula (4) is used for the compound of the general formula (2) and / or (3). The amount of the compound (1) is usually equimolar (2 times equivalent) or more, and equimolar to 2
A double molar range is desirable. Since the viscosity of the reaction product increases with the progress of the reaction, the reaction temperature is raised as necessary to complete the reaction.
【００１９】得られる反応物中には、一般式（１）の化
合物、上記塩類の他に、条件によって異なるが、一般式
（４）の変成物または分解物と一般式（２）及び／また
は（３）の化合物の脱ハロゲン化水素反応で生じる低分
子量の燐酸エステルアミド等が少量含まれる。このうち
塩類は、水洗等により除去できる。生成物を同重量程度
の、親水性溶媒に溶解し、２倍量以上の水と混合する事
により、効率の良い洗浄を行う事が出来る。ここで用い
る親水性溶媒としては、例えばメタノール・エタノール
等のアルコール類、アセトン・メチルエチルケトンなど
のケトン類、テトラヒドロフラン等のエーテル類などが
挙げられる。In the reaction product obtained, in addition to the compound of the general formula (1) and the above-mentioned salts, the modified or decomposed product of the general formula (4) and the general formula (2) and / or A small amount of low molecular weight phosphoric acid ester amide and the like produced by the dehydrohalogenation reaction of the compound (3) is contained. Of these, salts can be removed by washing with water or the like. Efficient washing can be performed by dissolving the product in a hydrophilic solvent of about the same weight and mixing with water in an amount not less than twice the amount. Examples of the hydrophilic solvent used here include alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, and ethers such as tetrahydrofuran.
【００２０】この様にして合成された含窒素有機燐化合
物は、何れも燐と窒素の含有率が高く、熱安定性が優れ
ており、特に樹脂用難燃剤として利用する場合、少量で
高い効果が得られる。Each of the nitrogen-containing organic phosphorus compounds synthesized in this manner has a high phosphorus and nitrogen content and excellent thermal stability. Especially when used as a flame retardant for resins, a small amount is highly effective. Is obtained.
【００２１】[0021]
【実施例】以下、実施例により具体的に説明する。EXAMPLES The present invention will be specifically described below with reference to examples.
【００２２】[0022]
【実施例１】ジフェニルホスホリッククロリド１３５ｇ
（０．５モル）と尿素４５ｇ（０．７５モル）をかくは
ん機付きの３００ｍｌ３ツ口フラスコに仕込み、乾燥窒
素気流下、８０℃で４時間反応し、やや白濁した極めて
粘調な反応物を得た。この反応物にメタノール１００ｇ
を加えて加熱・かくはんして無色透明な均一溶液とな
し、これをかくはんしている純水５００ｍｌ中に注ぎ込
んだ。白色ワックス状の成分を回収、減圧乾燥して、化
合物１２３ｇを得た。Example 1 135 g of diphenylphosphoric chloride
(0.5 mol) and 45 g (0.75 mol) of urea were charged into a 300 ml three-necked flask equipped with a stirrer and reacted under a dry nitrogen stream at 80 ° C. for 4 hours to give a slightly cloudy and extremely viscous reaction product. Obtained. 100 g of methanol is added to this reaction product.
Was added and heated and stirred to form a colorless transparent homogeneous solution, which was poured into 500 ml of stirred pure water. The white waxy component was recovered and dried under reduced pressure to obtain 123 g of the compound.
【００２３】得られた組成物の元素分析値は、Ｃ：５
４．３ｗｔ％，Ｈ：４．６ｗｔ％，Ｎ：６．０ｗｔ％，
Ｏ：２３．１ｗｔ％，Ｐ：１２．０ｗｔ％，Ｃｌ：０．
０２ｗｔ％で、構造式（Ａ）の化合物の理論値（Ｃ：５
７．３ｗｔ％，Ｈ：４．２ｗｔ％，Ｎ：５．３ｗｔ％，
Ｏ：２１．４ｗｔ％，Ｐ：１１．８ｗｔ％）とほぼ一致
した。The elemental analysis value of the obtained composition was C: 5.
4.3 wt%, H: 4.6 wt%, N: 6.0 wt%,
O: 23.1 wt%, P: 12.0 wt%, Cl: 0.
The theoretical value of the compound of the structural formula (A) (C: 5) at 02 wt%.
7.3 wt%, H: 4.2 wt%, N: 5.3 wt%,
O: 21.4 wt%, P: 11.8 wt%).
【００２４】[0024]
【化１２】 [Chemical 12]
【００２５】[0025]
【実施例２】ジ（２，６ジメチルフェニル）ホスホリッ
ククロリド１６２ｇ（０．５モル）とグアニジン４５ｇ
（０．７５モル）をかくはん機付きの３００ｍｌ３ツ口
フラスコに仕込み、乾燥窒素気流下、８０℃で２時間１
００℃で４時間反応し、白色沈澱の分散した粘調な反応
物を得た。Example 2 162 g (0.5 mol) of di (2,6-dimethylphenyl) phosphoric chloride and 45 g of guanidine
(0.75 mol) was charged into a 300 ml three-necked flask equipped with a stirrer, and dried at 80 ° C for 2 hours under a dry nitrogen stream.
The reaction was carried out at 00 ° C. for 4 hours to obtain a viscous reaction product in which a white precipitate was dispersed.
【００２６】この反応物にメタノール１００ｇを加えて
加熱・かくはんして無色透明な均一溶液となし、これを
かくはんしている純水５００ｍｌ中に注ぎ込んだ。白色
ワックス状の成分を回収、減圧乾燥して、化合物１４５
ｇを得た。得られた組成物の元素分析値は、Ｃ：６１．
０ｗｔ％，Ｈ：６．７ｗｔ％，Ｎ：７．２ｗｔ％，Ｏ：
１５．５ｗｔ％，Ｐ：９．５ｗｔ％，Ｃｌ：０．０４ｗ
ｔ％で、構造式（Ｂ）の化合物の理論値（Ｃ：６２．３
ｗｔ％，Ｈ：６．３ｗｔ％，Ｎ：６．６ｗｔ％，Ｏ：１
５．１ｗｔ％，Ｐ：９．７ｗｔ％）とほぼ一致した。100 g of methanol was added to this reaction product, and the mixture was heated and stirred to form a colorless transparent uniform solution, which was poured into 500 ml of stirring pure water. A white waxy component was recovered and dried under reduced pressure to give compound 145
g was obtained. The elemental analysis value of the obtained composition is C: 61.
0 wt%, H: 6.7 wt%, N: 7.2 wt%, O:
15.5 wt%, P: 9.5 wt%, Cl: 0.04w
The theoretical value of the compound of the structural formula (B) at t% (C: 62.3).
wt%, H: 6.3 wt%, N: 6.6 wt%, O: 1
(5.1 wt%, P: 9.7 wt%).
【００２７】[0027]
【化１３】 [Chemical 13]
【００２８】[0028]
【実施例３】実施例１、２で得られた含窒素有機燐化合
物の加熱減量挙動をＴＧＡで測定した（図１）。トリフ
ェニルホスフェート、トリクレジルホスフェートに対
し、高い熱安定性がみられた。 測定条件 試 料 量 ： 約２０ｍｇ 測定雰囲気 ： Ｈｅ １００ｍｌ／分 昇温速度 ： ２０℃／分Example 3 The weight loss behavior of the nitrogen-containing organic phosphorus compounds obtained in Examples 1 and 2 was measured by TGA (FIG. 1). High thermal stability was observed for triphenyl phosphate and tricresyl phosphate. Measurement conditions Sample amount: Approximately 20 mg Measurement atmosphere: He 100 ml / min Heating rate: 20 ° C / min
【００２９】[0029]
【実施例４】実施例１、２で得られた含窒素有機燐化合
物を、ポリフェニレンエーテル５０％，ポリスチレン５
０％からなる変成ＰＰＥ樹脂に混合し、難燃性テストを
行った結果、少量の添加によって高い難燃性を示した。Example 4 The nitrogen-containing organic phosphorus compound obtained in Examples 1 and 2 was added to polyphenylene ether 50%, polystyrene 5
When mixed with 0% modified PPE resin and subjected to a flame retardancy test, high flame retardancy was exhibited by adding a small amount.
【００３０】[0030]
【発明の効果】実施例から明らかなように、本発明によ
れば、燐と窒素の含有率が高く、かつ熱安定性の良い、
特に樹脂用難燃剤として有用な、新規な含窒素有機燐化
合物を得る事が出来る。As is apparent from the examples, according to the present invention, the phosphorus and nitrogen contents are high and the thermal stability is good.
In particular, a novel nitrogen-containing organic phosphorus compound useful as a flame retardant for resins can be obtained.
【図１】本発明の含窒素有機燐化合物のＴＧＡ加熱減量
を示す図。FIG. 1 is a graph showing the TGA heating loss of the nitrogen-containing organic phosphorus compound of the present invention.
１：実施例１で得られた含窒素有機燐化合物についての
加熱減量を示す曲線 ２：実施例２で得られた含窒素有機燐化合物についての
加熱減量を示す曲線 ３：トリフェニルホスフェートの加熱減量を示す曲線 ４：トリクレジルホスフェートの加熱減量を示す曲線1: Curve showing heating loss for the nitrogen-containing organic phosphorus compound obtained in Example 2: Curve showing heating loss for the nitrogen-containing organic phosphorus compound obtained in Example 2: 3: Heating loss of triphenyl phosphate Showing the curve 4: Curve showing the heat loss of tricresyl phosphate
Claims (2)
燐化合物。 【化１】 1. A nitrogen-containing organic phosphorus compound represented by the following general formula (1). Embedded image
れる、単一または異種混合物であるハロ燐酸ジエステル
及び／またはジハロ燐酸エステルドと、一般式（４）で
示される、分子内に２つのアミノ基を有する化合物を、
脱ハロゲン化水素反応させる特許請求の範囲第１項記載
の化合物の製造方法。 【化２】 【化３】 （ＸはＣｌまたはＢｒ、Ｒ1，Ｒ2は独立に、Ｃ1〜Ｃ10
のアルキル基、アルケニル基、シクロアルキル基、また
は 【化４】 （ここで、Ｒ3はＣ1〜Ｃ4のアルキル基を示し、ｌは０
〜３の整数を示す）で表されるアリール基を示す。） 【化５】 2. A halophosphoric acid diester and / or a dihalophosphoric acid ester represented by the general formula (2) and / or (3), which is a single or a heterogeneous mixture, and an intramolecular compound represented by the general formula (4). A compound having two amino groups,
The method for producing a compound according to claim 1, wherein a dehydrohalogenation reaction is carried out. Embedded image Embedded image (X is Cl or Br, R 1 and R 2 are independently C 1 to C 10
An alkyl group, an alkenyl group, a cycloalkyl group, or (Here, R 3 represents a C 1 -C 4 alkyl group, and l is 0
Represents an integer of 3). ) [Chemical 5]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14156894A JPH0812688A (en) | 1994-06-23 | 1994-06-23 | New nitrogen-containing organic phosphorus compound and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14156894A JPH0812688A (en) | 1994-06-23 | 1994-06-23 | New nitrogen-containing organic phosphorus compound and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0812688A true JPH0812688A (en) | 1996-01-16 |
Family
ID=15295009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14156894A Withdrawn JPH0812688A (en) | 1994-06-23 | 1994-06-23 | New nitrogen-containing organic phosphorus compound and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0812688A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001354836A (en) * | 2000-06-14 | 2001-12-25 | Asahi Denka Kogyo Kk | Flame retardant epoxy resin composition |
| WO2013191227A1 (en) * | 2012-06-18 | 2013-12-27 | 大京化学株式会社 | Method for producing phosphoric acid ester amides |
-
1994
- 1994-06-23 JP JP14156894A patent/JPH0812688A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001354836A (en) * | 2000-06-14 | 2001-12-25 | Asahi Denka Kogyo Kk | Flame retardant epoxy resin composition |
| WO2013191227A1 (en) * | 2012-06-18 | 2013-12-27 | 大京化学株式会社 | Method for producing phosphoric acid ester amides |
| KR20150018837A (en) * | 2012-06-18 | 2015-02-24 | 다이쿄 케미칼 컴퍼니, 리미티드 | Method for producing phosphoric acid ester amides |
| CN104395329A (en) * | 2012-06-18 | 2015-03-04 | 大京化学株式会社 | Method for producing phosphoric acid ester amides |
| JPWO2013191227A1 (en) * | 2012-06-18 | 2016-05-26 | 大京化学株式会社 | Method for producing phosphoric ester amides |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1236621A (en) | Fire retardant composition | |
| JP2016216463A (en) | Manufacturing method of mixture of alkyl phosphite and dialkylphosphinate | |
| EP3553068A1 (en) | Hydroxymethylphosphonate, polyurethane foam-forming compositions, polyurethane foam and articles made therefrom | |
| JP4695080B2 (en) | Flame retardant phosphonate additives for thermoplastics | |
| EP0363321B1 (en) | Flame retardants | |
| US2960529A (en) | Process for preparing neutral phosphates | |
| EP1403272B1 (en) | Process for preparation of phosphoric esters | |
| KR900006036B1 (en) | Stabilized polymer composition | |
| JPH0812688A (en) | New nitrogen-containing organic phosphorus compound and its production | |
| ITMI941088A1 (en) | NEW POLI (PENTAERITRIL DIPHOSPHONATE) AND ITS USE IN SELF-EXTINGUISHING THERMOPLASTIC POLYMERIC COMPOSITIONS | |
| US3970726A (en) | Polycyclic phosphate esters and process for preparing same | |
| US3201437A (en) | Neoalkyl phosphites | |
| JPH0812692A (en) | New nitrogen-containing organic phosphorus compound and its production | |
| US4407765A (en) | Synthesis of organic phosphate-phosphonates | |
| JPS62273987A (en) | Production of liquid triaryl thiophosphate mixture | |
| US4118435A (en) | Catalyzed production of phosphorous and phosphonous acid ester chlorides | |
| WO2004060900A1 (en) | Process for the production of pentaerythritol diphosphonates | |
| US3318982A (en) | Process for the manufacture of mixtures of acid orthophosphoric acid esters | |
| JP4065701B2 (en) | Pentaerythritol diphosphonate compound and method for producing the same | |
| US2834797A (en) | Method of producing mono- and dialkyl hydrogen phosphites | |
| JPH06172373A (en) | Production of 6-chloro-(6h)-dibenz(c,e9))1,2)- oxaphosphorin | |
| JP2882763B2 (en) | Flame retardant composition for polyurethane foam | |
| CN1135755A (en) | Bis (Pentaerythritol phosphate alcohol) alkylphosphonate | |
| US4054543A (en) | Phosphorus-containing polyols as flame retardant agents for polyurethanes | |
| JPH03157390A (en) | Novel aminomethanephophonic acid arylester and its preparation and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20010904 |