JP2857793B2 - Phosphorus-containing imide compound and method for producing the same - Google Patents
Phosphorus-containing imide compound and method for producing the sameInfo
- Publication number
- JP2857793B2 JP2857793B2 JP15322790A JP15322790A JP2857793B2 JP 2857793 B2 JP2857793 B2 JP 2857793B2 JP 15322790 A JP15322790 A JP 15322790A JP 15322790 A JP15322790 A JP 15322790A JP 2857793 B2 JP2857793 B2 JP 2857793B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphorus
- formula
- represented
- imide compound
- resin
- 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
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、難燃剤、樹脂改質剤、樹脂相溶化剤として
有用な含燐イミド化合物及びその製造方法に関するもの
である。Description: TECHNICAL FIELD The present invention relates to a phosphorus-containing imide compound useful as a flame retardant, a resin modifier, and a resin compatibilizer, and a method for producing the same.
従来技術 一般にプラスチックスの利用範囲は高温領域、複合
化、機械的、電気的特性の向上、長期的使用の際の耐候
性の向上等の領域へと拡大している。また、その使用範
囲も汎用樹脂からエンジニアリングプラスチックスへと
拡大している。2. Description of the Related Art In general, the range of use of plastics has been expanded to areas such as a high-temperature region, compounding, improvement of mechanical and electrical properties, and improvement of weather resistance in long-term use. The range of use has also been expanded from general-purpose resins to engineering plastics.
このような状況の中で、イミド結合を有する化合物は
耐熱性が高く、物性低下が少ないことから注目されてい
る。Under such circumstances, a compound having an imide bond has attracted attention because of its high heat resistance and little decrease in physical properties.
発明が解決しようとする課題 本発明は、新規な含燐イミド結合を有する化合物及び
その製造方法を提供することを課題とする。Problem to be Solved by the Invention It is an object of the present invention to provide a compound having a novel phosphorus-containing imide bond and a method for producing the same.
課題を解決するための手段 本発明では、一般式（１）で示す含燐イミド化合物及
びその製造方法を提供するものである。Means for Solving the Problems The present invention provides a phosphorus-containing imide compound represented by the general formula (1) and a method for producing the same.
（但し、式（１）のＲは式（２）又は（３）で示される
基であり、 R1は炭素数１〜６の分岐又は直鎖状脂肪族系炭化水素基
又は芳香族系炭化水素基であり、 R2はハロゲン化芳香族系炭化水素基であり、 R3は炭素数１〜20の脂肪族系炭化水素基、水素原子、脂
環族系炭化水素基又はハロゲン原子である。） 本発明の式（１）で示される含燐イミド化合物の具体
的なものとしては、例えば 等が挙げられる。 (However, R in the formula (1) is a group represented by the formula (2) or (3), R 1 is a branched or linear aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 6 carbon atoms, R 2 is a halogenated aromatic hydrocarbon group, R 3 is a carbon number 1 To 20 aliphatic hydrocarbon groups, hydrogen atoms, alicyclic hydrocarbon groups or halogen atoms. Specific examples of the phosphorus-containing imide compound represented by the formula (1) of the present invention include, for example, And the like.
式（１）で示される化合物は、式（４）で示される含
燐ジカルボン酸と式（５）で示されるジカルボン酸無水
物との混合物と、式（６）で示されるジアミノ化合物
を、不活性溶媒の存在下で所定量のモル比にて脱水反応
せしめることにより得られる。The compound represented by the formula (1) is obtained by converting a mixture of the phosphorus-containing dicarboxylic acid represented by the formula (4) and the dicarboxylic anhydride represented by the formula (5) with a diamino compound represented by the formula (6). It is obtained by performing a dehydration reaction at a predetermined molar ratio in the presence of an active solvent.
（ただし、Ｒ、R1及びR2は前述と同様である。） 式（４）で示される含燐ジカルボン酸としては 等の化合物が挙げられ、式（５）で示されるハロゲン化
芳香族系ジカルボン酸無水物の代表的なものとしては、
例えばテトラブロモフタール酸、テトラクロル無水フタ
ール酸、テトラブロム無水フタール酸、ジクロル無水フ
タール酸、ジブロム無水フタール酸等がある。 (However, R, R 1 and R 2 are the same as described above.) As the phosphorus-containing dicarboxylic acid represented by the formula (4), And typical examples of the halogenated aromatic dicarboxylic anhydride represented by the formula (5) include:
For example, there are tetrabromophthalic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, dichlorophthalic anhydride, dibromophthalic anhydride and the like.
また、式（６）で示されるジアミノ化合物としては、
例えばエチレンジアミン、ヘキサメチレンジアミン、プ
ロピレンジアミン、フェニレンジアミン、キシリレンジ
アミン、4,4′−メチレンビスジフェニルアミン等が挙
げられる。Further, as the diamino compound represented by the formula (6),
For example, ethylenediamine, hexamethylenediamine, propylenediamine, phenylenediamine, xylylenediamine, 4,4'-methylenebisdiphenylamine and the like can be mentioned.
次に、本発明の反応で使用する不活性溶媒としては、
例えばキシレン、トルエン、ジメチルホルムアミド、ジ
メチルアセトアミド、ベンゼン、シクロヘキサン、ジメ
チルスルホオキシド、メチルピロリドン等が挙げられ、
これらは二種以上混合して使用してもよい。Next, as the inert solvent used in the reaction of the present invention,
For example, xylene, toluene, dimethylformamide, dimethylacetamide, benzene, cyclohexane, dimethylsulfoxide, methylpyrrolidone, and the like,
These may be used as a mixture of two or more.
なお、不活性溶媒の使用量は、任意であるが、一般に
好ましいのは、反応混合物の１〜10倍程度である。The amount of the inert solvent to be used is arbitrary, but is generally preferably about 1 to 10 times the reaction mixture.
次に、本発明における式（１）の含燐イミド化合物の
製造方法を反応式で表すと、次の通りである。Next, the method for producing the phosphorus-containing imide compound of the formula (1) in the present invention is represented by the following reaction formula.
本発明では、上記の如く、式（４）で示される含燐ジ
カルボン酸と式（５）で示されるハロゲン化芳香族ジカ
ルボン酸無水物との混合物と、式（６）で示されるジア
ミノ化合物を不活性溶媒中で脱水反応せしめるものであ
るが、その具体的な操作法は次の通りである。 In the present invention, as described above, a mixture of the phosphorus-containing dicarboxylic acid represented by the formula (4) and the halogenated aromatic dicarboxylic anhydride represented by the formula (5) and the diamino compound represented by the formula (6) are used. The dehydration reaction is carried out in an inert solvent. The specific operation method is as follows.
まず最初に、式（４）で示される含燐ジカルボン酸と
式（５）で示されるハロゲン化芳香族ジカルボン酸無水
物との混合物（混合割合はモル比で1.0〜1.1:1.1〜1.0
である）を不活性溶媒に溶解し、その中に、撹拌しなが
ら、式（６）で示されるジアミノ化合物１モルを滴下す
る。First, a mixture of the phosphorus-containing dicarboxylic acid represented by the formula (4) and the halogenated aromatic dicarboxylic anhydride represented by the formula (5) (the mixing ratio is 1.0 to 1.1: 1.1 to 1.0 in terms of molar ratio)
Is dissolved in an inert solvent, and 1 mol of the diamino compound represented by the formula (6) is added dropwise thereto with stirring.
この際、温度を60〜150℃に保ち、式（６）で示され
るジアミノ化合物の滴下終了後、系内を100〜150℃に保
ち、撹拌反応せしめる。At this time, the temperature is maintained at 60 to 150 ° C., and after the completion of the dropwise addition of the diamino compound represented by the formula (6), the inside of the system is maintained at 100 to 150 ° C. to carry out a stirring reaction.
次に、所定量の水の留出を認めた後、不活性溶媒を減
圧留去し、反応生成物を水洗、乾燥するか、又はメタノ
ール、イソプロパノール、アセトン、メチルエチルケト
ン等により洗浄した後、乾燥し、目的物を得る。Next, after a predetermined amount of water was distilled off, the inert solvent was distilled off under reduced pressure, and the reaction product was washed with water and dried, or washed with methanol, isopropanol, acetone, methyl ethyl ketone, etc., and then dried. , Get the object.
本発明の式（１）で示される含燐イミド化合物は、燐
とハロゲンを併含するものであり、難燃化剤、樹脂改質
剤、樹脂相溶化剤として、汎用の合成樹脂、例えば、ポ
リスチレン樹脂、ポリエチレン樹脂、ポリプロピレン樹
脂、ABS樹脂、アクリル系樹脂、塩化ビニル樹脂、ポリ
フェニレンオキシド樹脂、ポリカーボネート樹脂、ポリ
アミド樹脂、飽和又は不飽和ポリエステル樹脂、メラミ
ン樹脂、エポキシ樹脂、フェノール樹脂等、あるいはエ
ンジニアリングプラスチック等に効果的に使用できるも
のである。The phosphorus-containing imide compound of the present invention represented by the formula (1) contains both phosphorus and halogen. As a flame retardant, a resin modifier, and a resin compatibilizer, a general-purpose synthetic resin, for example, Polystyrene resin, polyethylene resin, polypropylene resin, ABS resin, acrylic resin, vinyl chloride resin, polyphenylene oxide resin, polycarbonate resin, polyamide resin, saturated or unsaturated polyester resin, melamine resin, epoxy resin, phenol resin, etc., or engineering plastic Etc. can be used effectively.
更に、水分散体として、繊維用、紙、ゴム等の添加剤
として使用可能であり、いずれにおいても優れた効果が
期待できる。Further, it can be used as an aqueous dispersion as an additive for fibers, paper, rubber and the like, and excellent effects can be expected in any case.
なお、本発明の式（１）で示される含燐イミド化合物
は、他のハロゲン系及び／又は燐系難燃剤、難燃化樹脂
（例えば、ブロム化エポキシ樹脂、ポリブロム化スチレ
ン、含燐ポリエステル、塩素化ポリエチレン等）と併用
してもよく、更に、酸化防止剤、紫外線吸収剤、赤外線
吸収剤、帯電防止剤、無機充填剤、溶剤、可塑剤、結晶
核剤、顔料等の添加剤との併用も可能である。The phosphorus-containing imide compound represented by the formula (1) of the present invention may be used in combination with another halogen-based and / or phosphorus-based flame retardant, a flame-retardant resin (for example, a brominated epoxy resin, a polybrominated styrene, a phosphorus-containing polyester, Chlorinated polyethylene, etc.) and additives such as antioxidants, ultraviolet absorbers, infrared absorbers, antistatic agents, inorganic fillers, solvents, plasticizers, crystal nucleating agents, and pigments. Combinations are also possible.
本発明の（１）で示される含燐イミド化合物の添加量
は、適宜選択できるが、組成物中に0.2〜40重量％存在
するような量が好ましく、また添加方法は例えば、本発
明の化合物を直接添加してもよく、または溶媒に溶解し
た形態、水中もしくは油中に分散せしめたエマルジョン
の形態いずれで添加してもよい。The addition amount of the phosphorus-containing imide compound represented by (1) of the present invention can be appropriately selected, but is preferably an amount such that the compound is present in an amount of 0.2 to 40% by weight in the composition. May be added directly or in the form of a solution dissolved in a solvent or an emulsion dispersed in water or oil.
作用 本発明の式（１）で示される含燐イミド化合物は、高
分子物質に対して優れた難燃性、樹脂改質性、相溶性を
付与できるものであり、しかも、その難燃性は大であ
り、耐候性にも優れている。Action The phosphorus-containing imide compound of the present invention represented by the formula (1) is capable of imparting excellent flame retardancy, resin modifying property, and compatibility to a polymer substance. It is large and has excellent weather resistance.
実施例 次に本発明を実施例に従って説明するが、本発明はか
かる実施例によって限定されるものではない。EXAMPLES Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
実施例１ 撹拌機、冷却コンデンサー、温度計、滴下ロートを有
する四ツ口フラスコ中に、次の式で示される含燐カルボ
ン酸346部 とテトラブロモ無水フタール酸464部、キシレン800部、
DMF750部を加え、80〜100℃に保ちながら、エチレンジ
アミン61部を滴下する。滴下完了後120〜135℃に保ち、
窒素気流中で反応させ、留出水をトラップにより分離
し、理論量以上の留出水が出たことを確認した後、反応
を終了させた。Example 1 In a four-necked flask having a stirrer, a cooling condenser, a thermometer, and a dropping funnel, 346 parts of a phosphorus-containing carboxylic acid represented by the following formula was added. And tetrabromophthalic anhydride 464 parts, xylene 800 parts,
Add 750 parts of DMF, and add 61 parts of ethylenediamine dropwise while maintaining the temperature at 80 to 100 ° C. After completion of dropping, keep at 120-135 ° C,
The reaction was carried out in a nitrogen stream, the distillate was separated by a trap, and after confirming that a distillate of a theoretical amount or more was generated, the reaction was terminated.
次いで、反応溶媒を減圧留去する。 Next, the reaction solvent is distilled off under reduced pressure.
生成物をメタノール2000部で洗浄し、濾別、乾燥し
て、淡黄色粉末を得た。The product was washed with 2000 parts of methanol, separated by filtration and dried to obtain a pale yellow powder.
この製品の分析結果は次の通りであり、この結果か
ら、下記の含燐イミド化合物が得られたことが確認され
た。The analysis results of this product are as follows. From the results, it was confirmed that the following phosphorus-containing imide compound was obtained.
反応生成物799部（計算値835部） 分析値 Ｐ％ 3.69（計算値 3.71） Br％ 39.11（計算値38.32） Ｎ％ 3.29（計算値 3.35） DTA 10％減量 391.1℃ 50％減量 424.4℃ 融点 354.4℃ 実施例２ ABS樹脂100部に、実施例１で得られた含燐イミド化合
物18部及び三酸化アンチモン５部を加え260℃で６分間
混練し、ペレット化した後、成型し、UL−94に基づく燃
焼試験用テストピース（1/8″厚）を作成し、燃焼性を
測定した。その結果を、含燐イミド化合物の代わりに、
市販の難燃剤（デカブロモビフェニルエーテル）を使用
した場合と比較して次表に示す。Reaction product 799 parts (calculated value 835 parts) Analytical value P% 3.69 (calculated value 3.71) Br% 39.11 (calculated value 38.32) N% 3.29 (calculated value 3.35) DTA 10% weight loss 391.1 ° C 50% weight loss 424.4 ° C Melting point 354.4 ° C Example 2 18 parts of the phosphorus-containing imide compound obtained in Example 1 and 5 parts of antimony trioxide were added to 100 parts of an ABS resin, kneaded at 260 ° C for 6 minutes, pelletized, molded, and subjected to UL-94. A test piece (1/8 "thick) was prepared based on the flammability test, and the flammability was measured.
The following table shows a comparison with the case where a commercially available flame retardant (decabromobiphenyl ether) is used.
発明の効果 本発明では、難燃剤、樹脂改質剤、樹脂相溶化剤とし
て有用な新規な含燐イミド化合物が得られる。 Effects of the Invention According to the present invention, a novel phosphorus-containing imide compound useful as a flame retardant, a resin modifier, or a resin compatibilizer can be obtained.
Claims (2)
物。 （但し、式（１）のＲは式（２）又は（３）で示される
基であり、 R1は炭素数１〜６の分岐又は直鎖状脂肪族系炭化水素基
又は芳香族系炭化水素基であり、 R2はハロゲン化芳香族系炭化水素基であり、 R3は炭素数１〜20の脂肪族系炭化水素基、水素原子、脂
環族系炭化水素基又はハロゲン原子である。）1. A phosphorus-containing imide compound represented by the following formula (1). (However, R in the formula (1) is a group represented by the formula (2) or (3), R 1 is a branched or linear aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 6 carbon atoms, R 2 is a halogenated aromatic hydrocarbon group, R 3 is a carbon number 1 To 20 aliphatic hydrocarbon groups, hydrogen atoms, alicyclic hydrocarbon groups or halogen atoms. )
酸と下記の式（５）で示されるハロゲン化芳香族ジカル
ボン酸無水物との混合物に、下記の式（６）で示される
ジアミノ化合物を、不活性溶媒中で反応させることを特
徴とする請求項１記載の式（１）で示される含燐イミド
化合物の製造方法。 （ただし、Ｒ、R1及びR2は前記同様である。）2. A mixture of a phosphorus-containing dicarboxylic acid represented by the following formula (4) and a halogenated aromatic dicarboxylic anhydride represented by the following formula (5) is represented by the following formula (6). The method for producing a phosphorus-containing imide compound represented by the formula (1) according to claim 1, wherein the diamino compound is reacted in an inert solvent. (However, R, R 1 and R 2 are the same as described above.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15322790A JP2857793B2 (en) | 1990-06-11 | 1990-06-11 | Phosphorus-containing imide compound and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15322790A JP2857793B2 (en) | 1990-06-11 | 1990-06-11 | Phosphorus-containing imide compound and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0446187A JPH0446187A (en) | 1992-02-17 |
| JP2857793B2 true JP2857793B2 (en) | 1999-02-17 |
Family
ID=15557838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15322790A Expired - Fee Related JP2857793B2 (en) | 1990-06-11 | 1990-06-11 | Phosphorus-containing imide compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2857793B2 (en) |
-
1990
- 1990-06-11 JP JP15322790A patent/JP2857793B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0446187A (en) | 1992-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2857793B2 (en) | Phosphorus-containing imide compound and method for producing the same | |
| JP3508360B2 (en) | Flame retardant and flame retardant resin composition | |
| EP0326163B1 (en) | Method of producing imide bond-containing resins and flame retardants comprising said resins | |
| JP5337297B2 (en) | Aryl alkenyl ether oligomers and polymers and their use in the production of flame retardants | |
| WO2001048072A1 (en) | Resin additive composition and process for producing the same | |
| US4940802A (en) | 4,4'-bis(phthalimido)diphenyl sulfone compounds, processes for their production and flame retardant polymer compositions containing them | |
| US4602111A (en) | Polybromo tertiary amine | |
| KR101671758B1 (en) | Preparation method of non halogen-based flame-retardant polypropylene resin, polypropylene resin prepared thereby, and flame-retardant polymer resin composition comprising them | |
| KR950008150B1 (en) | Method of producing imide bond-containing resins and flame retardants comprising said resins | |
| KR930007844B1 (en) | Method for producing sulfur-containing halogenate esters of neopeutyl alcohol | |
| KR100842205B1 (en) | Phosphorous containing cyclic compound, method of preparing thereof and flameproof thermoplastic resin composition using the same | |
| US5086114A (en) | Method of producing imide bond-containing resins | |
| JP2005307219A (en) | Flame retardant, method for producing the same and flame-retardant thermoplastic resin composition containing the same | |
| JP2653142B2 (en) | Flame-retardant polymer composition containing 4,4'-bis (phthalimide) diphenylsulfone derivative | |
| JPH08120117A (en) | Flame-retardant thermoplastic resin composition | |
| JP3815804B2 (en) | Tribromoneopentyl alcohol derivative | |
| JP2723593B2 (en) | Flame retardant resin composition | |
| JP2518325B2 (en) | Flame-retardant polymer composition containing bis (biphenyl) diester derivative | |
| JPH01149753A (en) | Bis(biphenyl)diester derivative and production thereof | |
| CN112442167A (en) | Reactive flame retardant and preparation method and application thereof | |
| JPH01199944A (en) | Production of halogen-containing compound and flame-retardant composed of said compound | |
| JPS61145256A (en) | Flame-retardant thermoplastic resin composition | |
| JPS60166333A (en) | Flame retardant | |
| JPH03229790A (en) | Flame-retardant for use in organic polymer substance | |
| JPS60166636A (en) | Bromine-containing phenol derivative |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |