JP2742582B2 - Method for producing high molecular weight flame retardant - Google Patents
Method for producing high molecular weight flame retardantInfo
- Publication number
- JP2742582B2 JP2742582B2 JP63009104A JP910488A JP2742582B2 JP 2742582 B2 JP2742582 B2 JP 2742582B2 JP 63009104 A JP63009104 A JP 63009104A JP 910488 A JP910488 A JP 910488A JP 2742582 B2 JP2742582 B2 JP 2742582B2
- Authority
- JP
- Japan
- Prior art keywords
- flame retardant
- molecular weight
- reaction
- high molecular
- group
- 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 - Lifetime
Links
Description
【発明の詳細な説明】 本発明は、高分子量型難燃剤の製造方法に関するもの
である。Description: The present invention relates to a method for producing a high molecular weight flame retardant.
更に詳しくは、ハロゲン化ジヒドロキシ化合物と、ハ
ロゲン化ジグリシジルエーテル化合物を、触媒存在下、
水を含まない有機溶媒中で加熱反応を行い、反応終了
後、反応液にイオン交換樹脂を添加、攪拌した後過を
行うか、或は、イオン交換樹脂を充填したカラム中に反
応液を通液することにより触媒を除いた後、溶媒を除去
乾燥することにより、分子量10,000以上の、直鎖状で着
色が少なく、熱安定性のよい高分子量型難燃剤を製造す
る方法に関するものである。More specifically, a halogenated dihydroxy compound and a halogenated diglycidyl ether compound, in the presence of a catalyst,
Perform the heating reaction in an organic solvent that does not contain water.After the reaction is completed, add the ion exchange resin to the reaction solution and stir, or pass the reaction solution through a column filled with the ion exchange resin. The present invention relates to a method for producing a high-molecular-weight flame retardant having a molecular weight of 10,000 or more, which is linear, less colored, and has good heat stability, by removing the catalyst by removing the solvent, followed by drying.
近年、プラスチックの需要量が高まるとともに、難燃
剤の需要量も増大してきている。そして更に、難燃性の
向上も要求されており、難燃剤の添加によるプラスチッ
ク自体の機械強度や特性の低下を防止することが必要で
あり、樹脂の種類による難燃剤の選択がますます重要と
なってきている。このような中で、ハロゲン含有エポキ
シ樹脂タイプの難燃剤は、その特徴として、昇華、ブリ
ードアウトがなく、耐熱性の良さ、耐光性の良さ、樹脂
との相溶性の良さ、各種機械特性のバランスの良さなど
があり、ポリエステル系樹脂、スチレン系樹脂等に現在
徐々に使用されてきている。しかしながら、その内比較
的低分子量の物は、樹脂の種類、使用条件の違いによ
り、熱安定性の点で問題が起こる場合もあり、さらなる
耐熱性の向上が要求され、より高分子量型の難燃剤が要
求されてきている。In recent years, as the demand for plastics has increased, the demand for flame retardants has also increased. Furthermore, there is a demand for improved flame retardancy, and it is necessary to prevent the mechanical strength and properties of the plastic itself from deteriorating due to the addition of the flame retardant. It has become to. Under these circumstances, halogen-containing epoxy resin type flame retardants are characterized by no sublimation or bleed-out, good heat resistance, good light resistance, good compatibility with resin, and a balance of various mechanical properties. It has been gradually used in polyester resins, styrene resins and the like at present. However, among them, those having a relatively low molecular weight may cause a problem in terms of thermal stability depending on the type of resin and the use conditions, and further improvement in heat resistance is required. Fuel agents have been required.
この様なハロゲン含有エポキシ樹脂タイプの難燃剤の
製造法として、比較的低分子量型の難燃剤は、ハロゲン
化ジヒドロキシ化合物と、ハロゲン化ジグリシジル化合
物を適当な比率で、触媒の存在下、120〜200℃の温度条
件下で、比較的容易に直接反応ができる。しかしなが
ら、平均分子量10,000以上の製造となると、直接に反応
させた場合、粘度の大幅な上昇により、より高温下で反
応を進行させねばならず、加熱による着色が大きくな
り、また、加熱条件が厳しいことにより、エポキシ基の
開環により生成した水酸基とエポキシ基の副反応も起こ
るため、直鎖状の高分子量型難燃剤の合成は非常に困難
であった。また、特開昭58-34854では、反応を二段階に
分け、直接に攪拌下で予備反応させた後、加温下に保持
して反応させる方法が提示されている。しかしながらこ
の場合にも、上記と同様の着色や副反応が起るため、直
鎖状で着色が少なく、熱安定性のよい高分子量型難燃剤
の製造は、困難であると共に、反応も非常に長時間とな
る。As a method for producing such a halogen-containing epoxy resin type flame retardant, a relatively low molecular weight type flame retardant is a halogenated dihydroxy compound and a halogenated diglycidyl compound in an appropriate ratio in the presence of a catalyst at 120 to 200 The reaction can be performed relatively easily under the temperature condition of ° C. However, when the average molecular weight is 10,000 or more, when directly reacted, due to a significant increase in viscosity, the reaction must proceed at a higher temperature, the coloring by heating increases, and heating conditions are severe As a result, a side reaction between the hydroxyl group generated by ring opening of the epoxy group and the epoxy group also occurs, so that it was extremely difficult to synthesize a linear high molecular weight flame retardant. JP-A-58-34854 proposes a method in which the reaction is divided into two stages, and a preliminary reaction is directly performed with stirring, and then the reaction is performed while maintaining the temperature under heating. However, also in this case, since the same coloring and side reactions as described above occur, it is difficult to produce a high molecular weight type flame retardant which is linear and has little coloring, and has good heat stability, and the reaction is also extremely difficult. It will be a long time.
本発明者らは、これらの欠点を改良すべく鋭意検討を
重ねた結果、ハロゲン化ジヒドロキシ化合物と、ハロゲ
ン化ジグリシジルエーテル化合物を、触媒存在下、水を
含まない有機溶媒中で加熱反応を行い、反応終了後、反
応液にイオン交換樹脂を添加、攪拌した後過を行う
か、或は、イオン交換樹脂を充填したカラム中に反応液
を通液することにより触媒を除いた後、該有機溶媒を除
去乾燥することにより、より低温で容易に、分子量10,0
00以上の、直鎖状で着色が少なく、熱安定性のよい高分
子量型難燃剤の製造が可能なことを見いだし本発明に至
った。The present inventors have conducted intensive studies to improve these drawbacks, and as a result, a halogenated dihydroxy compound and a halogenated diglycidyl ether compound were heated and reacted in an organic solvent containing no water in the presence of a catalyst. After the completion of the reaction, an ion-exchange resin is added to the reaction solution, and the mixture is stirred, followed by filtration, or the catalyst is removed by passing the reaction solution through a column filled with the ion-exchange resin to remove the organic compound. By removing the solvent and drying, the molecular weight is easily reduced to 10,000
The present inventors have found that it is possible to produce a high molecular weight type flame retardant of at least 00, which is linear, has little coloration, and has good thermal stability, and has reached the present invention.
本発明で言う、ハロゲン化ジヒドロキシ化合物とは、
一般式 （式中Ｘはハロゲン原子、ｐ、ｑは１〜４の整数、R1
は炭素数１〜４のアルキリデン基、アルキレン基または
−SO2−基を示す。）で表されるものであり、例えば、
テトラブロモビスフェノールＡ、テトラクロロビスフェ
ノールＡ、テトラブロモビスフェノールＦ、テトラブロ
モビスフェノールＳ等が挙げられる。In the present invention, the halogenated dihydroxy compound is
General formula (Where X is a halogen atom, p and q are integers of 1 to 4, R 1
The alkylidene group having 1 to 4 carbon atoms, an alkylene group or -SO 2 - shows a group. ), For example,
Examples thereof include tetrabromobisphenol A, tetrachlorobisphenol A, tetrabromobisphenol F, and tetrabromobisphenol S.
また、ハロゲン化ジグリシジルエーテル化合物とは、
一般式 （式中Ｙはハロゲン原子、ｒ、ｓは１〜４の整数、ｎ
は０〜15の整数、R2は炭素数１〜４のアルキリデン基、
アルキレン基または−SO2−基を示す。）で表されるも
のであり、例えば、テトラブロモビスフェノールＡのジ
グリシジルエーテル、テトラクロロビスフェノールＡの
ジグリシジルエーテル、テトラブロモビスフェノールＦ
のジグリシジルエーテル、テトラブロモビスフェノール
Ｓのジグリシジルエーテル等のモノマー及びこれらのモ
ノマーより誘導されるオリゴマー等が挙げられる。The halogenated diglycidyl ether compound is
General formula (Wherein Y is a halogen atom, r and s are integers of 1-4, n
Is an integer of 0 to 15, R 2 is an alkylidene group having 1 to 4 carbon atoms,
A group - alkylene group or -SO 2. ), For example, diglycidyl ether of tetrabromobisphenol A, diglycidyl ether of tetrachlorobisphenol A, tetrabromobisphenol F
And diglycidyl ether of tetrabromobisphenol S, and oligomers derived from these monomers.
本発明で用いる水を含まない有機溶媒としては、高分
子量型難燃剤を溶解するものであれば特に制限されるも
のではなく、例えば、ベンゼン、トルエン、キシレンの
ような芳香族系炭化水素、アニソールのようなアルコキ
シ置換された芳香族系炭化水素、ジオキサン、ジエチレ
ングリコールジメチルエーテル、ブチルセロソルブのよ
うなエーテル類、クロロホルム、塩化メチレンのような
ハロゲン化炭化水素、ジメチルスルホオキシド、ジメチ
ルホルムアミドなどが挙げられる。また、これらの２種
或はそれ以上の混合溶媒でも良い。The water-free organic solvent used in the present invention is not particularly limited as long as it dissolves a high molecular weight type flame retardant. For example, benzene, toluene, aromatic hydrocarbons such as xylene, anisole Alkoxy-substituted aromatic hydrocarbons, such as dioxane, diethylene glycol dimethyl ether, ethers such as butyl cellosolve, chloroform, halogenated hydrocarbons such as methylene chloride, dimethyl sulfoxide, dimethylformamide, and the like. Further, a mixed solvent of two or more of these may be used.
触媒としては、一般に公知のものが使用できるが、例
えば、水酸化リチウム、水酸化ナトリウム、塩化リチウ
ムのようなアルカリ金属の水酸化物またはハロゲン化
物、トリブチルアミン、ジブチルアミン、テトラメチル
アンモニウムクロライドのようなアミン類、トリフェニ
ルホスフェート、トリフェニルベンジルホスホニウムク
ロライドのようなリン化合物などが挙げられる。As the catalyst, generally known ones can be used, and examples thereof include lithium hydroxide, sodium hydroxide, and hydroxides or halides of alkali metals such as lithium chloride, tributylamine, dibutylamine, and tetramethylammonium chloride. Amines, phosphorus compounds such as triphenyl phosphate and triphenylbenzylphosphonium chloride.
本発明による高分子量型難燃剤の製造方法としては、
ハロゲン化ジヒドロキシ化合物とハロゲン化ジグリシジ
ルエーテル化合物とを水を含まない有機溶媒（以下、単
に溶媒という。）中で、触媒の存在下、加熱条件により
反応を進行させる。即ち、反応が進むに従って伴う反応
液の粘度上昇、反応速度の低下は、溶媒を添加すること
により抑制することが出来る。ところが、溶媒を使用し
ない場合には、粘度の大幅な上昇により、分子量10,000
程度で攪拌が困難となり、反応は非常に進みにくく副反
応も生じやすい。また厳しい加熱条件にて長時間反応さ
せることにより、着色が起こりやすくなる。このことよ
り、本発明では、溶媒を使用することで反応のスムーズ
な進行と、着色を防止しているが、溶媒の使用量として
は、多く入れ過ぎると反応が遅くなりまた少な過ぎると
充分な粘度低下がなくなるため、反応物と溶媒の割合
は、反応物に対し溶媒0.5〜５倍量程度が好ましい。本
反応は、溶媒の還流温度以下で行うが、着色防止の点で
80〜150℃の温度範囲がより好ましい。また、本反応
は、窒素のような不活性ガスの雰囲気下で行うことによ
り、より着色の少ないものとなる。As a method for producing a high molecular weight type flame retardant according to the present invention,
The reaction proceeds between a halogenated dihydroxy compound and a halogenated diglycidyl ether compound in an organic solvent not containing water (hereinafter, simply referred to as a solvent) in the presence of a catalyst under heating conditions. That is, the increase in the viscosity of the reaction solution and the decrease in the reaction rate accompanying the progress of the reaction can be suppressed by adding a solvent. However, when a solvent is not used, the molecular weight is 10,000 due to a large increase in viscosity.
In such a case, stirring becomes difficult, and the reaction is very difficult to proceed, and a side reaction is likely to occur. In addition, coloring is likely to occur by reacting under severe heating conditions for a long time. For this reason, in the present invention, the smooth progress of the reaction and the prevention of coloring are prevented by using a solvent.However, when the amount of the solvent used is too large, the reaction is slowed down. Since the viscosity does not decrease, the ratio of the reactant to the solvent is preferably about 0.5 to 5 times the amount of the solvent relative to the reactant. This reaction is carried out at a temperature not higher than the reflux temperature of the solvent.
A temperature range of 80-150 ° C is more preferred. In addition, by carrying out this reaction in an atmosphere of an inert gas such as nitrogen, coloring becomes less.
また、本反応で得られた反応液は、反応終了後、高分
子量生成物の末端基であるエポキシ基またはフェノール
性水酸基を、官能基を持った化合物で封鎖しても何等差
し支えなく、末端がエポキシ基の場合には、活性水素
（水酸基、フェノール性水酸基、アミノ基、カルボキシ
ル基等）を持った化合物とを、また末端がフェノール性
水酸基の場合には、モノグリシジルエーテルのような一
官能エポキシ基を持った化合物とを反応させてもよい。In addition, after the reaction is completed, the reaction solution obtained by this reaction may be any one of which can block the epoxy group or the phenolic hydroxyl group, which is the terminal group of the high molecular weight product, with a compound having a functional group, and the terminal ends. In the case of an epoxy group, a compound having active hydrogen (hydroxyl group, phenolic hydroxyl group, amino group, carboxyl group, etc.) is used. When the terminal is a phenolic hydroxyl group, a monofunctional epoxy such as monoglycidyl ether is used. It may be reacted with a compound having a group.
次に溶媒中からの高分子量型難燃剤の収得は、まず、
反応終了溶液にイオン交換樹脂を添加し攪拌した後過
を行い触媒を取り除くか、または反応終了溶液をイオン
交換樹脂を充填したカラムに通液して触媒を取り除く。
触媒除去のため、使用するイオン交換樹脂としては、通
常市販されている陽イオン交換樹脂及び陰イオン交換樹
脂でよいが、有機溶剤を使用するため通常の処方に従い
再生したイオン交換樹脂をメタノール、イソプロピルア
ルコールなどで前もって残存水を取り除き、この後、使
用する溶媒で置換するのが好ましい。このとき、イオン
交換樹脂の破砕などが、有機溶媒の使用のため起こるこ
ともあるため有機溶媒で使用可能な樹脂の選択がより好
ましい。次に、溶媒の除去乾燥は、一般に知られている
ドラム式乾燥装置や噴霧式乾燥装置、真空式乾燥装置な
どが使用でき、溶媒をより安全に、ロスを少なくして回
収するためには、真空式乾燥装置がより好ましい。Next, to obtain the high molecular weight type flame retardant from the solvent, first,
Add the ion-exchange resin to the reaction-terminated solution and stir to remove the catalyst, or remove the catalyst by passing the reaction-terminated solution through a column filled with the ion-exchange resin.
For the removal of the catalyst, the ion exchange resin used may be a commercially available cation exchange resin or anion exchange resin. It is preferable to remove residual water in advance with an alcohol or the like, and then replace the solvent with a solvent to be used. At this time, crushing of the ion exchange resin and the like may occur due to the use of an organic solvent, and therefore, selection of a resin usable in the organic solvent is more preferable. Next, removal and drying of the solvent can be performed using a commonly known drum-type drying device, spray-type drying device, vacuum-type drying device, and the like.To recover the solvent more safely and with less loss, A vacuum dryer is more preferred.
以上のようにして製造された高分子量生成物の分析値
は、仕込割合から推察される理論エポキシ当量や理論酸
価にほぼ等しいものであり、フェノール性水酸基のみ反
応に関与した場合のエポキシ当量から計算される酸価と
ほぼ一致した。このことより直鎖状に近い反応物が生成
していることが推定される。The analytical value of the high molecular weight product produced as described above is almost equal to the theoretical epoxy equivalent or the theoretical acid value inferred from the charge ratio, and from the epoxy equivalent when only the phenolic hydroxyl group participates in the reaction. It almost coincided with the calculated acid value. From this, it is presumed that a reaction product close to a straight chain was generated.
本発明の高分子量型難燃剤の用途としては、ポリエチ
レンテレフタレート、ポリブチレンテレフタレート等の
ポリエステル、ポリアミド、ポリカーボネート、ポリウ
レタン、ポリフェニレンエーテル、ポリエチレン、ポリ
プロピレン、エチレン／酢酸ビニル共重合体、ポリフェ
ニレンサルファイド、ポリスチレン、ABSなどの合成樹
脂があげられるが、この他、高分子量型難燃剤であるた
め、本難燃剤自体を通常の合成樹脂と同様に取り扱うこ
とも可能であり、各種樹脂とのポリマーアロイの用途も
可能である。Uses of the high molecular weight flame retardant of the present invention include polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides, polycarbonates, polyurethanes, polyphenylene ethers, polyethylene, polypropylene, ethylene / vinyl acetate copolymers, polyphenylene sulfide, polystyrene, ABS However, since it is a high molecular weight flame retardant, the flame retardant itself can be handled in the same way as ordinary synthetic resins, and polymer alloys with various resins can be used. It is.
本発明の難燃剤の使用にあたっては、他の公知の難燃
剤（窒素系化合物、リン化合物、ハロゲン系化合物）と
併用してもよく、また、必要に応じて難燃助剤（酸化ア
ンチモン、酸化モリブデン、酸化スズなど）などの公知
の化合物と併用してもよい。When using the flame retardant of the present invention, it may be used in combination with other known flame retardants (nitrogen-based compounds, phosphorus compounds, halogen-based compounds). Known compounds such as molybdenum and tin oxide).
以下に実施例を挙げて本発明を具体的に説明するが、
本発明は、その要旨をこえないかぎり、以下にしめす合
成例及び実施例に制約されるものではない。Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited to the synthesis examples and examples shown below unless the gist of the invention is exceeded.
実施例１ テトラブロモビスフェノールＡ（以下TBAと略す）544
g（１モル）とテトラブロモビスフェノールＡのジグリ
シジルエーテル（エポキシ当量331、以下TBAGEと略す）
682g（1.031モル）とジオキサン600gをフラスコにと
り、トリブチルアミン5gを添加したのち、窒素気流下、
還流温度（約100℃）にて、24時間反応した。反応終了
後、ジオキサン2000g、陽イオン交換樹脂（登録商標・
アンバーリスト15（オルガノ製））60ml、陰イオン交換
樹脂（登録商標・ダイヤイオンWA-20（三菱化成工業
製））90mlを加え、50〜60℃で１時間撹拌した。この溶
液を過し、イオン交換樹脂を除去した後、炉液中の溶
媒を真空乾燥装置で除去し、平均分子量42,000、エポキ
シ当量19,800、酸価0.3、色相ガードナー１（50％アニ
ソール溶液の色相）の白色粉末の生成物を得た。Example 1 Tetrabromobisphenol A (hereinafter abbreviated as TBA) 544
g (1 mol) and diglycidyl ether of tetrabromobisphenol A (epoxy equivalent 331, hereinafter abbreviated as TBAGE)
682 g (1.031 mol) and 600 g of dioxane were placed in a flask, and 5 g of tributylamine was added.
The reaction was performed at a reflux temperature (about 100 ° C.) for 24 hours. After completion of the reaction, 2000 g of dioxane, a cation exchange resin (registered trademark,
60 ml of Amberlyst 15 (manufactured by Organo) and 90 ml of an anion exchange resin (registered trademark, Diaion WA-20 (manufactured by Mitsubishi Kasei Kogyo)) were added, followed by stirring at 50 to 60 ° C. for 1 hour. After passing the solution and removing the ion exchange resin, the solvent in the furnace liquid was removed by a vacuum dryer, and the average molecular weight was 42,000, the epoxy equivalent was 19,800, the acid value was 0.3, and the hue Gardner 1 (the hue of a 50% anisole solution). A white powder product was obtained.
実施例２ TBA544g（１モル）とTBAGE642g（0.970モル）とキシ
レン600gをフラスコにとり、テトラメチルアンモニウム
クロライド5gを添加したのち、窒素気流下、135℃に
て、24時間反応した。反応終了後、ジオキサン2000gを
更に加え、この溶液を、陽イオン交換樹脂（登録商標・
アンバーリスト15）60mlと、陰イオン交換樹脂（登録商
標・ダイヤイオンWA-20）90mlを混合して充填したカラ
ムに通液（通液速度SV＝１）し、得られた溶液の溶媒を
真空乾燥装置で除去し、平均分子量39,000、酸価3.1、
色相ガードナー１（50％アニソール溶液の色相）の白色
粉末の生成物を得た。Example 2 544 g (1 mol) of TBA, 642 g (0.970 mol) of TBAGE and 600 g of xylene were placed in a flask, 5 g of tetramethylammonium chloride was added, and the mixture was reacted at 135 ° C. for 24 hours under a nitrogen stream. After the reaction was completed, 2000 g of dioxane was further added, and the solution was added to a cation exchange resin (registered trademark,
Amberlist 15) 60 ml and anion-exchange resin (registered trademark, Diaion WA-20) 90 ml were mixed and passed through a packed column (flow rate SV = 1), and the solvent of the obtained solution was vacuumed. Removed by drying equipment, average molecular weight 39,000, acid value 3.1,
A white powder product of Hud Gardner 1 (hue of 50% anisole solution) was obtained.
次に、比較のため、一般のエポキシオリゴマー型難燃
剤の合成法及び二段階反応による高分子量型難燃剤の合
成法で、高分子量型難燃剤の合成を、以下のとおり行っ
た。Next, for comparison, a high-molecular-weight flame retardant was synthesized as follows by a general method of synthesizing an epoxy oligomer-type flame retardant and a method of synthesizing a high-molecular-weight flame retardant by a two-step reaction.
比較例１ TBA544g（１モル）とTBAGE682g（1.031モル）をフラ
スコにとり、トリブチルアミン0.6gを添加したのち、窒
素気流下160℃にて、６時間反応したが、この時点で攪
拌不能となった。これを取り出し、冷却、粉砕し、淡黄
色粉末の生成物を得た。この生成物は、平均分子量8,00
0、エポキシ当量6,800、酸価5.8、色相ガードナー３（5
0％アニソール溶液の色相）であった。Comparative Example 1 544 g (1 mol) of TBA and 682 g (1.031 mol) of TBAGE were placed in a flask, 0.6 g of tributylamine was added, and the mixture was reacted at 160 ° C. for 6 hours under a nitrogen stream. At this point, stirring became impossible. This was taken out, cooled and pulverized to obtain a product as a pale yellow powder. This product has an average molecular weight of 8,000
0, epoxy equivalent 6,800, acid value 5.8, hue Gardner 3 (5
0% anisole solution).
比較例２ TBA544g（１モル）とTBAGE682g（1.031モル）をフラ
スコにとり、テトラメチルアンモニウムクロライド0.6g
を添加したのち、窒素気流下160℃で、４時間攪拌し、
更に190℃で２時間反応した。つぎにテトラメチルアン
モニウムクロライド0.6gを添加し、均一に溶融混合した
後、反応生成物をバットに移し、160℃の加熱炉で更に3
6時間加熱した。加熱終了後、冷却、粉砕し、褐色粉末
の生成物を得た。この生成物は、平均分子量22,000、エ
ポキシ当量15,200、酸価3.0、色相ガードナー６（50％
アニソール溶液の色相）であった。Comparative Example 2 544 g (1 mol) of TBA and 682 g (1.031 mol) of TBAGE were placed in a flask, and 0.6 g of tetramethylammonium chloride was placed in a flask.
After stirring at 160 ° C. under a nitrogen stream for 4 hours,
Further, the reaction was performed at 190 ° C. for 2 hours. Next, 0.6 g of tetramethylammonium chloride was added, and after melt-mixing uniformly, the reaction product was transferred to a vat and further heated in a heating furnace at 160 ° C. for 3 hours.
Heated for 6 hours. After completion of the heating, the mixture was cooled and pulverized to obtain a brown powder product. This product had an average molecular weight of 22,000, an epoxy equivalent of 15,200, an acid value of 3.0 and a hue Gardner 6 (50%
Hue of anisole solution).
以上の結果を整理し第１表にまとめて示した。 The above results are arranged and summarized in Table 1.
次に実施例１及び２で得た生成物15重量部をポリブチ
レンテレフタレート樹脂100重量部に、三酸化アンチモ
ン８重量部と共に混合し、押出機にてペレタイズし、射
出成形機にて成形したものは、UL-94燃焼試験でＶ−０
に合格した。 Next, 15 parts by weight of the products obtained in Examples 1 and 2 were mixed with 100 parts by weight of polybutylene terephthalate resin together with 8 parts by weight of antimony trioxide, pelletized by an extruder, and molded by an injection molding machine. Is V-0 in UL-94 combustion test
Passed.
以上の結果のごとく、本発明の高分子量型難燃剤の製
造方法では、高分子量の難燃剤が得られ、また色相も良
く、難燃性にも優れている。As described above, according to the method for producing a high molecular weight flame retardant of the present invention, a high molecular weight flame retardant can be obtained, and a good hue and excellent flame retardancy can be obtained.
Claims (3)
ン化ジグリシジルエーテル化合物を、触媒の存在下、水
を含まない有機溶媒中で加熱反応を行い、反応終了後、
反応液をイオン交換樹脂で処理し触媒を除いた後、該有
機溶媒を除去乾燥することにより、分子量10,000以上の
難燃剤を得ることを特徴とする高分子量型難燃剤の製造
方法。1. A heating reaction between a halogenated dihydroxy compound and a halogenated diglycidyl ether compound in an organic solvent containing no water in the presence of a catalyst.
A method for producing a high molecular weight flame retardant, comprising treating the reaction solution with an ion exchange resin to remove the catalyst, removing the organic solvent, and drying to obtain a flame retardant having a molecular weight of 10,000 or more.
炭素数１〜４のアルキリデン基、アルキレン基または−
SO2−基を示す。）で表される特許請求の範囲第１項記
載の高分子量型難燃剤の製造方法。2. The method according to claim 1, wherein the halogenated dihydroxy compound has a general formula (Where X is a halogen atom, p and q are integers of 1 to 4, R 1 is an alkylidene group, alkylene group or alkylene group having 1 to 4 carbon atoms.
Represents an SO 2 — group. 2. The method for producing a high molecular weight type flame retardant according to claim 1, wherein the method comprises:
が、一般式 （式中Ｙはハロゲン原子、ｒ、ｓは１〜４の整数、ｎは
０〜15の整数、R2は炭素数１〜４のアルキリデン基、ア
ルキレン基または−SO2−基を示す。）で表される特許
請求の範囲第１項記載の高分子量型難燃剤の製造方法。3. A halogenated diglycidyl ether compound represented by the general formula: (In the formula, Y is a halogen atom, r and s are integers of 1 to 4, n is an integer of 0 to 15, and R 2 represents an alkylidene group, an alkylene group or a —SO 2 — group having 1 to 4 carbon atoms.) The method for producing a high molecular weight flame retardant according to claim 1, wherein the flame retardant is represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63009104A JP2742582B2 (en) | 1988-01-18 | 1988-01-18 | Method for producing high molecular weight flame retardant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63009104A JP2742582B2 (en) | 1988-01-18 | 1988-01-18 | Method for producing high molecular weight flame retardant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01185323A JPH01185323A (en) | 1989-07-24 |
| JP2742582B2 true JP2742582B2 (en) | 1998-04-22 |
Family
ID=11711321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63009104A Expired - Lifetime JP2742582B2 (en) | 1988-01-18 | 1988-01-18 | Method for producing high molecular weight flame retardant |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2742582B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4104257A (en) * | 1977-07-27 | 1978-08-01 | The Dow Chemical Company | Process for preparing high molecular weight polyether resins from bisphenols and epoxy resins |
| JPS6143629A (en) * | 1984-08-07 | 1986-03-03 | Mitsui Toatsu Chem Inc | Method for purifying polyether |
-
1988
- 1988-01-18 JP JP63009104A patent/JP2742582B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01185323A (en) | 1989-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1250993A (en) | Polyhydroxyethers from hydroxybiphenyls | |
| EP0019852B1 (en) | Phosphonium phenoxide catalysts, epoxy resin containing same and process for promoting reaction of epoxides with phenols and/or carboxylic acids | |
| EP0278720A2 (en) | Aromatic polymer | |
| US3542828A (en) | Hexafluoroantimonate amine catalysts | |
| AU750750B2 (en) | Process for preparing hydroxy-functionalized polyesters | |
| JP2742582B2 (en) | Method for producing high molecular weight flame retardant | |
| CA2024947A1 (en) | Thermoformable, thermosettable epoxy/polyester reaction products | |
| US3341495A (en) | Ferrocene polymers | |
| JPH10139753A (en) | Quaternary bisphenolate, and its production and application | |
| EP4337713A1 (en) | Process for the preparation of functionalized terpolymers from epoxides and carbon dioxide | |
| US4347351A (en) | Linear polyesters from aromatic dicarboxylic acids and cyclic alkylene carbonates prepared using six-membered aromatic nitrogen-containing heterocyclic groups | |
| JPH01240520A (en) | Production of high-molecular weight type flame retardant | |
| EP0400139B1 (en) | Process for preparing a thermoplastic polymer | |
| JPH03203962A (en) | Production of flame retardant | |
| RU2005737C1 (en) | Process for preparing poly- and copolyether sulfones | |
| JPH0413683A (en) | Cyclophosphazene derivative containing p-vinyl-phenoxy group, its production, its polymer and curable composition thereof | |
| EP0159020B1 (en) | Polyphosphazene process | |
| Takekoshi et al. | Macrocyclic oligoimides. I. Preparation of macrocyclic oligoetherimides via Kricheldorf substitution polymerization | |
| JPS6049621B2 (en) | Method for producing glycol ether of tetrabromobisphenol A | |
| JP2543522B2 (en) | Process for producing alkylene oxide adduct of bisphenol compound | |
| Matsuda | Synthesis of Polymers by Using Divalent Metal Salts of Mono (hydroxyethyl) Phthalate: Metal-Containing Three-Dimensional Polyesters from Metal Salts, Pyromellitic Dianhydride, and Epoxides | |
| JP3849209B2 (en) | Brominated p-cumylphenol and derivatives thereof, production method thereof, and flame retardant resin composition comprising them | |
| JP2691618B2 (en) | Method for producing alkylene oxide adduct of tetrabromobisphenol S | |
| JPS6328469B2 (en) | ||
| JPH01256526A (en) | New aromatic polysulfone and preparation thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |