JP5120682B2 - Alkenyl group-containing polyoxyalkylene derivative and method for producing the same - Google Patents
Alkenyl group-containing polyoxyalkylene derivative and method for producing the same Download PDFInfo
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本発明は、アルケニル基含有ポリオキシアルキレン誘導体及びその製造方法に関する。さらに詳しくは、抗酸化剤が無添加の条件下でも変性材料との反応性が初期ばかりでなく、長期的に良好なアルケニル基含有ポリオキシアルキレン誘導体及びその製造方法に関する。 The present invention relates to an alkenyl group-containing polyoxyalkylene derivative and a method for producing the same. More specifically, the present invention relates to an alkenyl group-containing polyoxyalkylene derivative that is not only reactive at the initial stage even under the condition where no antioxidant is added, but also has a long-term favorable property, and a method for producing the same.
アルケニル基を含有するポリオキシアルキレン誘導体は、二重結合の反応性を利用して他の反応性モノマーとの共重合原料や、反応性オルガノポリシロキサンの変性材等の用途で広く利用されている。また、末端に水酸基を有するアルケニル基含有ポリオキシアルキレン誘導体は、水酸基が他の官能基と反応してゲル化する等の理由により、水酸基をアルキル基もしくはアルケニル基でエーテル置換されたポリオキシアルキレン誘導体も多く使用されている。 Polyoxyalkylene derivatives containing alkenyl groups are widely used as raw materials for copolymerization with other reactive monomers and reactive organopolysiloxane modifiers using the reactivity of double bonds. . In addition, an alkenyl group-containing polyoxyalkylene derivative having a hydroxyl group at the terminal is a polyoxyalkylene derivative in which the hydroxyl group is ether-substituted with an alkyl group or an alkenyl group, for example, because the hydroxyl group reacts with other functional groups to form a gel. Many are also used.
アルケニル基含有ポリオキシアルキレン誘導体は、長期保管すると経時変化によって過酸化物等の不純物が増加し、変性材料としての反応性が低下することは知られている。例えば、製造後３ヶ月が経過したアルケニル基含有ポリオキシアルキレン誘導体とハイドロジェンオルガノポリシロキサンとの反応は完結するが、２年以上経過したアルケニル基含有ポリオキシアルキレン誘導体を使用すると、過酸化物が増加する影響により反応が完結しない。そのため過酸化物を低減する手段としてアスコルビン酸及びその塩、あるいはクエン酸及びその塩を０．０１〜２０重量％で加熱処理する方法（例えば特許文献１）が提案されている。しかし、この方法は工程が増えて煩雑になり、効率的ではない。
また、反応性の向上を目的に抗酸化剤の添加が知られている。例えば、酸化防止剤を添加後、吸着処理を行う方法（例えば特許文献２）が提案されている。しかし、ヒドロシリル化前のポリエーテルの処理方法として添加剤を添加する方法は変性シリコーンの純度を低下させ、且つ除去が困難であり、また使用用途によっては添加剤の混入が好ましくないことがある。
本発明は、抗酸化剤が無添加の条件下でも変性材料との反応性が初期ばかりでなく、長期的に良好なアルケニル基含有ポリオキシアルキレン誘導体の製造方法を提供することを目的とする。 An object of the present invention is to provide a method for producing an alkenyl group-containing polyoxyalkylene derivative which is not only initially reactive with a modified material even under the condition where an antioxidant is not added, but also has a long-term favorable condition.
上記の課題を解決すべく鋭意検討を重ねた結果、特定の条件を満たすアルケニル基含有ポリオキシアルキレン誘導体は、抗酸化剤が無添加の条件下でも変性材料との反応性が初期ばかりでなく、長期的に良好であることを見いだし、この知見に基づいて本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the alkenyl group-containing polyoxyalkylene derivative satisfying specific conditions is not only initially reactive with the modified material even under the condition that no antioxidant is added, Based on this finding, the present invention has been completed.
すなわち、本発明は、原料アルコールにアルキレンオキシドを開環重合させて、末端水酸基を有するポリオキシアルキレン誘導体を含む中間生成物を得るアルキレンオキシド付加反応工程、この中間生成物に有機ハロゲン化物を反応させて、末端エーテル基を有するポリオキシアルキレン誘導体を含むエーテル化反応生成物を得るエーテル化反応工程、およびこのエーテル化反応生成物を精製して精製物を得る精製工程によって得られ、下記条件を満たす、下記式（１）で表されるアルケニル基含有ポリオキシアルキレン誘導体の精製物である。
Ａ．過酸化物価 １０．０meq／kg以下
Ｂ．ＣＰＲ ５．０以下
Ｃ．Ｎａ分＋Ｋ分 ３．０ppm以下
Ｄ．水分 ０．２%以下
Ｅ．燐分 ５〜７０ｐｐｍ
Ｆ．前記中間生成物の水酸基価および前記精製物の水酸基価より算出する前記末端水酸基のエーテル化反応率が９３％以上
Ｒ１Ｏ（ＡＯ）ｎＲ２ （１）
（式中、Ｒ１は、末端に二重結合を有する炭素数３〜５のアルケニル基であり、ＡＯは、炭素数２〜４のオキシアルキレン基であり、ｎ＝１〜１５０、Ｒ２は、炭素数１〜２４のアルキル基もしくはアルケニル基である。）
That is, the present invention provides an alkylene oxide addition reaction step in which an alkylene oxide is ring-opened polymerized to a raw material alcohol to obtain an intermediate product containing a polyoxyalkylene derivative having a terminal hydroxyl group, and an organic halide is reacted with the intermediate product. Obtained by an etherification reaction step for obtaining an etherification reaction product containing a polyoxyalkylene derivative having a terminal ether group, and a purification step for purifying the etherification reaction product to obtain a purified product. These are purified products of alkenyl group-containing polyoxyalkylene derivatives represented by the following formula (1).
A. Peroxide value: 10.0 meq / kg or less CPR 5.0 or less Na content + K content 3.0 ppm or less Moisture 0.2% or less Phosphorus content 5-70ppm
F. The etherification reaction rate of the terminal hydroxyl group calculated from the hydroxyl value of the intermediate product and the hydroxyl value of the purified product is 93% or more.
R 1 O (AO) nR 2 (1)
(In the formula, R 1 is an alkenyl group having 3 to 5 carbon atoms having a double bond at the terminal, AO is an oxyalkylene group having 2 to 4 carbon atoms, n = 1 to 150, and R 2 is And an alkyl group or an alkenyl group having 1 to 24 carbon atoms.)
さらに、下記に記す工程からなることを特徴とする式（１）で示されるアルケニル基含有ポリオキシアルキレン誘導体の製造方法である。
１． 原料ポリエーテルに対し、アルカリ触媒及び有機ハロゲン化物を加え、７０〜１３０℃の間でエーテル化するエーテル化工程
２． 水を加えてアルカリを分層除去するアルカリ除去工程
３． 中和剤を用いてｐＨを５．０〜７．０の間に調整する中和工程
４． 不活性ガス雰囲気下、温度７０〜１００℃の間で脱水する脱水工程
５． 不活性ガス雰囲気下、温度７０〜９０℃の間で吸着剤処理を行う吸着処理工程
６． 濾過により中和塩を除去する濾過工程
７． 燐酸を２０〜２００ｐｐｍ量添加する燐酸添加工程
Ｒ１Ｏ（ＡＯ）ｎＲ２ （１）
（式中、Ｒ１は、末端に二重結合を有する炭素数３〜５のアルケニル基であり、ＡＯは、炭素数２〜４のオキシアルキレン基であり、ｎ＝１〜１５０、Ｒ２は、炭素数１〜２４のアルキル基もしくはアルケニル基である。）
Furthermore, it is the manufacturing method of the alkenyl-group containing polyoxyalkylene derivative shown by Formula (1) characterized by including the process described below.
1. 1. Etherification step in which an alkali catalyst and an organic halide are added to the raw material polyether, and etherified at 70 to 130 ° C. 2. Alkali removal step in which water is added to separate the alkali layers. 3. Neutralization step of adjusting pH between 5.0 and 7.0 using a neutralizer. 4. Dehydration step of dehydrating at a temperature of 70 to 100 ° C. in an inert gas atmosphere 5. Adsorption treatment process in which an adsorbent treatment is performed at a temperature of 70 to 90 ° C. in an inert gas atmosphere. 6. Filtration step to remove neutralized salt by filtration Phosphoric acid addition step of adding phosphoric acid in an amount of 20 to 200 ppm R 1 O (AO) nR 2 (1)
(In the formula, R 1 is an alkenyl group having 3 to 5 carbon atoms having a double bond at the terminal, AO is an oxyalkylene group having 2 to 4 carbon atoms, n = 1 to 150, and R 2 is And an alkyl group or an alkenyl group having 1 to 24 carbon atoms.)
本発明のアルケニル基含有ポリオキシアルキレン誘導体及びその製造方法は、特定の条件を用いることにより、抗酸化剤が無添加の条件下でも変性材料との反応性が初期ばかりでなく、長期的に良好な性能を有することができる。したがって、他の反応性モノマーとの共重合原料や、反応性オルガノポリシロキサンの変性材等の用途として好適に使用することができる。特に、Ｆ．エーテル化反応前後の水酸基価より算出する反応率が９３％以上の誘導体であって、Ａ．過酸化物価１０．０meq／kg以下、Ｂ．ＣＰＲ ５．０以下、Ｄ．水分 ０．２%以下という前提の下に、Ｃ．Ｎａ分＋Ｋ分を３．０ppm以下に抑制しつつ、かつＥ．燐分を５〜７０ｐｐｍ添加することによって、抗酸化剤が無添加の条件下でも変性材料との反応性が長期的に良好となる。 The alkenyl group-containing polyoxyalkylene derivative and the method for producing the same of the present invention have good long-term reactivity not only in the initial stage, but also in the long term by using specific conditions, even when no antioxidant is added. Performance. Accordingly, it can be suitably used as a raw material for copolymerization with other reactive monomers, a modified material for reactive organopolysiloxane, and the like. In particular, F.A. A derivative having a reaction rate calculated from the hydroxyl value before and after the etherification reaction of 93% or more, Peroxide value of 10.0 meq / kg or less, B.I. CPR 5.0 or less, D.I. Under the assumption that moisture is 0.2% or less, C.I. While suppressing Na content + K content to 3.0 ppm or less, By adding 5 to 70 ppm of phosphorus, the reactivity with the modified material is improved in the long term even under the condition where no antioxidant is added.
また、本発明の製造方法によれば、アルカリ除去のための濾過工程後に燐酸添加工程を設けることによって、適当な量の燐分を誘導体中に含有させ、これによって、抗酸化剤が無添加の条件下でも変性材料との反応性が初期ばかりでなく、長期的に良好な性能をもたらすことができる。 In addition, according to the production method of the present invention, a phosphoric acid addition step is provided after the filtration step for alkali removal, so that an appropriate amount of phosphorus content is contained in the derivative, whereby no antioxidant is added. Even under conditions, the reactivity with the modified material is not only in the initial stage, but can provide good performance in the long term.
式（１）において、Ｒ１は末端に二重結合を有する炭素数３〜５のアルケニル基であり、例えば、アリル基、３−ブテニル基、メタリル基、２−メチル−３−ブテニル基、３−メチル−３−ブテニル基、１，１，−ジメチル−２−プロペニル基、４−ペンテニル基などのアルケニル基が挙げられ、好ましくはアリル基である。 In the formula (1), R 1 is an alkenyl group having 3 to 5 carbon atoms having a double bond at the terminal, for example, an allyl group, 3-butenyl group, methallyl group, 2-methyl-3-butenyl group, 3 Examples include alkenyl groups such as -methyl-3-butenyl group, 1,1, -dimethyl-2-propenyl group, and 4-pentenyl group, with allyl group being preferred.
ＡＯは炭素数２〜４のオキシアルキレン基を表し、オキシエチレン基、オキシプロピレン基、オキシブチレン基、オキシトリメチレン基、オキシテトラメチレン基等が挙げられ、好ましくはオキシエチレン基、オキシプロピレン基である。ＡＯは１種または２種以上でもよく、ブロック状に結合していても良く、ランダム状に結合しても良い。ｎはオキシアルキレン基の平均付加モル数を表し、１〜１５０であり、好ましくは３〜１００、より好ましくは５〜７０である。 AO represents an oxyalkylene group having 2 to 4 carbon atoms, and examples thereof include an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxytrimethylene group, and an oxytetramethylene group, preferably an oxyethylene group and an oxypropylene group. is there. AO may be one kind or two or more kinds, may be bound in a block shape, or may be bound in a random shape. n represents the average addition mole number of an oxyalkylene group, and is 1-150, Preferably it is 3-100, More preferably, it is 5-70.
Ｒ２は炭素数１〜２４のアルキル基もしくはアルケニル基であり、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基、イソペンチル基、ヘキシル基、イソヘプチル基、２−エチルヘキシル基、オクチル基、イソノニル基、デシル基、ドデシル基、イソトリデシル基、テトラデシル基、ヘキサデシル基、イソセチル基、オクタデシル基、イソステアリル基、ドコシル基などのアルキル基、アリル基、３−ブテニル基、メタリル基、２−メチル−３−ブテニル基、３−メチル−３−ブテニル基、１，１，−ジメチル−２−プロペニル基、４−ペンテニル基、オレイル基などのアルケニル基が挙げられ、好ましくはメチル基、ブチル基、アリル基であり、より好ましくはメチル基、ブチル基である。 R 2 is an alkyl group or alkenyl group having 1 to 24 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, hexyl group. Alkyl groups such as isoheptyl group, 2-ethylhexyl group, octyl group, isononyl group, decyl group, dodecyl group, isotridecyl group, tetradecyl group, hexadecyl group, isocetyl group, octadecyl group, isostearyl group, docosyl group, allyl group, Alkenyl groups such as 3-butenyl group, methallyl group, 2-methyl-3-butenyl group, 3-methyl-3-butenyl group, 1,1, -dimethyl-2-propenyl group, 4-pentenyl group and oleyl group Preferably a methyl group, a butyl group, an allyl group, more preferably a methyl group, It is a butyl group.
式（１）で表されるアルケニル基含有ポリオキシアルキレン誘導体は、次に記す物性値を全て満たすのが好ましい。 The alkenyl group-containing polyoxyalkylene derivative represented by the formula (1) preferably satisfies all the following physical property values.
（Ａ．過酸化物価 １０．０meq／kg以下）
過酸化物価とは誘導体１ｋｇ中に含まれる過酸化物をミリ当量で表したものであるが、過酸化物価は１０．０meq／kg以下であり、更に好ましくは５．０meq／kg以下である。過酸化物価が１０．０meq／kgを超えると、アルケニル基含有ポリオキシアルキレン誘導体とハイドロジェンジメチルポリシロキサン等の変性材との反応において、過酸化物の存在が反応を遅延し反応性を低下させるため、好ましくない。
(A. Peroxide value 10.0 meq / kg or less)
The peroxide value is expressed in milliequivalents of the peroxide contained in 1 kg of the derivative, and the peroxide value is 10.0 meq / kg or less, more preferably 5.0 meq / kg or less. When the peroxide value exceeds 10.0 meq / kg, in the reaction of the alkenyl group-containing polyoxyalkylene derivative with a modifier such as hydrogen dimethylpolysiloxane, the presence of the peroxide delays the reaction and lowers the reactivity. Therefore, it is not preferable.
（Ｂ．ＣＰＲ ５．０以下）
ＣＰＲとは、JIS K 1557 ポリウレタン用ポリエーテル試験方法 6.8に記載のある、Controlled
Polymerization Rate の略称で、誘導体中に存在する微量の塩基性物質の量を表示する方法である。具体的には、試料３０ｇを中和するのに要するＮ／１００塩酸の使用量（ｍｌ）を１０倍した数値を言う。ＣＰＲは５．０以下、好ましくは３．０以下である。ＣＰＲが５．０を超えると塩基性物質の影響によりハイドロジェンジメチルポリシロキサン等の変性材同士の脱水素による縮合が起こり、目的とする化合物の純度が低下するため、好ましくない。
(B. CPR 5.0 or less)
CPR means Controlled as described in JIS K 1557 Polyurethane Testing Method for Polyurethane 6.8
Abbreviation for Polymerization Rate, which is a method for displaying the amount of trace amounts of basic substances present in derivatives. Specifically, it is a value obtained by multiplying the amount of use (ml) of N / 100 hydrochloric acid required to neutralize 30 g of the sample by 10 times. CPR is 5.0 or less, preferably 3.0 or less. If the CPR exceeds 5.0, condensation due to dehydrogenation between the modifiers such as hydrogen dimethylpolysiloxane occurs due to the influence of the basic substance, which is not preferable.
（Ｃ．Ｎａ分＋Ｋ分 ３．０ppm以下）
誘導体中に含まれるＮａ分＋Ｋ分は３．０ppm以下、好ましくは２．０ppmである。Ｎａ分＋Ｋ分が３．０ppmを超えるとアルケニル基含有ポリオキシアルキレン誘導体とハイドロジェンジメチルポリシロキサン等の変性材との反応において、反応性が低下する恐れがあるため、好ましくない。
(C. Na content + K content 3.0ppm or less)
The Na content + K content contained in the derivative is 3.0 ppm or less, preferably 2.0 ppm. If the Na content + K content exceeds 3.0 ppm, the reactivity between the alkenyl group-containing polyoxyalkylene derivative and a modifier such as hydrogen dimethylpolysiloxane may be lowered, which is not preferable.
（Ｄ．水分 ０．２%以下）
水分は０．２％以下、好ましくは０．１％以下である。水分が０．２％を超えるとハイドロジェンジメチルポリシロキサンとの反応性が低下する恐れが生じるため、好ましくない。
(D. Moisture 0.2% or less)
The moisture is 0.2% or less, preferably 0.1% or less. If the water content exceeds 0.2%, the reactivity with hydrogen dimethylpolysiloxane may decrease, which is not preferable.
（Ｅ．燐分 ５〜７０ｐｐｍ）
燐分は５〜７０ｐｐｍ、好ましくは５〜３０ｐｐｍである。燐分が７０ｐｐｍを超えると、酸性度が高くなる。本発明においては、燐分を５ｐｐｍ以上とすることによって、長期的に良好な反応性を有することができる。
(E. Phosphorus content 5 to 70 ppm)
The phosphorus content is 5 to 70 ppm, preferably 5 to 30 ppm. When phosphorus content exceeds 70 ppm, acidity will become high. In the present invention, by setting the phosphorus content to 5 ppm or more, good reactivity can be obtained in the long term.
（Ｆ．中間生成物の水酸基価および精製物の水酸基価より算出する末端水酸基のエーテル化反応率が９３％以上）
前記反応率が９３％以上、好ましくは９５％以上である。反応率が９０％に満たないと水酸基が他の官能基と反応して副生物が増加し、得られる化合物の純度が低くなるため、好ましくない。
(F. Etherification reaction rate of terminal hydroxyl group calculated from hydroxyl value of intermediate product and hydroxyl value of purified product is 93% or more)
The reaction rate is 93% or more, preferably 95% or more. If the reaction rate is less than 90%, the hydroxyl group reacts with other functional groups to increase by-products, and the purity of the resulting compound decreases, which is not preferable.
式（１）で表されるアルケニル基含有ポリオキシアルキレン誘導体は、アルキレンオキシド付加反応、エーテル化反応、精製工程の各工程を経て得られるが、具体的には下記に記す製造法により製造することができる。 The alkenyl group-containing polyoxyalkylene derivative represented by the formula (1) can be obtained through each step of an alkylene oxide addition reaction, an etherification reaction, and a purification step. Specifically, it should be produced by the production method described below. Can do.
（１．アルキレンオキシド付加反応工程）
アルキレンオキシド付加反応は、原料アルコールと触媒の存在下にアルキレンオキシドを少量ずつ仕込みながら開環重合させて、末端水酸基を有するポリオキシアルキレン誘導体（原料ポリエーテル）とし、中間生成物を得る工程である。
(1. Alkylene oxide addition reaction step)
The alkylene oxide addition reaction is a step of obtaining an intermediate product by ring-opening polymerization while charging alkylene oxide in small amounts in the presence of a raw material alcohol and a catalyst to obtain a polyoxyalkylene derivative having a terminal hydroxyl group (raw material polyether). .
使用する原料アルコールは、メタノール、エタノール、プロパノール、ブタノール、２−エチルヘキサノール、ラウリルアルコール、ステアリルアルコール、アリルアルコール、メタリルアルコール、オレイルアルコール等の炭素数１−２４の飽和あるいは不飽和アルコール；エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，４−ブタンジオール等のジオール化合物が挙げられる。
触媒は、金属ナトリウムや金属カリウム等のアルカリ金属；水酸化カリウム、水酸化ナトリウム、水酸化リチウム、水酸化セシウム等のアルカリ金属の水酸化物；ナトリウムメトシキド、カリウム−ｔ−ブトキシド等のアルカリ金属のアルコキシド；三フッ化硼素およびそれらのアルキルエーテル錯体や四塩化錫等のルイス酸；固体酸触媒；酢酸カリウム、プロピオン酸カリウム等のカルボン酸から由来するアルカリ金属塩等が挙げられる。
アルキレンオキシドは、炭素数２〜４のアルキレンオキシドを用いることができ、エチレンオキシド、プロピレンオキシド、１，２−ブチレンオキシド、イソブチレンオキシド、テトラヒドロフラン等が挙げられる。
アルキレンオキシド付加反応の条件は、例えば、アルカリ触媒を用いて行う場合、触媒量は原料アルコールとアルキレンオキシドの合計量に対して、０．０１重量％〜２重量％、反応温度を６０〜１６０℃、好ましくは８０〜１４０℃の範囲でアルキレンオキシドの開環重合反応を行うのが好ましい。また、酸触媒を用いて行う場合、触媒量は原料アルコールとアルキレンオキシドの合計量に対して０．１〜５重量％、反応温度を０〜１００℃、好ましくは２０〜７０℃の範囲でアルキレンオキシドの開環重合反応を行うのが好ましい。
The starting alcohol used is a saturated or unsaturated alcohol having 1 to 24 carbon atoms such as methanol, ethanol, propanol, butanol, 2-ethylhexanol, lauryl alcohol, stearyl alcohol, allyl alcohol, methallyl alcohol, oleyl alcohol, etc .; ethylene glycol And diol compounds such as diethylene glycol, propylene glycol, dipropylene glycol, and 1,4-butanediol.
Catalysts are alkali metals such as metallic sodium and metallic potassium; alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide and cesium hydroxide; alkali metals such as sodium methoxide and potassium t-butoxide Alkoxides of the above; Lewis acids such as boron trifluoride and their alkyl ether complexes and tin tetrachloride; solid acid catalysts; alkali metal salts derived from carboxylic acids such as potassium acetate and potassium propionate.
As the alkylene oxide, an alkylene oxide having 2 to 4 carbon atoms can be used, and examples thereof include ethylene oxide, propylene oxide, 1,2-butylene oxide, isobutylene oxide, and tetrahydrofuran.
The conditions for the alkylene oxide addition reaction are, for example, when an alkali catalyst is used, the catalyst amount is 0.01% to 2% by weight with respect to the total amount of the raw material alcohol and the alkylene oxide, and the reaction temperature is 60 to 160 ° C. Preferably, the alkylene oxide is subjected to a ring-opening polymerization reaction in the range of 80 to 140 ° C. When the acid catalyst is used, the catalyst amount is 0.1 to 5% by weight with respect to the total amount of the raw material alcohol and the alkylene oxide, and the reaction temperature is 0 to 100 ° C., preferably 20 to 70 ° C. It is preferable to perform a ring-opening polymerization reaction of the oxide.
（２．エーテル化工程）
エーテル化反応は、アルキレンオキシド付加反応工程で得られたポリオキシアルキレン誘導体（原料ポリエーテル）の中間生成物に、アルカリ触媒と有機ハロゲン化物を仕込み、特定条件下に反応させて末端エーテル基を有するポリオキシアルキレン誘導体を生成させ、エーテル化反応生成物を得る工程である。
アルカリ触媒は、水酸化カリウム、水酸化ナトリウム、水酸化リチウム、水酸化セシウム等のアルカリ金属の水酸化物が挙げられ、有機ハロゲン化物は、塩化メチル、塩化ブチル、塩化ｓ−ブチル、塩化イソブチル、塩化ペンチル、２−塩化ペンチル、塩化イソペンチル、塩化ｔ−ペンチル、塩化ネオペンチル、塩化ヘキシル、塩化ヘプチル、塩化オクチル、塩化ノニル、塩化デシル、塩化アリル、塩化メタリル、臭化メチル、臭化エチル、臭化プロピル、臭化イソプロピル、臭化ブチル、臭化イソブチル、臭化ペンチル、臭化イソペンチル、臭化ヘキシル、臭化アリル、ヨウ化プロピル、ヨウ化イソメロピル、ヨウ化ブチル、ヨウ化イソブチル、ヨウ化ペンチル、ヨウ化イソペンチル、ヨウ化アリル等が挙げられる。
エーテル化反応条件は、例えば、原料ポリエーテルの水酸基１当量に対して、アルカリ触媒を１．０〜５．０当量、好ましくは１．３〜３．５当量、有機ハロゲン化物を１．０〜２．０当量、好ましくは１．１〜１．６当量の範囲で添加し、反応温度は７０〜１３０℃、好ましくは８０〜１２０℃の間で反応を行うのが好ましい。反応温度が７０℃に満たないと反応が進行しないことがあり、１３０℃を超えるとアルケニル基が内部転移しやすくなるため、好ましくない。また、アルキレンオキシド付加反応工程で得られたポリオキシアルキレン誘導体が末端にアルケニル基を有しない場合は、この反応に用いる有機ハロゲン化物は末端にアルケニル基を有するものを選択する必要がある。
(2. Etherification step)
In the etherification reaction, an intermediate product of the polyoxyalkylene derivative (raw polyether) obtained in the alkylene oxide addition reaction step is charged with an alkali catalyst and an organic halide and reacted under specific conditions to have a terminal ether group. This is a step of producing a polyoxyalkylene derivative to obtain an etherification reaction product .
Examples of the alkali catalyst include hydroxides of alkali metals such as potassium hydroxide, sodium hydroxide, lithium hydroxide and cesium hydroxide, and organic halides include methyl chloride, butyl chloride, s-butyl chloride, isobutyl chloride, Pentyl chloride, 2-pentyl chloride, isopentyl chloride, t-pentyl chloride, neopentyl chloride, hexyl chloride, heptyl chloride, octyl chloride, nonyl chloride, decyl chloride, allyl chloride, methallyl chloride, methyl bromide, ethyl bromide, bromide Propyl, isopropyl bromide, butyl bromide, isobutyl bromide, pentyl bromide, isopentyl bromide, hexyl bromide, allyl bromide, propyl iodide, isopropyl iodide, butyl iodide, isobutyl iodide, pentyl iodide, Examples include isopentyl iodide and allyl iodide.
The etherification reaction conditions are, for example, 1.0 to 5.0 equivalents, preferably 1.3 to 3.5 equivalents of an alkali catalyst, and 1.0 to 3.5 equivalents of an organic halide with respect to 1 equivalent of a hydroxyl group of a raw material polyether. It is preferably added in an amount of 2.0 equivalents, preferably 1.1 to 1.6 equivalents, and the reaction temperature is 70 to 130 ° C, preferably 80 to 120 ° C. If the reaction temperature is less than 70 ° C., the reaction may not proceed. If it exceeds 130 ° C., the alkenyl group tends to undergo internal transition, which is not preferable. Moreover, when the polyoxyalkylene derivative obtained in the alkylene oxide addition reaction step does not have an alkenyl group at the terminal, it is necessary to select an organic halide having an alkenyl group at the terminal as the organic halide used in this reaction.
（３．アルカリ除去工程）
エーテル化反応後、残存アルカリ触媒及び反応により生成した金属ハロゲン化物の除去を効率的に行うため、水を加えて塩析を行う。水洗の方法としては水を加えて撹拌の上静置させる方法と、水を下部より仕込み撹拌せずに静置させる方法があり、誘導体の構造及び分子量によって選択する。分層後、下層のアルカリと金属ハロゲン化物を含む水層の除去を行う。
(3. Alkali removal step)
After the etherification reaction, salting out is performed by adding water in order to efficiently remove the residual alkali catalyst and the metal halide produced by the reaction. Methods for washing with water include a method in which water is added and allowed to stand after stirring, and a method in which water is charged from the lower portion and left to stand without stirring, and is selected according to the structure and molecular weight of the derivative. After the layer separation, the lower layer aqueous layer containing alkali and metal halide is removed.
（４．中和工程）
水洗工程終了後、残存アルカリ触媒を酸で中和させる。中和剤としては、硫酸、塩酸、燐酸、酢酸、ｐ−トルエンスルホン酸などの酸、好ましくは燐酸、酢酸、塩酸を用いて公知の方法で中和を行うことができる。中和工程の効率を向上させる目的で必要により水を添加することもできる。中和剤を添加後撹拌し、ｐＨを５．０〜７．０の間に調整させる。
(4. Neutralization process)
After completion of the water washing step, the remaining alkali catalyst is neutralized with an acid. As the neutralizing agent, neutralization can be performed by a known method using acids such as sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, p-toluenesulfonic acid, preferably phosphoric acid, acetic acid and hydrochloric acid. Water can be added as necessary for the purpose of improving the efficiency of the neutralization step. The neutralizing agent is added and stirred to adjust the pH between 5.0 and 7.0.
（５．脱水工程）
中和工程終了後は脱水を行う。脱水は不活性ガスを吹き込みながら常圧で脱水する方法や、真空条件下で脱水する方法など、公知の方法を用いることができるが、脱水温度７０〜１００℃、好ましくは８０〜９０℃の間で不活性ガスを吹き込みながら水を留出させて塩を結晶化し、水の留出後は系内を真空とし引き続き不活性ガスを吹き込みながら３０分〜５時間、好ましくは１〜３時間脱水を行う。また、脱水中は攪拌羽根を用いて混合しながら行っても良い。
(5. Dehydration process)
Dehydration is performed after the neutralization step. For the dehydration, a known method such as a method of dehydrating at normal pressure while blowing an inert gas or a method of dehydrating under a vacuum condition can be used, but a dehydration temperature of 70 to 100 ° C., preferably between 80 to 90 ° C. Then, water is distilled while blowing an inert gas to crystallize the salt, and after distilling the water, the system is evacuated and then the inert gas is blown for 30 minutes to 5 hours, preferably 1 to 3 hours. Do. Further, during dehydration, mixing may be performed using a stirring blade.
（６．吸着処理工程）
脱水工程終了後は吸着剤を添加して吸着処理を行う。吸着処理は不活性ガスを吹き込みながら常圧で処理する方法や、加圧あるいは真空条件下で処理する方法など、公知の方法を用いて行うことができるが、脱水温度７０〜９０℃、好ましくは８０〜９０℃の間で不活性ガスを吹き込みながら２０分〜３時間、好ましくは３０分〜２時間吸着処理を行うのがより好ましい。また、吸着処理中は攪拌羽根を用いて混合しながら行っても良い。吸着剤としては例えば合成吸着剤、活性白土、合成ゼオライト、活性炭、活性アルミナ、シリガゲル、マグネシアなどが挙げられ、中でも合成吸着剤が好ましく、市販の吸着剤としては、キョーワード１００、キョーワード２００、キョーワード３００、キョーワード４００、キョーワード５００、キョーワード６００、キョーワード７００、キョーワード１０００、キョーワード２０００（協和化学工業（株）製）、トミックスＡＤ１００、トミックスＡＤ２００、トミックスＡＤ３００、トミックスＡＤ４００、トミックスＡＤ５００、トミックスＡＤ６００、トミックスＡＤ７００、トミックスＡＤ８００（冨田製薬（株）製）などを例示することができる。
(6. Adsorption treatment process)
After the dehydration process is completed, an adsorbent is added to perform an adsorption process. The adsorption treatment can be performed using a known method such as a method of treating at normal pressure while blowing an inert gas, or a method of treating under pressure or vacuum conditions, but a dehydration temperature of 70 to 90 ° C., preferably It is more preferable to perform the adsorption treatment for 20 minutes to 3 hours, preferably 30 minutes to 2 hours while blowing an inert gas between 80 to 90 ° C. Moreover, you may carry out during an adsorption process, mixing using a stirring blade. Examples of the adsorbent include synthetic adsorbent, activated clay, synthetic zeolite, activated carbon, activated alumina, silica gel, and magnesia. Among them, synthetic adsorbent is preferable, and commercially available adsorbents include Kyoward 100, Kyoward 200, KYOWARD 300, KYODWARD 400, KYODWARD 500, KYOWARD 600, KYODWARD 700, KYOWARD 1000, KYOWARD 2000 (manufactured by Kyowa Chemical Industry Co., Ltd.), TOMICS AD100, TOMIX AD200, TOMICS AD300, TOMICS AD400, TOMICS Examples include AD500, Tomix AD600, Tomix AD700, Tomix AD800 (manufactured by Iwata Pharmaceutical Co., Ltd.), and the like.
吸着剤の添加量は、主原料仕込み量１００重量部に対して０．５〜２．０重量部の範囲内、さらに好ましくは０．３〜１重量部で添加するのが好ましい。ここで、主原料仕込み量とは、原料アルコール、アルキレンオキシドおよびハロゲン化物の仕込み量の合計量を指す。添加量が０．２重量部未満であると微量金属分の吸着除去が低下する恐れがあり、２．０重量部を超えると吸着能が向上しない上に濾過効率が低下する恐れがある。また、本工程は複数の吸着剤を用いて処理を行うこともできる。 The amount of adsorbent added is preferably 0.5 to 2.0 parts by weight, more preferably 0.3 to 1 part by weight, with respect to 100 parts by weight of the main raw material charged. Here, the amount of main raw material charged refers to the total amount of raw material alcohol, alkylene oxide and halide charged. If the amount added is less than 0.2 parts by weight, the adsorption removal of trace metals may be reduced, and if it exceeds 2.0 parts by weight, the adsorption ability may not be improved and the filtration efficiency may be reduced. Moreover, this process can also process using several adsorption agent.
（７．濾過工程）
吸着処理工程終了後は濾過を行う。濾紙及び濾過助剤を用いて塩及び吸着剤を濾別する。濾過は加圧もしくは減圧で行うのが好ましく、また、外観が透明になるまで繰り返し行っても良い。
(7. Filtration process)
Filtration is performed after completion of the adsorption process. The salt and adsorbent are filtered off using filter paper and filter aid. Filtration is preferably performed under pressure or reduced pressure, and may be repeated until the appearance becomes transparent.
（８．燐酸添加工程）
濾過工程終了後は燐酸を添加して目的のアルケニル基含有ポリオキシアルキレン誘導体を得る。燐酸は８５％燐酸か、あるいは水で希釈したものを用いて添加し、添加量は燐酸換算で２０〜２００ｐｐｍ、より好ましくは３０〜１００ｐｐｍの間で添加する。燐酸の添加量が２０ｐｐｍ未満であると長期的な反応性向上に効果が無く、２００ｐｐｍを超えると酸性度が高くなり好ましくない。また、製造後の保管方法については酸化による反応性低下の影響を避けるため、気密容器に密充填し、不活性ガスで置換の上保管することが好ましい。
(8. Phosphoric acid addition step)
After completion of the filtration step, phosphoric acid is added to obtain the desired alkenyl group-containing polyoxyalkylene derivative. Phosphoric acid is added using 85% phosphoric acid or one diluted with water, and the addition amount is 20 to 200 ppm, more preferably 30 to 100 ppm in terms of phosphoric acid. If the addition amount of phosphoric acid is less than 20 ppm, there is no effect in improving the long-term reactivity, and if it exceeds 200 ppm, the acidity increases, which is not preferable. Moreover, about the storage method after manufacture, in order to avoid the influence of the reactivity fall by oxidation, it is preferable to close-pack with an airtight container and to store after replacing with an inert gas.
以下に、実施例を挙げて本発明をさらに詳細に説明する。なお、得られた化合物の分析は下記に示す方法で行った。 Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the analysis of the obtained compound was performed by the method shown below.
過酸化物価 ：２００ｍｌ共栓付き三角フラスコに試料約１ｇを秤量し、クロロホルム１０ｍｌを加え完全に溶解させる。次に酢酸１５ｍｌを加え共栓し、良く振り混ぜた後フラスコ全体を黒色ビニール袋で遮光し、ヨウ化カリウムのメタノール飽和溶液２ｍｌを加え、常温で３０分間放置する。イオン交換水３０ｍｌを加え、遊離ヨウ素を水層に移行させ、水層が無色になるまでＮ／１００チオ硫酸ナトリウム標準液で滴定する。
ＣＰＲ ：試料約３０ｇを２００ｍｌビーカーに秤量し、これにメチルアルコール１００ｍｌを加えてよく溶かし、Ｎ／１００塩酸で電位差滴定を行う。
Peroxide value: About 1 g of a sample is weighed into a 200 ml Erlenmeyer flask with a stopper, and 10 ml of chloroform is added and completely dissolved. Next, 15 ml of acetic acid is added and stoppered. After shaking well, the whole flask is shielded from light with a black plastic bag, 2 ml of a saturated methanol solution of potassium iodide is added, and the mixture is allowed to stand at room temperature for 30 minutes. Add 30 ml of ion-exchanged water, transfer free iodine to the aqueous layer, and titrate with N / 100 sodium thiosulfate standard solution until the aqueous layer is colorless.
CPR: Approximately 30 g of a sample is weighed into a 200 ml beaker, 100 ml of methyl alcohol is added and dissolved well, and potentiometric titration is performed with N / 100 hydrochloric acid.
Ｎａ分及びＫ分 ：規定量の試料を５０ｍｌメスフラスコに秤量し、精製水にてメスアップする。原子吸光分析装置を用いて測定し、標準溶液の検量線から試験液中のＮａ分及びＫ分の含有量を求める。非水溶性試料の場合は試料を白金皿に秤量し、ガスバーナーで完全に燃焼させて灰化させる。灰化物を５０ｍｌメスフラスコに入れ、精製水でメスアップして溶解させる。 Na content and K content: A specified amount of sample is weighed into a 50 ml volumetric flask and diluted with purified water. Measurement is performed using an atomic absorption spectrometer, and the contents of Na and K in the test solution are determined from the calibration curve of the standard solution. In the case of a water-insoluble sample, the sample is weighed in a platinum dish and completely burned with a gas burner to be incinerated. The incinerated product is placed in a 50 ml volumetric flask and dissolved in purified water.
水分 ：試料約３ｇを秤量し、よくかきまぜながらカールフィッシャー試薬で滴定する。
燐分 ：３００ｍｌ共栓付き三角フラスコに試料約２５ｇを秤量し、純水１００ｇを加え９０〜１００℃の定温浴中で時々振り混ぜながら５分間加熱する。次に定温浴から取り出し、６０〜７０℃になるまで放冷する。当初の試料重量になるまで純水を加え、共栓をして良く振り混ぜた後、室温になるまで放置後Ｎｏ．５Ｃの濾紙で試料溶液を濾過する。濾液約１０ｇを５０ｍｌメスフラスコに秤量し、２％モリブデン酸アンモニウム溶液５ｍｌおよび０．２％硫酸ヒドラジン溶液２ｍｌを加え、水で標線を合わせてから良く混合する。沸騰湯浴中に１０分間フラスコを浸けて加熱発色させた後、室温まで冷却する。発色させた試験溶液を吸収セル１０ｍｍにとり、分光光度計により波長８２３．６ｎｍで空試験液を対照液として吸光度を測定し、予め作成しておいた検量線から燐含有量を求める。
Moisture: Weigh about 3 g of sample and titrate with Karl Fischer reagent while stirring well.
Phosphorus content: About 25 g of sample is weighed into a 300 ml conical stoppered flask, 100 g of pure water is added, and heated for 5 minutes with occasional shaking in a 90-100 ° C. constant temperature bath. Next, it is taken out from the constant temperature bath and allowed to cool to 60-70 ° C. Add pure water until the initial sample weight is reached, plug it well, shake well, leave it to room temperature, and then select No. Filter the sample solution with 5C filter paper. About 10 g of the filtrate is weighed into a 50 ml volumetric flask, 5 ml of 2% ammonium molybdate solution and 2 ml of 0.2% hydrazine sulfate solution are added, and the mark is adjusted with water, and then mixed well. Immerse the flask in a boiling water bath for 10 minutes to develop color by heating, and then cool to room temperature. The colored test solution is placed in an absorption cell of 10 mm, the absorbance is measured with a spectrophotometer at a wavelength of 823.6 nm using a blank test solution as a control solution, and the phosphorus content is determined from a calibration curve prepared in advance.
水酸基価 ：規定量の試料と無水フタル酸のピリジン溶液２５ｍｌをエステル化用フラスコに加え、共栓を付け９８℃の定温浴中で時々おだやかに振り動かしながら２時間加熱する。次に定温浴から取り出し、室温になるまで放置したのち、共栓を取りはずしピリジンで洗浄後Ｎ／２水酸化ナトリウム溶液５０ｍｌ、フェノールフタレインのピリジン溶液１０滴を加え、Ｎ／２水酸化ナトリウム溶液で滴定する。 Hydroxyl value: Add a specified amount of sample and 25 ml of a pyridine solution of phthalic anhydride to an esterification flask, attach a stopper, and heat for 2 hours while gently shaking in a constant temperature bath at 98 ° C. Next, after taking out from the constant temperature bath and leaving to room temperature, remove the stopper, wash with pyridine, add 50 ml of N / 2 sodium hydroxide solution and 10 drops of phenolphthalein pyridine solution, and add N / 2 sodium hydroxide solution. Titrate with.
動粘度 ：校正済みキャノン−フェンスケ粘度計に試料を加え、試験温度に保持した恒温槽に入れ試料が試験温度に達するまで静置する。次に粘度計の毛管内の上下の測時標線の間を自然流下するのに要した流出時間を測定し、流出時間に粘度計の粘度計定数を乗じて求める。 Kinematic viscosity: Add the sample to a calibrated Canon-Fenske viscometer, place it in a thermostatic chamber maintained at the test temperature, and leave it until the sample reaches the test temperature. Next, the outflow time required for the natural flow between the upper and lower time measurement lines in the capillary of the viscometer is measured, and the outflow time is obtained by multiplying the viscometer constant of the viscometer.
不飽和度 ：酢酸第二水銀のメチルアルコール溶液２５ｍｌを１００ｍｌ三角フラスコにとり、これに試料約１５ｇを秤量し、よく溶かし室温で３０分間放置する。放置後臭化ナトリウムを加え振り混ぜ、次いでフェノールフタレインのアルコール溶液を加え、Ｎ／１０水酸化カリウムのメチルアルコール溶液で滴定する。 Unsaturation degree: 25 ml of a methyl alcohol solution of mercuric acetate is placed in a 100 ml Erlenmeyer flask, and about 15 g of a sample is weighed into this and dissolved well, and left at room temperature for 30 minutes. After standing, sodium bromide is added and shaken, and then an alcohol solution of phenolphthalein is added and titrated with a methyl alcohol solution of N / 10 potassium hydroxide.
（実施例１：分子量１６００のポリオキシエチレンポリオキシプロピレンアリルメチルエーテルの合成）
アリルアルコール８８．２ｇ（１．５２モル）、および水酸化カリウム４．５ｇ（０．０８モル）を５リットル容オートクレーブに仕込み、系中を窒素で置換した後、撹拌しながら１０５℃まで昇温し、エチレンオキシド１１６８．２ｇ（２６．６モル）及びプロピレンオキシド１５３９．９ｇ（２６．６モル）の混合物を計量槽に計り取り、１０５℃、０．５ＭＰａ（ゲージ圧力）以下の条件でエチレンオキシド及びプロピレンオキシドの混合物を２０時間かけて圧入し、さらに４時間反応を続けた。次に８５℃まで降温し、未反応のエチレンオキシド及びプロピレンオキシドを−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で除去を行った。反応物の一部を抜き取り、中和、脱水及び濾過により精製サンプルを得、分析を行ったところ反応中間生成物の水酸基価は３６．３ＫＯＨｍｇ／ｇ、動粘度（２５℃）は２０４．０ｍｍ２／ｓであった。
(Example 1: Synthesis of polyoxyethylene polyoxypropylene allyl methyl ether having a molecular weight of 1600)
Allyl alcohol 88.2 g (1.52 mol) and potassium hydroxide 4.5 g (0.08 mol) were charged into a 5 liter autoclave and the system was replaced with nitrogen. A mixture of 1168.2 g (26.6 mol) of ethylene oxide and 1539.9 g (26.6 mol) of propylene oxide was weighed into a measuring tank, and ethylene oxide and propylene were subjected to conditions of 105 ° C. and 0.5 MPa (gauge pressure) or less. The oxide mixture was injected over 20 hours and the reaction was continued for an additional 4 hours. Next, the temperature was lowered to 85 ° C., and unreacted ethylene oxide and propylene oxide were removed in nitrogen bubbling at −0.097 MPa (gauge pressure) or less. A part of the reaction product was extracted, a purified sample was obtained by neutralization, dehydration and filtration, and analyzed. As a result, the hydroxyl value of the reaction intermediate product was 36.3 KOHmg / g, and the kinematic viscosity (25 ° C.) was 204.0 mm 2. / S.
５０℃以下まで冷却後、水酸化カリウム２６９．３ｇ（４．８モル）を仕込み、系中を窒素で置換した後−０．０９７ＭＰａ（ゲージ圧力）以下とし、８５℃まで昇温後メチルクロリド１１３．１ｇ（２．２モル）を仕込み、さらに１２５℃まで昇温し４時間メチルエーテル化反応を行った。終了後８５℃まで降温し、未反応のメチルクロリドを−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で除去を行った。次に水１０７７ｇを加えて１０分間撹拌後２時間静置させて分層した水層の除去を行い、希酢酸で中和しｐＨを６．２に調整した。 After cooling to 50 ° C. or lower, 269.3 g (4.8 mol) of potassium hydroxide was charged, and the system was replaced with nitrogen, adjusted to −0.097 MPa (gauge pressure) or lower, raised to 85 ° C., and then methyl chloride 113 0.1 g (2.2 mol) was added, and the temperature was further raised to 125 ° C. to conduct methyl etherification reaction for 4 hours. After completion, the temperature was lowered to 85 ° C., and unreacted methyl chloride was removed at −0.097 MPa (gauge pressure) or less in nitrogen bubbling. Next, 1077 g of water was added, stirred for 10 minutes and allowed to stand for 2 hours to remove the separated aqueous layer, neutralized with dilute acetic acid, and adjusted to pH 6.2.
水１４０ｇを加え、窒素を吹き込みながら９０℃で常圧脱水し、水の留出が止まってから９０℃、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリングで１時間水分の除去を行った。８０℃迄冷却後、キョーワード６００（協和化学工業（株）製）を２８ｇ添加し、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリングで吸着処理を１時間実施した。濾過器に５種Ａ濾紙をセットし、濾紙上に濾過助剤としてオプライトＷ−３０５０（オプライト鉱業（株）製）を添加し、濾過を行った後８５％燐酸０．０６ｇを加え、撹拌混合により式（２）に示す化合物２５２６ｇを得た。得られた化合物の物性値は過酸化物価３．４ｍｅｑ／ｋｇ、ＣＰＲ０．２、Ｎａ０．１ｐｐｍ、Ｋ０．５ｐｐｍ、水分０．０２％、燐分６．１ｐｐｍ、水酸基価０．５ＫＯＨｍｇ／ｇ、動粘度（２５℃）１５９．９ｍｍ２／ｓ、不飽和度０．５４ｍｅｑ／ｇ、エーテル化反応前後の水酸基価より算出する反応率９８．６％であった。 140 g of water was added and dehydrated at 90 ° C. while blowing nitrogen, and after the distillation of water stopped, water was removed by nitrogen bubbling for 1 hour at 90 ° C., −0.097 MPa (gauge pressure) or less. After cooling to 80 ° C., 28 g of KYOWARD 600 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and adsorption treatment was carried out for 1 hour by nitrogen bubbling at −0.097 MPa (gauge pressure) or less. Set 5 kinds A filter paper on the filter, add Oplite W-3050 (manufactured by Oplite Mining Co., Ltd.) as a filter aid on the filter paper, and after filtration, add 0.06 g of 85% phosphoric acid, and stir and mix Gave 2526 g of the compound represented by formula (2). The physical properties of the obtained compound were peroxide value 3.4 meq / kg, CPR 0.2, Na 0.1 ppm, K 0.5 ppm, moisture 0.02%, phosphorus content 6.1 ppm, hydroxyl value 0.5 KOH mg / g, dynamic value. The viscosity (25 ° C.) was 159.9 mm 2 / s, the degree of unsaturation was 0.54 meq / g, and the reaction rate was 98.6% calculated from the hydroxyl value before and after the etherification reaction.
ＣＨ２＝ＣＨＣＨ２Ｏ（ＥＯ／ＰＯ）ｎＣＨ３ （２） CH 2 = CHCH 2 O (EO / PO) nCH 3 (2)
（実施例２：分子量６００のポリオキシエチレンアリルメチルエーテルの合成）
メタノール１０６．８ｇ（３．３４モル）、およびナトリウムメチラート（２８重量％）メタノール溶液（製品名：液体ソジウムメチラート 「日本曹達株式会社製」）２４．０ｇ（０．６７モル）を５リットル容オートクレーブに仕込み、系中を窒素で置換した後、撹拌しながら１００℃まで昇温し、エチレンオキシド２１２９．１ｇ（４８．４モル）を計量槽に計り取り、１２０℃、０．５ＭＰａ（ゲージ圧力）以下の条件でエチレンオキシドを８時間かけて圧入し、さらに１時間反応を続けた。次に８５℃まで降温し、未反応のエチレンオキシドを−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で除去を行った。反応物の一部を抜き取り、中和、脱水及び濾過により精製サンプルを得、分析を行ったところ反応中間生成物の水酸基価は９９．５ＫＯＨｍｇ／ｇ、動粘度（１００℃）は６．９３ｍｍ２／ｓであった。
(Example 2: Synthesis of polyoxyethylene allyl methyl ether having a molecular weight of 600)
Methanol solution (product name: liquid sodium methylate “manufactured by Nippon Soda Co., Ltd.”) 104.0 g (3.34 mol) of methanol and sodium methylate (28 wt%) 5 After charging in a liter autoclave and replacing the system with nitrogen, the temperature was raised to 100 ° C. while stirring, and 2219.1 g (48.4 mol) of ethylene oxide was weighed into a measuring tank, and 120 ° C., 0.5 MPa (gauge Pressure) Ethylene oxide was injected over 8 hours under the following conditions, and the reaction was further continued for 1 hour. Next, the temperature was lowered to 85 ° C., and unreacted ethylene oxide was removed at −0.097 MPa (gauge pressure) or less in nitrogen bubbling. A part of the reaction product was extracted, a purified sample was obtained by neutralization, dehydration and filtration, and analyzed. As a result, the hydroxyl value of the reaction intermediate product was 99.5 KOHmg / g, and the kinematic viscosity (100 ° C.) was 6.93 mm 2. / S.
５０℃以下まで冷却後、水酸化ナトリウム４００．０ｇ（１０．０モル）を仕込み、系中を窒素で置換した後アリルクロリド３６７．２ｇ（４．８モル）を仕込み、さらに８０℃まで昇温し３時間アリルエーテル化反応を行った。終了後未反応のアリルクロリドを−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で除去を行った。次に水１６００ｇを加えて５分間撹拌後１時間静置させて分層した水層の除去を行い、希燐酸で中和しｐＨを６．１に調整した。 After cooling to 50 ° C. or lower, 400.0 g (10.0 mol) of sodium hydroxide was charged, and after replacing the system with nitrogen, 367.2 g (4.8 mol) of allyl chloride was charged, and the temperature was further raised to 80 ° C. Then, the allyl etherification reaction was carried out for 3 hours. After completion, unreacted allyl chloride was removed in nitrogen bubbling at a pressure of −0.097 MPa (gauge pressure) or less. Next, 1600 g of water was added, stirred for 5 minutes, and allowed to stand for 1 hour to remove the separated aqueous layer, neutralized with dilute phosphoric acid, and adjusted to pH 6.1.
窒素を吹き込みながら８５℃で常圧脱水し、水の留出が止まってから８５℃、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリングで２時間水分の除去を行った。７５℃迄冷却後、キョーワード６００（協和化学工業（株）製）を１３ｇ添加し、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリングで吸着処理を１時間実施した。濾過器に５種Ａ濾紙をセットし、濾紙上に濾過助剤としてオプライトＷ−３０５０（オプライト鉱業（株）製）を添加し、濾過を行った後８５％燐酸０．１１ｇを加え、撹拌混合により式（３）に示す化合物２２０７ｇを得た。得られた化合物の物性値は過酸化物価４．１ｍｅｑ／ｋｇ、ＣＰＲ０．５、Ｎａ１．２ｐｐｍ、Ｋ０．２ｐｐｍ、水分０．０５％、燐分１５．４ｐｐｍ、水酸基価１．３ＫＯＨｍｇ／ｇ、動粘度（１００℃）５．２６ｍｍ２／ｓ、不飽和度１．７０ｍｅｑ／ｇ、エーテル化反応前後の水酸基価より算出する反応率９８．６％であった。 Water was removed by nitrogen bubbling for 2 hours at 85 ° C., −0.097 MPa (gauge pressure) or less after water was stopped distilling while nitrogen was blown in at atmospheric pressure. After cooling to 75 ° C., 13 g of KYOWARD 600 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and an adsorption treatment was carried out for 1 hour by nitrogen bubbling at −0.097 MPa (gauge pressure) or less. Set 5 kinds A filter paper on the filter, add Oplite W-3050 (manufactured by Oplite Mining Co., Ltd.) as a filter aid on the filter paper, filter, add 0.11 g of 85% phosphoric acid, and stir and mix Gave 2207 g of the compound represented by formula (3). The physical properties of the obtained compound were peroxide value 4.1 meq / kg, CPR 0.5, Na 1.2 ppm, K 0.2 ppm, moisture 0.05%, phosphorus content 15.4 ppm, hydroxyl value 1.3 KOH mg / g, dynamic value. The viscosity (100 ° C.) was 5.26 mm 2 / s, the degree of unsaturation was 1.70 meq / g, and the reaction rate was 98.6% calculated from the hydroxyl value before and after the etherification reaction.
ＣＨ２＝ＣＨＣＨ２Ｏ（ＥＯ）ｎＣＨ３ （３） CH 2 = CHCH 2 O (EO ) nCH 3 (3)
（実施例３：分子量１６００のポリオキシエチレンポリオキシプロピレンアリルブチルエーテルの合成）
ｎ−ブタノール１２０．２ｇ（１．６２モル）、およびナトリウムメチラート９．５ｇ（０．１８モル）を５リットル容オートクレーブに仕込み、系中を窒素で置換した後、撹拌しながら１００℃まで昇温し、エチレンオキシド１３２１．５ｇ（３０．０モル）及びプロピレンオキシド１４２５．３ｇ（２４．６モル）の混合物を計量槽に計り取り、１００℃、０．５ＭＰａ（ゲージ圧力）以下の条件でエチレンオキシド及びプロピレンオキシドの混合物を１６時間かけて圧入し、さらに２時間反応を続けた。次に８５℃まで降温し、未反応のエチレンオキシド及びプロピレンオキシドを−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で除去を行った。反応物の一部を抜き取り、中和、脱水及び濾過により精製サンプルを得、分析を行ったところ反応中間生成物の水酸基価は３６．９ＫＯＨｍｇ／ｇ、動粘度（２５℃）は１７０．８ｍｍ２／ｓであった。
(Example 3: Synthesis of polyoxyethylene polyoxypropylene allyl butyl ether having a molecular weight of 1600)
After charging 120.2 g (1.62 mol) of n-butanol and 9.5 g (0.18 mol) of sodium methylate in a 5-liter autoclave, the system was replaced with nitrogen, and the temperature was raised to 100 ° C. with stirring. Warm, a mixture of 1321.5 g (30.0 mol) of ethylene oxide and 1425.3 g (24.6 mol) of propylene oxide was weighed into a measuring tank, and the ethylene oxide and ethylene oxide were analyzed under the conditions of 100 ° C. and 0.5 MPa (gauge pressure) or less. The mixture of propylene oxide was injected over 16 hours and the reaction was continued for another 2 hours. Next, the temperature was lowered to 85 ° C., and unreacted ethylene oxide and propylene oxide were removed in nitrogen bubbling at −0.097 MPa (gauge pressure) or less. A part of the reaction product was extracted, a purified sample was obtained by neutralization, dehydration and filtration, and analyzed. As a result, the hydroxyl value of the reaction intermediate product was 36.9 KOHmg / g, and the kinematic viscosity (25 ° C.) was 170.8 mm 2. / S.
５０℃以下まで冷却後、水酸化カリウム３６３．５ｇ（６．５モル）を仕込み、系中を窒素で置換した後８５℃まで昇温しアリルクロリド１９２．８ｇ（２．５モル）を仕込み、さらに１２５℃まで昇温し３時間アリルエーテル化反応を行った。終了後８５℃まで降温し、未反応のアリルクロリドを−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で除去を行った。次に水１４５０ｇを加えて１０分間撹拌後２時間静置させて分層した水層の除去を行い、希酢酸で中和しｐＨを６．５に調整した。 After cooling to 50 ° C. or less, 363.5 g (6.5 mol) of potassium hydroxide was charged, and the system was replaced with nitrogen, then the temperature was raised to 85 ° C., and 192.8 g (2.5 mol) of allyl chloride was charged. The temperature was further raised to 125 ° C., and an allyl etherification reaction was carried out for 3 hours. After completion, the temperature was lowered to 85 ° C., and unreacted allyl chloride was removed at −0.097 MPa (gauge pressure) or less in nitrogen bubbling. Next, 1450 g of water was added, stirred for 10 minutes, and allowed to stand for 2 hours to remove the separated aqueous layer, neutralized with dilute acetic acid, and adjusted to pH 6.5.
水１５０ｇを加え、窒素を吹き込みながら９０℃で常圧脱水し、水の留出が止まってから９０℃、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリングで１時間水分の除去を行った。７５℃迄冷却後、キョーワード１０００及びキョーワード７００（協和化学工業（株）製）をそれぞれ９ｇずつ添加し、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリングで吸着処理を１時間実施した。濾過器に５種Ａ濾紙をセットし、濾紙上に濾過助剤としてオプライトＷ−３０５０（オプライト鉱業（株）製）を添加し、濾過を行った後８５％燐酸０．３２ｇを加え、撹拌混合により式（４）に示す化合物２７７２ｇを得た。得られた化合物の物性値は過酸化物価３．２ｍｅｑ／ｋｇ、ＣＰＲ０．８、Ｎａ０．７ｐｐｍ、Ｋ０．９ｐｐｍ、水分０．０３％、燐分３０．７ｐｐｍ、水酸基価０．３ＫＯＨｍｇ／ｇ、動粘度（２５℃）１３０．９ｍｍ２／ｓ、不飽和度０．６５ｍｅｑ／ｇ、エーテル化反応前後の水酸基価より算出する反応率９９．２％であった。 150 g of water was added, and atmospheric pressure dehydration was performed at 90 ° C. while blowing nitrogen. After the distillation of water stopped, water was removed by nitrogen bubbling at 90 ° C. and −0.097 MPa (gauge pressure) or less. After cooling to 75 ° C., 9 g each of Kyoward 1000 and Kyoward 700 (manufactured by Kyowa Chemical Industry Co., Ltd.) were added, and adsorption treatment was carried out for 1 hour by nitrogen bubbling at −0.097 MPa (gauge pressure) or less. Set 5 kinds A filter paper in the filter, add Oplite W-3050 (manufactured by Oplite Mining Co., Ltd.) as a filter aid on the filter paper, filter, add 0.32 g of 85% phosphoric acid, and stir and mix Gave 2772 g of the compound represented by formula (4). The physical properties of the obtained compound were peroxide value 3.2 meq / kg, CPR 0.8, Na 0.7 ppm, K 0.9 ppm, moisture 0.03%, phosphorus content 30.7 ppm, hydroxyl value 0.3 KOH mg / g, dynamic value. The viscosity (25 ° C.) was 130.9 mm 2 / s, the degree of unsaturation was 0.65 meq / g, and the reaction rate was 99.2% calculated from the hydroxyl value before and after the etherification reaction.
ＣＨ２＝ＣＨＣＨ２Ｏ（ＥＯ／ＰＯ）ｎＣ４Ｈ９ （４） CH 2 = CHCH 2 O (EO / PO) nC 4 H 9 (4)
（実施例４：分子量１６００のポリオキシエチレンポリオキシプロピレンアリルメチルエーテルの合成）
アリルアルコール８８．２ｇ（１．５２モル）、および水酸化カリウム４．５ｇ（０．０８モル）を５リットル容オートクレーブに仕込み、系中を窒素で置換した後、撹拌しながら１０５℃まで昇温し、エチレンオキシド１７３７．８ｇ（３９．５モル）及びプロピレンオキシド９８２．２ｇ（１６．９モル）の混合物を計量槽に計り取り、１０５℃、０．５ＭＰａ（ゲージ圧力）以下の条件でエチレンオキシド及びプロピレンオキシドの混合物を１４時間かけて圧入し、さらに２時間反応を続けた。次に８５℃まで降温し、未反応のエチレンオキシド及びプロピレンオキシドを−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で除去を行った。反応物の一部を抜き取り、中和、脱水及び濾過により精製サンプルを得、分析を行ったところ反応中間生成物の水酸基価は３５．２ＫＯＨｍｇ／ｇ、動粘度（２５℃）は２４２．２ｍｍ２／ｓであった。
(Example 4: Synthesis of polyoxyethylene polyoxypropylene allyl methyl ether having a molecular weight of 1600)
Allyl alcohol 88.2 g (1.52 mol) and potassium hydroxide 4.5 g (0.08 mol) were charged into a 5 liter autoclave and the system was replaced with nitrogen. A mixture of 1737.8 g (39.5 mol) of ethylene oxide and 982.2 g (16.9 mol) of propylene oxide was weighed into a measuring tank, and ethylene oxide and propylene were measured at 105 ° C. and 0.5 MPa (gauge pressure) or less. The oxide mixture was injected over 14 hours and the reaction was continued for another 2 hours. Next, the temperature was lowered to 85 ° C., and unreacted ethylene oxide and propylene oxide were removed in nitrogen bubbling at −0.097 MPa (gauge pressure) or less. A part of the reaction product was extracted, a purified sample was obtained by neutralization, dehydration and filtration, and analyzed. As a result, the hydroxyl value of the reaction intermediate product was 35.2 KOHmg / g, and the kinematic viscosity (25 ° C.) was 242.2 mm 2. / S.
５０℃以下まで冷却後、水酸化カリウム２６９．３ｇ（４．８モル）を仕込み、系中を窒素で置換した後−０．０９７ＭＰａ（ゲージ圧力）以下とし、８５℃まで昇温後メチルクロリド１１３．１ｇ（２．２モル）を仕込み、さらに１２５℃まで昇温し４時間メチルエーテル化反応を行った。終了後８５℃まで降温し、未反応のメチルクロリドを−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で除去を行った。次に水１０７７ｇを加えて１０分間撹拌後１時間静置させて分層した水層の除去を行い、希塩酸で中和しｐＨを５．２に調整した。 After cooling to 50 ° C. or lower, 269.3 g (4.8 mol) of potassium hydroxide was charged, and the system was replaced with nitrogen, adjusted to −0.097 MPa (gauge pressure) or lower, raised to 85 ° C., and then methyl chloride 113 0.1 g (2.2 mol) was added, and the temperature was further raised to 125 ° C. to conduct methyl etherification reaction for 4 hours. After completion, the temperature was lowered to 85 ° C., and unreacted methyl chloride was removed at −0.097 MPa (gauge pressure) or less in nitrogen bubbling. Next, 1077 g of water was added, stirred for 10 minutes and allowed to stand for 1 hour to remove the separated aqueous layer, neutralized with dilute hydrochloric acid and adjusted to pH 5.2.
水１４０ｇを加え、窒素を吹き込みながら９０℃で常圧脱水し、水の留出が止まってから９０℃、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリングで１時間水分の除去を行った。８０℃迄冷却後、キョーワード３００およびキョーワード７００（協和化学工業（株）製）をそれぞれ１４ｇ添加し、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリングで吸着処理を１時間実施した。濾過器に５種Ａ濾紙をセットし、濾紙上に濾過助剤としてオプライトＷ−３０５０（オプライト鉱業（株）製）を添加し、濾過を行った後８５％燐酸０．６４ｇを加え、撹拌混合により式（２）に示す化合物２５８５ｇを得た。得られた化合物の物性値は過酸化物価２．５ｍｅｑ／ｋｇ、ＣＰＲ０．３、Ｎａ０．２ｐｐｍ、Ｋ０．５ｐｐｍ、水分０．０４％、燐分６２．２ｐｐｍ、水酸基価２．２ＫＯＨｍｇ／ｇ、動粘度（２５℃）１９３．４ｍｍ２／ｓ、不飽和度０．５４ｍｅｑ／ｇ、エーテル化反応前後の水酸基価より算出する反応率９５．７％であった。 140 g of water was added and dehydrated at 90 ° C. while blowing nitrogen, and after the distillation of water stopped, water was removed by nitrogen bubbling for 1 hour at 90 ° C., −0.097 MPa (gauge pressure) or less. After cooling to 80 ° C., 14 g of KYOWARD 300 and KYOWARD 700 (manufactured by Kyowa Chemical Industry Co., Ltd.) were added, respectively, and adsorption treatment was carried out for 1 hour by nitrogen bubbling at −0.097 MPa (gauge pressure) or less. Set 5 kinds A filter paper on the filter, add Oplite W-3050 (manufactured by Oplite Mining Co., Ltd.) as a filter aid on the filter paper, and after filtration, add 0.64 g of 85% phosphoric acid, and stir and mix Gave 2585 g of the compound represented by formula (2). The physical properties of the obtained compound were: peroxide value 2.5 meq / kg, CPR 0.3, Na 0.2 ppm, K 0.5 ppm, moisture 0.04%, phosphorus content 62.2 ppm, hydroxyl value 2.2 KOH mg / g, dynamic value. The viscosity (25 ° C.) was 193.4 mm 2 / s, the degree of unsaturation was 0.54 meq / g, and the reaction rate was 95.7% calculated from the hydroxyl value before and after the etherification reaction.
（実施例５：分子量７００のポリオキシエチレンポリオキシプロピレンアリルメチルエーテルの合成）
メタノール７７．６ｇ（２．４３モル）、およびナトリウムメチラート（２８重量％）メタノール溶液３８．８ｇ（１．０７モル）を５リットル容オートクレーブに仕込み、系中を窒素で置換した後、撹拌しながら１１０℃まで昇温し、エチレンオキシド１４３２．６ｇ（３２．６モル）及びプロピレンオキシド８０９．６ｇ（１４．０モル）の混合物を計量槽に計り取り、１１０℃、０．５ＭＰａ（ゲージ圧力）以下の条件でエチレンオキシド及びプロピレンオキシドの混合物を８時間かけて圧入し、さらに１時間反応を続けた。次に８５℃まで降温し、未反応のエチレンオキシド及びプロピレンオキシドを−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で除去を行った。反応物の一部を抜き取り、中和、脱水及び濾過により精製サンプルを得、分析を行ったところ反応中間生成物の水酸基価は８１．６ＫＯＨｍｇ／ｇ、動粘度（２５℃）は５７．７ｍｍ２／ｓであった。
(Example 5: Synthesis of polyoxyethylene polyoxypropylene allyl methyl ether having a molecular weight of 700)
77.6 g (2.43 mol) of methanol and 38.8 g (1.07 mol) of methanol solution of sodium methylate (28 wt%) were charged into a 5-liter autoclave, and the system was purged with nitrogen and stirred. The temperature was raised to 110 ° C., and a mixture of 1432.6 g (32.6 mol) of ethylene oxide and 809.6 g (14.0 mol) of propylene oxide was weighed into a measuring tank, and 110 ° C. and 0.5 MPa (gauge pressure) or less. Then, a mixture of ethylene oxide and propylene oxide was injected over 8 hours, and the reaction was continued for another hour. Next, the temperature was lowered to 85 ° C., and unreacted ethylene oxide and propylene oxide were removed in nitrogen bubbling at −0.097 MPa (gauge pressure) or less. A part of the reaction product was extracted, a purified sample was obtained by neutralization, dehydration and filtration, and analyzed. As a result, the hydroxyl value of the reaction intermediate product was 81.6 KOHmg / g, and the kinematic viscosity (25 ° C.) was 57.7 mm 2. / S.
５０℃以下まで冷却後、水酸化カリウム４９０．９ｇ（８．８モル）を仕込み、系中を窒素で置換した後８５℃まで昇温しアリルクロリド３２１．３ｇ（４．２モル）を仕込み、さらに１２５℃まで昇温し２時間アリルエーテル化反応を行った。終了後８５℃まで降温し、未反応のアリルクロリドを−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で除去を行った。次に水１４７０ｇを加えて１０分間撹拌後１時間静置させて分層した水層の除去を行い、希燐酸で中和しｐＨを５．６に調整した。 After cooling to 50 ° C. or lower, 490.9 g (8.8 mol) of potassium hydroxide was charged, the system was replaced with nitrogen, the temperature was raised to 85 ° C., and 321.3 g (4.2 mol) of allyl chloride was charged, The temperature was further raised to 125 ° C., and an allyl etherification reaction was carried out for 2 hours. After completion, the temperature was lowered to 85 ° C., and unreacted allyl chloride was removed at −0.097 MPa (gauge pressure) or less in nitrogen bubbling. Next, 1470 g of water was added, stirred for 10 minutes, and allowed to stand for 1 hour to remove the separated aqueous layer, neutralized with dilute phosphoric acid, and adjusted to pH 5.6.
水１２０ｇを加え、窒素を吹き込みながら８０℃で常圧脱水し、水の留出が止まってから８０℃、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリングで２時間水分の除去を行った。７０℃迄冷却後、キョーワード６００（協和化学工業（株）製）を１３ｇ添加し、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリングで吸着処理を１時間実施した。濾過器に５種Ａ濾紙をセットし、濾紙上に濾過助剤としてオプライトＷ−３０５０（オプライト鉱業（株）製）を添加し、濾過を行った後８５％燐酸０．１７ｇを加え、撹拌混合により式（２）に示す化合物２３９７ｇを得た。得られた化合物の物性値は過酸化物価４．４ｍｅｑ／ｋｇ、ＣＰＲ０．６、Ｎａ０．８ｐｐｍ、Ｋ１．３ｐｐｍ、水分０．１２％、燐分２１．５ｐｐｍ、水酸基価１．９ＫＯＨｍｇ／ｇ、動粘度（２５℃）３５．２ｍｍ２／ｓ、不飽和度１．３８ｍｅｑ／ｇ、エーテル化反応前後の水酸基価より算出する反応率９７．７％であった。 120 g of water was added, dehydrated at 80 ° C. while blowing nitrogen, and after the distillation of water stopped, water was removed by nitrogen bubbling at 80 ° C. and −0.097 MPa (gauge pressure) or less. After cooling to 70 ° C., 13 g of KYOWARD 600 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and adsorption treatment was carried out for 1 hour with nitrogen bubbling at −0.097 MPa (gauge pressure) or less. Set 5 kinds A filter paper on the filter, add Oplite W-3050 (manufactured by Oplite Mining Co., Ltd.) as a filter aid on the filter paper, and after filtration, add 0.17 g of 85% phosphoric acid, and stir and mix Gave 2397 g of the compound represented by formula (2). The physical properties of the obtained compound were peroxide value 4.4 meq / kg, CPR 0.6, Na 0.8 ppm, K 1.3 ppm, moisture 0.12%, phosphorus content 21.5 ppm, hydroxyl value 1.9 KOH mg / g, dynamic value. The viscosity (25 ° C.) was 35.2 mm 2 / s, the degree of unsaturation was 1.38 meq / g, and the reaction rate calculated from the hydroxyl value before and after the etherification reaction was 97.7%.
（比較例１：分子量１６００のポリオキシエチレンポリオキシプロピレンアリルメチルエーテルの合成）
アリルアルコール８８．２ｇ（１．５２モル）、および水酸化カリウム４．５ｇ（０．０８モル）を５リットル容オートクレーブに仕込み、系中を窒素で置換した後、撹拌しながら１００℃まで昇温し、エチレンオキシド１１６８．２ｇ（２６．６モル）及びプロピレンオキシド１５３９．９ｇ（２６．６モル）の混合物を計量槽に計り取り、１００℃、０．５ＭＰａ（ゲージ圧力）以下の条件でエチレンオキシド及びプロピレンオキシドの混合物を２１時間かけて圧入し、さらに４時間反応を続けた。次に８５℃まで降温し、未反応のエチレンオキシド及びプロピレンオキシドを−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で除去を行った。反応物の一部を抜き取り、中和、脱水及び濾過により精製サンプルを得、分析を行ったところ反応中間生成物の水酸基価は３６．０ＫＯＨｍｇ／ｇ、動粘度（２５℃）は２０１．９ｍｍ２／ｓであった。
(Comparative Example 1: Synthesis of polyoxyethylene polyoxypropylene allyl methyl ether having a molecular weight of 1600)
Allyl alcohol 88.2 g (1.52 mol) and potassium hydroxide 4.5 g (0.08 mol) were charged into a 5 liter autoclave and the system was replaced with nitrogen. A mixture of 1168.2 g (26.6 mol) of ethylene oxide and 1539.9 g (26.6 mol) of propylene oxide was weighed into a measuring tank, and ethylene oxide and propylene were subjected to conditions of 100 ° C. and 0.5 MPa (gauge pressure) or less. The oxide mixture was injected over 21 hours and the reaction was continued for another 4 hours. Next, the temperature was lowered to 85 ° C., and unreacted ethylene oxide and propylene oxide were removed in nitrogen bubbling at −0.097 MPa (gauge pressure) or less. A part of the reaction product was extracted, a purified sample was obtained by neutralization, dehydration and filtration, and analyzed. As a result, the hydroxyl value of the reaction intermediate product was 36.0 KOHmg / g, and the kinematic viscosity (25 ° C.) was 201.9 mm 2. / S.
５０℃以下まで冷却後、水酸化カリウム２６９．３ｇ（４．８モル）を仕込み、系中を窒素で置換した後−０．０９７ＭＰａ（ゲージ圧力）以下とし、８５℃まで昇温後メチルクロリド１１３．１ｇ（２．２モル）を仕込み、さらに１２５℃まで昇温し４時間メチルエーテル化反応を行った。終了後８５℃まで降温し、未反応のメチルクロリドを−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で除去を行った。次に水１０７７ｇを加えて１０分間撹拌後２時間静置させて分層した水層の除去を行い、希塩酸で中和しｐＨを５．９に調整した。 After cooling to 50 ° C. or lower, 269.3 g (4.8 mol) of potassium hydroxide was charged, and the system was replaced with nitrogen, adjusted to −0.097 MPa (gauge pressure) or lower, raised to 85 ° C., and then methyl chloride 113 0.1 g (2.2 mol) was added, and the temperature was further raised to 125 ° C. to conduct methyl etherification reaction for 4 hours. After completion, the temperature was lowered to 85 ° C., and unreacted methyl chloride was removed at −0.097 MPa (gauge pressure) or less in nitrogen bubbling. Next, 1077 g of water was added, stirred for 10 minutes and allowed to stand for 2 hours to remove the separated aqueous layer, neutralized with dilute hydrochloric acid, and adjusted to pH 5.9.
水１４０ｇを加え、窒素を吹き込みながら８０℃で常圧脱水し、水の留出が止まってから８０℃、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリングで１時間水分の除去を行った。次いで、キョーワード１０００及びキョーワード７００（協和化学工業（株）製）をそれぞれ１２ｇずつ添加し、８０℃、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリングで吸着処理を１時間実施した。濾過器に５種Ａ濾紙をセットし、濾紙上に濾過助剤としてオプライトＷ−３０５０（オプライト鉱業（株）製）を添加し、濾過を行った後８５％燐酸は加えず式（２）に示す化合物２５１２ｇを得た。得られた化合物の物性値は過酸化物価４．０ｍｅｑ／ｋｇ、ＣＰＲ０．８、Ｎａ０．２ｐｐｍ、Ｋ０．８ｐｐｍ、水分０．０８％、燐分０ｐｐｍ、水酸基価１．０ＫＯＨｍｇ／ｇ、動粘度（２５℃）１６２．５ｍｍ２／ｓ、不飽和度０．５５ｍｅｑ／ｇ、エーテル化反応前後の水酸基価より算出する反応率９７．２％であった。 140 g of water was added and dehydrated at 80 ° C. while blowing nitrogen, and after the distillation of water stopped, water was removed by nitrogen bubbling for 1 hour at 80 ° C., −0.097 MPa (gauge pressure) or less. Next, 12 g each of Kyoward 1000 and Kyoward 700 (manufactured by Kyowa Chemical Industry Co., Ltd.) were added, and adsorption treatment was carried out for 1 hour at 80 ° C. and −0.097 MPa (gauge pressure) or less with nitrogen bubbling. Set 5 kinds A filter paper in the filter, add Oplite W-3050 (manufactured by Oplite Mining Co., Ltd.) as a filter aid on the filter paper, and after filtration, 85% phosphoric acid is not added and the formula (2) 2512 g of the compound shown are obtained. The physical properties of the obtained compound were peroxide value 4.0 meq / kg, CPR 0.8, Na 0.2 ppm, K 0.8 ppm, moisture 0.08%, phosphorus content 0 ppm, hydroxyl value 1.0 KOH mg / g, kinematic viscosity ( 25 ° C.) 162.5 mm 2 / s, degree of unsaturation 0.55 meq / g, and the reaction rate calculated from the hydroxyl value before and after the etherification reaction was 97.2%.
（比較例２）
比較例１記載の製造方法の濾過後、アスコルビン酸０．５０ｇを加えた以外は比較例１と同条件で合成を行い、式（２）に示す化合物２５２３ｇを得た。反応中間生成物の水酸基価は３６．７ＫＯＨｍｇ／ｇ、動粘度（２５℃）は２０１．１ｍｍ２／ｓであった。また、得られた化合物の物性値は過酸化物価３．８ｍｅｑ／ｋｇ、ＣＰＲ０．９、Ｎａ０．１ｐｐｍ、Ｋ１．２ｐｐｍ、水分０．１１％、燐分０ｐｐｍ、水酸基価０．８ＫＯＨｍｇ／ｇ、動粘度（２５℃）１６３．８ｍｍ２／ｓ、不飽和度０．５５ｍｅｑ／ｇ、エーテル化反応前後の水酸基価より算出する反応率９７．８％であった。
(Comparative Example 2)
After filtration of the production method described in Comparative Example 1, synthesis was performed under the same conditions as in Comparative Example 1 except that 0.50 g of ascorbic acid was added to obtain 2523 g of a compound represented by Formula (2). The hydroxyl value of the reaction intermediate product was 36.7 KOH mg / g, and the kinematic viscosity (25 ° C.) was 201.1 mm 2 / s. The physical properties of the obtained compound were peroxide value 3.8 meq / kg, CPR 0.9, Na 0.1 ppm, K 1.2 ppm, moisture 0.11%, phosphorus content 0 ppm, hydroxyl value 0.8 KOH mg / g, dynamic value. The viscosity (25 ° C.) was 163.8 mm 2 / s, the degree of unsaturation was 0.55 meq / g, and the reaction rate was 97.8% calculated from the hydroxyl value before and after the etherification reaction.
（比較例３）
比較例１記載の製造方法の濾過後、３８％塩酸０．３３ｇを加えた以外は比較例１と同条件で合成を行い、式（２）に示す化合物２５３５ｇを得た。反応中間生成物の水酸基価は３６．５ＫＯＨｍｇ／ｇ、動粘度（２５℃）は２０３．６ｍｍ２／ｓであった。また、得られた化合物の物性値は過酸化物価４．５ｍｅｑ／ｋｇ、ＣＰＲ０、Ｎａ０．１ｐｐｍ、Ｋ０．６ｐｐｍ、水分０．０９％、燐分０ｐｐｍ、水酸基価０．７ＫＯＨｍｇ／ｇ、動粘度（２５℃）１６０．２ｍｍ２／ｓ、不飽和度０．５４ｍｅｑ／ｇ、エーテル化反応前後の水酸基価より算出する反応率９８．１％であった。
(Comparative Example 3)
After filtration of the production method described in Comparative Example 1, synthesis was performed under the same conditions as Comparative Example 1 except that 0.33 g of 38% hydrochloric acid was added to obtain 2535 g of a compound represented by the formula (2). The hydroxyl value of the reaction intermediate product was 36.5 KOH mg / g, and the kinematic viscosity (25 ° C.) was 203.6 mm 2 / s. The physical properties of the obtained compound were as follows: peroxide value 4.5 meq / kg, CPR0, Na0.1 ppm, K0.6 ppm, moisture 0.09%, phosphorus content 0 ppm, hydroxyl value 0.7 KOHmg / g, kinematic viscosity ( 25 ° C.) 160.2 mm 2 / s, degree of unsaturation 0.54 meq / g, and the reaction rate calculated from the hydroxyl value before and after the etherification reaction was 98.1%.
（比較例４）
比較例１記載の製造方法の濾過後、酢酸０．２５ｇを加えた以外は比較例１と同条件で合成を行い、式（２）に示す化合物２５２０ｇを得た。反応中間生成物の水酸基価は３６．２ＫＯＨｍｇ／ｇ、動粘度（２５℃）は２０３．１ｍｍ２／ｓであった。また、得られた化合物の物性値は過酸化物価４．２ｍｅｑ／ｋｇ、ＣＰＲ１．２、Ｎａ０．２ｐｐｍ、Ｋ１．０ｐｐｍ、水分０．０７％、燐分０ｐｐｍ、水酸基価１．２ＫＯＨｍｇ／ｇ、動粘度（２５℃）１６１．５ｍｍ２／ｓ、不飽和度０．５５ｍｅｑ／ｇ、エーテル化反応前後の水酸基価より算出する反応率９６．７％であった。
(Comparative Example 4)
After filtration of the production method described in Comparative Example 1, synthesis was performed under the same conditions as in Comparative Example 1 except that 0.25 g of acetic acid was added to obtain 2520 g of a compound represented by Formula (2). The hydroxyl value of the reaction intermediate product was 36.2 KOH mg / g, and the kinematic viscosity (25 ° C.) was 203.1 mm 2 / s. The physical properties of the obtained compound were peroxide value 4.2 meq / kg, CPR 1.2, Na 0.2 ppm, K 1.0 ppm, moisture 0.07%, phosphorus content 0 ppm, hydroxyl value 1.2 KOH mg / g, dynamic value. The viscosity (25 ° C.) was 161.5 mm 2 / s, the degree of unsaturation was 0.55 meq / g, and the reaction rate was 96.7% calculated from the hydroxyl value before and after the etherification reaction.
（比較例５：分子量６５０のポリオキシプロピレンアリルメチルエーテルの合成）
アリルアルコール１９２．７ｇ（３．３２モル）、およびナトリウムメチラート９．６ｇ（０．１８モル）を５リットル容オートクレーブに仕込み、系中を窒素で置換した後、撹拌しながら１００℃まで昇温し、プロピレンオキシド２１３１．５ｇ（３６．８モル）を計量槽に計り取り、１００℃、０．５ＭＰａ（ゲージ圧力）以下の条件でプロピレンオキシドの混合物を２２時間かけて圧入し、さらに２時間反応を続けた。次に８５℃まで降温し、未反応のプロピレンオキシドを−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で除去を行った。反応物の一部を抜き取り、中和、脱水及び濾過により精製サンプルを得、分析を行ったところ反応中間生成物の水酸基価は８９．５ＫＯＨｍｇ／ｇ、動粘度（２５℃）は４０．３ｍｍ２／ｓであった。
(Comparative Example 5: Synthesis of polyoxypropylene allyl methyl ether having a molecular weight of 650)
192.7 g (3.32 mol) of allyl alcohol and 9.6 g (0.18 mol) of sodium methylate were charged into a 5 liter autoclave, the system was replaced with nitrogen, and the temperature was raised to 100 ° C. with stirring. Then, 2131.5 g (36.8 mol) of propylene oxide was weighed into a measuring tank, and a mixture of propylene oxide was injected over 22 hours under the conditions of 100 ° C. and 0.5 MPa (gauge pressure) or less, and further reacted for 2 hours. Continued. Next, the temperature was lowered to 85 ° C., and unreacted propylene oxide was removed in nitrogen bubbling at −0.097 MPa (gauge pressure) or less. A part of the reaction product was extracted, a purified sample was obtained by neutralization, dehydration and filtration, and analyzed. As a result, the hydroxyl value of the reaction intermediate product was 89.5 KOHmg / g, and the kinematic viscosity (25 ° C.) was 40.3 mm 2. / S.
５０℃以下まで冷却後、水酸化ナトリウム４０６．０ｇ（１０．２モル）を仕込み、系中を窒素で置換した後−０．０９７ＭＰａ（ゲージ圧力）以下とし、８５℃まで昇温後メチルクロリド２２０．９ｇ（４．４モル）を仕込み、さらに１２５℃まで昇温し４時間メチルエーテル化反応を行った。終了後８５℃まで降温し、未反応のメチルクロリドを−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で除去を行った。次に水１７００ｇを加えて１０分間撹拌後２時間静置させて分層した水層の除去を行い、希酢酸で中和しｐＨを６．４に調整した。 After cooling to 50 ° C. or lower, 406.0 g (10.2 mol) of sodium hydroxide was charged, and after replacing the system with nitrogen, the pressure was reduced to −0.097 MPa (gauge pressure) or lower. After raising the temperature to 85 ° C., methyl chloride 220 .9 g (4.4 mol) was added, and the temperature was further raised to 125 ° C. to conduct methyl etherification reaction for 4 hours. After completion, the temperature was lowered to 85 ° C., and unreacted methyl chloride was removed at −0.097 MPa (gauge pressure) or less in nitrogen bubbling. Next, 1700 g of water was added, stirred for 10 minutes, and allowed to stand for 2 hours to remove the separated aqueous layer, neutralized with dilute acetic acid, and adjusted to pH 6.4.
窒素を吹き込みながら８０℃で常圧脱水し、水の留出が止まってから８０℃、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリングで１時間水分の除去を行った。次いで濾過器に５種Ａ濾紙をセットし、濾紙上に濾過助剤としてオプライトＷ−３０５０（オプライト鉱業（株）製）を添加し、濾過を行った後８５％燐酸０．９５ｇを加え、撹拌混合により式（５）に示す化合物２１９５ｇを得た。得られた化合物の物性値は過酸化物価４．７ｍｅｑ／ｋｇ、ＣＰＲ２．５、Ｎａ７．９ｐｐｍ、Ｋ０．８ｐｐｍ、水分０．０５％、燐分１４．９ｐｐｍ、水酸基価１．６ＫＯＨｍｇ／ｇ、動粘度（２５℃）２２．７ｍｍ２／ｓ、不飽和度１．４１ｍｅｑ／ｇ、エーテル化反応前後の水酸基価より算出する反応率９８．２％であった。 Water was removed by nitrogen bubbling for 1 hour at 80 ° C., −0.097 MPa (gauge pressure) or less after water was stopped distilling while nitrogen was blown. Next, set 5 kinds A filter paper in the filter, add Oplite W-3050 (manufactured by Oplite Mining Co., Ltd.) as a filter aid on the filter paper, and after filtration, add 0.95 g of 85% phosphoric acid and stir By mixing, 2195 g of the compound represented by the formula (5) was obtained. The physical properties of the obtained compound were peroxide value 4.7 meq / kg, CPR 2.5, Na 7.9 ppm, K 0.8 ppm, moisture 0.05%, phosphorus content 14.9 ppm, hydroxyl value 1.6 KOH mg / g, dynamic value. The viscosity (25 ° C.) was 22.7 mm 2 / s, the degree of unsaturation was 1.41 meq / g, and the reaction rate was 98.2% calculated from the hydroxyl value before and after the etherification reaction.
ＣＨ２＝ＣＨＣＨ２Ｏ（ＰＯ）ｎＣＨ３ （５） CH 2 = CHCH 2 O (PO ) nCH 3 (5)
（比較例６：分子量１６００のポリオキシエチレンポリオキシプロピレンアリルブチルエーテルの合成）
ｎ−ブタノール１２０．２ｇ（１．６２モル）、およびナトリウムメチラート９．５ｇ（０．１８モル）を５リットル容オートクレーブに仕込み、系中を窒素で置換した後、撹拌しながら１００℃まで昇温し、エチレンオキシド１３２１．５ｇ（３０．０モル）及びプロピレンオキシド１４２５．３ｇ（２４．６モル）の混合物を計量槽に計り取り、１００℃、０．５ＭＰａ（ゲージ圧力）以下の条件でエチレンオキシド及びプロピレンオキシドの混合物を１６時間かけて圧入し、さらに２時間反応を続けた。次に８５℃まで降温し、未反応のエチレンオキシド及びプロピレンオキシドを−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で除去を行った。反応物の一部を抜き取り、中和、脱水及び濾過により精製サンプルを得、分析を行ったところ反応中間生成物の水酸基価は３６．４ＫＯＨｍｇ／ｇ、動粘度（２５℃）は１７１．１ｍｍ２／ｓであった。
(Comparative Example 6: Synthesis of polyoxyethylene polyoxypropylene allyl butyl ether having a molecular weight of 1600)
After charging 120.2 g (1.62 mol) of n-butanol and 9.5 g (0.18 mol) of sodium methylate in a 5-liter autoclave, the system was replaced with nitrogen, and the temperature was raised to 100 ° C. with stirring. Warm, a mixture of 1321.5 g (30.0 mol) of ethylene oxide and 1425.3 g (24.6 mol) of propylene oxide was weighed into a measuring tank, and the ethylene oxide and ethylene oxide were analyzed under the conditions of 100 ° C. and 0.5 MPa (gauge pressure) or less. The mixture of propylene oxide was injected over 16 hours and the reaction was continued for another 2 hours. Next, the temperature was lowered to 85 ° C., and unreacted ethylene oxide and propylene oxide were removed in nitrogen bubbling at −0.097 MPa (gauge pressure) or less. A part of the reaction product was extracted, a purified sample was obtained by neutralization, dehydration and filtration, and analyzed. As a result, the hydroxyl value of the reaction intermediate product was 36.4 KOHmg / g, and the kinematic viscosity (25 ° C.) was 171.1 mm 2. / S.
５０℃以下まで冷却後、水酸化ナトリウム２６０．０ｇ（６．５モル）を仕込み、系中を窒素で置換した後８５℃まで昇温しアリルクロリド１９２．８ｇ（２．５モル）を仕込み、さらに１２５℃まで昇温し３時間アリルエーテル化反応を行った。終了後８５℃まで降温し、未反応のアリルクロリドを−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリング中で除去を行った。次に水１４５０ｇを加えて１０分間撹拌後２時間静置させて分層した水層の除去を行い、希塩酸で中和しｐＨを５．４に調整した。 After cooling to 50 ° C. or lower, sodium hydroxide 260.0 g (6.5 mol) was charged, the system was replaced with nitrogen, the temperature was raised to 85 ° C., and allyl chloride 192.8 g (2.5 mol) was charged. The temperature was further raised to 125 ° C., and an allyl etherification reaction was carried out for 3 hours. After completion, the temperature was lowered to 85 ° C., and unreacted allyl chloride was removed at −0.097 MPa (gauge pressure) or less in nitrogen bubbling. Next, 1450 g of water was added, stirred for 10 minutes, and allowed to stand for 2 hours to remove the separated aqueous layer, neutralized with dilute hydrochloric acid, and adjusted to pH 5.4.
水１５０ｇを加え、窒素を吹き込みながら９０℃で常圧脱水し、水の留出が止まってから９０℃、−０．０９７ＭＰａ（ゲージ圧力）以下、窒素バブリングで１時間水分の除去を行った。次いで濾過器に５種Ａ濾紙をセットし、濾紙上に濾過助剤としてオプライトＷ−３０５０（オプライト鉱業（株）製）を添加し、濾過を行った後８５％燐酸０．２２ｇを加え、撹拌混合により式（４）に示す化合物２７１３ｇを得た。得られた化合物の物性値は過酸化物価３．９ｍｅｑ／ｋｇ、ＣＰＲ５．３、Ｎａ２．３ｐｐｍ、Ｋ０．３ｐｐｍ、水分０．０４％、燐分２１．１ｐｐｍ、水酸基価０．９ＫＯＨｍｇ／ｇ、動粘度（２５℃）１３１．９ｍｍ２／ｓ、不飽和度０．６４ｍｅｑ／ｇ、エーテル化反応前後の水酸基価より算出する反応率９７．５％であった。 150 g of water was added, and atmospheric pressure dehydration was performed at 90 ° C. while blowing nitrogen. After the distillation of water stopped, water was removed by nitrogen bubbling at 90 ° C. and −0.097 MPa (gauge pressure) or less. Next, set 5 kinds A filter paper in the filter, add Oplite W-3050 (manufactured by Oplite Mining Co., Ltd.) as a filter aid on the filter paper, and after filtration, add 0.22 g of 85% phosphoric acid and stir By mixing, 2713 g of the compound represented by the formula (4) was obtained. The physical properties of the obtained compound were as follows: peroxide value 3.9 meq / kg, CPR 5.3, Na 2.3 ppm, K 0.3 ppm, moisture 0.04%, phosphorus content 21.1 ppm, hydroxyl value 0.9 KOH mg / g. The viscosity (25 ° C.) was 131.9 mm 2 / s, the degree of unsaturation was 0.64 meq / g, and the reaction rate was 97.5% calculated from the hydroxyl value before and after the etherification reaction.
（実施例６〜１０、比較例７〜１２）
１リットル容四ツ口フラスコに撹拌装置、冷却管、窒素導入管を取り付け、式（６）で示されるハイドロジェンジメチルポリシロキサンと、実施例１〜５および比較例１〜６で得られたアルケニル基含有ポリオキシアルキレン誘導体をＳｉ−Ｈ基当量の１．２倍量の過剰量で仕込み、さらに触媒として塩化白金酸六水和物のイソプロピルアルコール溶液（１×１０−３モル／リットル）を白金換算で１０ｐｐｍとなるように仕込み、窒素雰囲気下８０℃で３時間撹拌を行った。反応終了後、サンプリングを行いＮ／１０水酸化カリウムのイソプロピルアルコール溶液を加えて水素ガス発生量を定量し、ヒドロシリル化反応率を求めた。反応の実施時期については製造直後と、１ｋｇ缶容器に１ｋｇ密充填し１年保管後に行った。結果を表１、２、３に示す。
(Examples 6 to 10, Comparative Examples 7 to 12)
A 1-liter four-necked flask was equipped with a stirrer, a condenser tube, and a nitrogen inlet tube, and hydrogen dimethylpolysiloxane represented by formula (6) and the alkenyl obtained in Examples 1 to 5 and Comparative Examples 1 to 6 were used. A group-containing polyoxyalkylene derivative is charged in an excess amount 1.2 times the Si-H group equivalent, and a chloroplatinic acid hexahydrate isopropyl alcohol solution (1 × 10 −3 mol / liter) is platinum as a catalyst. The mixture was prepared so as to be 10 ppm in terms of conversion, and stirred at 80 ° C. for 3 hours under a nitrogen atmosphere. After completion of the reaction, sampling was performed, an N / 10 potassium hydroxide isopropyl alcohol solution was added, and the amount of hydrogen gas generated was quantified to determine the hydrosilylation reaction rate. The reaction was carried out immediately after production and after 1 kg was packed in a 1 kg can container and stored for 1 year. The results are shown in Tables 1, 2, and 3.
実施例１、２、３、４、５の合成例による合成物を使用した実施例６、７、８、９、１０においては、製造から１年経過した後のヒドロシリル化反応率は１００％であった。 In Examples 6, 7, 8, 9, and 10 using the synthesized products of Examples 1, 2, 3, 4, and 5, the hydrosilylation reaction rate after 1 year from the production was 100%. there were.
比較例１の合成物（比較例７）では、燐酸添加処理を行っていない。比較例２、３、４（比較例８、９、１０）でも燐酸添加しておらず、その代りにアスコルビン酸、塩酸、酢酸を添加している。この結果、燐分は０ｐｐｍである。そして、製造直後におけるヒドロシリル化反応率は１００％であるが、１年保管後の反応率は６３、５２、３５、４１％と著しく低下していた。 In the composite of Comparative Example 1 (Comparative Example 7), no phosphoric acid addition treatment was performed. In Comparative Examples 2, 3, and 4 (Comparative Examples 8, 9, and 10), phosphoric acid is not added, and ascorbic acid, hydrochloric acid, and acetic acid are added instead. As a result, the phosphorus content is 0 ppm. The hydrosilylation reaction rate immediately after production was 100%, but the reaction rate after storage for one year was significantly reduced to 63, 52, 35, and 41%.
比較例５、６では、吸着剤による処理を行っていない。この結果、比較例５では、Ｋ＋Ｎａ量は８．５ｐｐｍとなっており、製造直後のヒドロシリル化反応率は５４％と低く、１年保管後には１２％に激減している。比較例６（比較例１２）では、ＣＰＲが５．３と高くなっているが、製造直後のヒドロシリル化反応率は７１％と低く、１年保管後には１９％に激減している。
In Comparative Examples 5 and 6, the treatment with the adsorbent is not performed. As a result, in Comparative Example 5, the amount of K + Na is 8.5 ppm, and the hydrosilylation reaction rate immediately after production is as low as 54%, which is drastically reduced to 12% after 1 year storage. In Comparative Example 6 (Comparative Example 12), the CPR was as high as 5.3, but the hydrosilylation reaction rate immediately after the production was as low as 71%, and decreased dramatically to 19% after 1 year storage.
Claims (5)
Ａ．過酸化物価 １０．０meq／kg以下
Ｂ．ＣＰＲ ５．０以下
Ｃ．Ｎａ分＋Ｋ分 ３．０ppm以下
Ｄ．水分 ０．２%以下
Ｅ．燐分 ５〜７０ｐｐｍ
Ｆ．前記中間生成物の水酸基価および前記精製物の水酸基価より算出する前記末端水酸基のエーテル化反応率が９３％以上
Ｒ１Ｏ（ＡＯ）ｎＲ２ （１）
（式中、Ｒ１は、末端に二重結合を有する炭素数３〜５のアルケニル基であり、ＡＯは、炭素数２〜４のオキシアルキレン基であり、ｎ＝１〜１５０、Ｒ２は、炭素数１〜２４のアルキル基もしくはアルケニル基である。） The alkylene oxide is subjected to ring-opening polymerization of the raw material alcohol to obtain an intermediate product containing a polyoxyalkylene derivative having a terminal hydroxyl group, an alkylene oxide addition reaction step, this intermediate product is reacted with an organic halide to form a terminal ether group. An etherification reaction step for obtaining an etherification reaction product containing a polyoxyalkylene derivative having, and a purification step for purifying the etherification reaction product to obtain a purified product satisfying the following condition (1) A purified product of an alkenyl group-containing polyoxyalkylene derivative represented by the formula:
A. Peroxide value: 10.0 meq / kg or less CPR 5.0 or less Na content + K content 3.0 ppm or less Moisture 0.2% or less Phosphorus content 5-70ppm
F. The etherification reaction rate of the terminal hydroxyl group calculated from the hydroxyl value of the intermediate product and the hydroxyl value of the purified product is 93% or more.
R 1 O (AO) nR 2 (1)
(In the formula, R 1 is an alkenyl group having 3 to 5 carbon atoms having a double bond at the terminal, AO is an oxyalkylene group having 2 to 4 carbon atoms, n = 1 to 150, and R 2 is And an alkyl group or an alkenyl group having 1 to 24 carbon atoms.)
１． 原料ポリエーテルに対し、アルカリ触媒及び有機ハロゲン化物を加え、７０〜１３０℃の間でエーテル化するエーテル化工程
２． 水を加えてアルカリを分層除去するアルカリ除去工程
３． 中和剤を用いてｐＨを５．０〜７．０の間に調整する中和工程
４． 不活性ガス雰囲気下、温度７０〜１００℃の間で脱水する脱水工程
５． 不活性ガス雰囲気下、温度７０〜９０℃の間で吸着剤処理を行う吸着処理工程
６．濾過により中和塩を除去する濾過工程
７．燐酸を２０〜２００ｐｐｍ量添加する燐酸添加工程
Ｒ１Ｏ（ＡＯ）ｎＲ２ （１）
（式中、Ｒ１は、末端に二重結合を有する炭素数３〜５のアルケニル基であり、ＡＯは、炭素数２〜４のオキシアルキレン基であり、ｎ＝１〜１５０、Ｒ２は、炭素数１〜２４のアルキル基もしくはアルケニル基である。） The manufacturing method of the alkenyl-group containing polyoxyalkylene derivative shown by following formula (1) characterized by having the following process.
1. 1. Etherification step in which an alkali catalyst and an organic halide are added to the raw material polyether, and etherified at 70 to 130 ° C. 2. Alkali removal step in which water is added to separate the alkali layers. 3. Neutralization step of adjusting pH between 5.0 and 7.0 using a neutralizer. 4. Dehydration step of dehydrating at a temperature of 70 to 100 ° C. in an inert gas atmosphere 5. Adsorption treatment process in which an adsorbent treatment is performed at a temperature of 70 to 90 ° C. in an inert gas atmosphere. 6. Filtration step to remove neutralized salt by filtration Phosphoric acid addition step of adding 20 to 200 ppm of phosphoric acid
R 1 O (AO) nR 2 (1)
(In the formula, R 1 is an alkenyl group having 3 to 5 carbon atoms having a double bond at the terminal, AO is an oxyalkylene group having 2 to 4 carbon atoms, n = 1 to 150, and R 2 is And an alkyl group or an alkenyl group having 1 to 24 carbon atoms.)
The production method according to claim 3 or 4, wherein the use of the alkenyl group-containing polyoxyalkylene derivative is silicone modification.
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| JP6889649B2 (en) * | 2016-12-09 | 2021-06-18 | 三洋化成工業株式会社 | Antistatic silicone resin composition |
| EP3360912B1 (en) | 2017-02-10 | 2019-07-03 | Evonik Degussa GmbH | Method for manufacture of polyoxyalkylene ethers that can be hydrosilylated |
| JP6741170B2 (en) * | 2017-10-31 | 2020-08-19 | Ａｇｃ株式会社 | Method for producing fluorine-containing ether compound, method for producing article |
| JP7285248B2 (en) * | 2018-04-16 | 2023-06-01 | 株式会社カネカ | Method for producing polyether |
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| CA2221389C (en) * | 1996-11-18 | 2009-01-27 | Kenrick M. Lewis | Treatment of polyethers prior to hydrosilylation |
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