JPH11140133A - Styrene oligomer and its production - Google Patents
Styrene oligomer and its productionInfo
- Publication number
- JPH11140133A JPH11140133A JP30198297A JP30198297A JPH11140133A JP H11140133 A JPH11140133 A JP H11140133A JP 30198297 A JP30198297 A JP 30198297A JP 30198297 A JP30198297 A JP 30198297A JP H11140133 A JPH11140133 A JP H11140133A
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- Prior art keywords
- monomer
- polymerization
- oligomer
- styrene
- group
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規な櫛型スチレ
ン系オリゴマーに関し、更に詳しくは、親水性基として
ポリエチレンオキシド鎖を側鎖に有し、重合度の比較的
低いスチレン系オリゴマーに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel comb-type styrene oligomer, and more particularly, to a styrene oligomer having a polyethylene oxide chain as a hydrophilic group in a side chain and a relatively low degree of polymerization. is there.
【０００２】[0002]
【従来の技術】ポリアルキレンオキシド誘導体は活性水
素を有する化合物にエチレンオキシド、プロピレンオキ
シド等のアルキレンオキシドを付加重合させ、必要に応
じて種々の変成を加えて合成され、原料化合物の組合せ
や使用量等により、低粘度から高粘度、油溶性から水溶
性、低融点から高融点等種々の特性を有するものが得ら
れる。広範な特性の誘導体が得られることから用途は医
薬化粧品、発酵工業、潤滑油、樹脂、シリコーン樹脂分
野等多岐に渡っている。又、変成技術の検討も活発に行
われており、それにより用途拡大が試みられている。2. Description of the Related Art Polyalkylene oxide derivatives are synthesized by addition-polymerizing an alkylene oxide such as ethylene oxide or propylene oxide to a compound having active hydrogen, and adding various modifications as necessary. Thus, those having various properties such as low to high viscosity, oil solubility to water solubility, low to high melting point, etc. can be obtained. Since derivatives having a wide range of properties can be obtained, the uses are widely used in the fields of pharmaceutical cosmetics, the fermentation industry, lubricating oils, resins, and silicone resins. In addition, metamorphic technology is being actively studied, and attempts are being made to expand applications.
【０００３】例えば、ポリアルキレンオキシド誘導体の
中で比較的分子量の大きい親水性オリゴマーは、樹脂や
繊維の帯電防止剤、親水化剤、吸水性付与剤、可塑剤、
高分子固体電解質、界面活性剤、潤滑油等の多方面の用
途で実用化されているが、現在も改良検討が継続されて
おり、更に新変成法開発により新たな市場ニーズへの対
応も考えられる。For example, among the polyalkylene oxide derivatives, hydrophilic oligomers having a relatively large molecular weight include antistatic agents for resins and fibers, hydrophilic agents, water-absorbing agents, plasticizers, and the like.
It has been put to practical use in a variety of applications such as solid polymer electrolytes, surfactants, and lubricating oils.However, improvements are still being studied, and further development of a new metamorphic method is expected to respond to new market needs. Can be
【０００４】まず、帯電防止剤には界面活性剤型低分子
化合物と高分子型永久帯電防止剤がある。現在実用化さ
れている代表的な高分子型帯電防止剤としては、赤松清
監修“帯電防止材料の最新技術と応用”、シーエムシ
ー、９９頁（１９９６）に記載されているように、ポリ
エチレングリコールメタクリレート共重合体、ポリエー
テルエステルアミド、ポリエーテルアミドイミド、ポリ
エチレンオキシドーエピクロルヒドリン共重合体等があ
るが、耐熱性、耐変色性、加工工程中での脱落、分子中
に反応性官能基を有する等において課題がある。主鎖及
び主鎖付近に芳香環を有するポリエチレンオキシド誘導
体としては、例えば、特許第２５２８７８４号（特開平
７ー７０２９３号公報）には帯電防止剤及び樹脂組成物
としてフェノール・ジビニルベンゼン付加重合体のポリ
オキシアルキレンエーテルが示されている。この化合物
はアルキレンオキシドの付加モル数は任意に変えること
ができるが、主鎖はフェノール類とジビニルベンゼン付
加物に固定される。First, the antistatic agent includes a surfactant type low molecular weight compound and a polymer type permanent antistatic agent. Representative polymer antistatic agents that are currently in practical use include polyethylene glycol as described in Kiyoshi Akamatsu, “Latest Techniques and Applications of Antistatic Materials,” CMC, p. 99 (1996). There are methacrylate copolymers, polyetheresteramides, polyetheramideimides, polyethylene oxide-epichlorohydrin copolymers, etc., but they have heat resistance, discoloration resistance, dropout during processing, and reactive functional groups in the molecule. There is a problem in such as. As a polyethylene oxide derivative having an aromatic ring in the main chain and in the vicinity of the main chain, for example, Japanese Patent No. 2528784 (JP-A-7-70293) discloses a phenol / divinylbenzene addition polymer as an antistatic agent and a resin composition. Polyoxyalkylene ethers are indicated. In this compound, the number of moles of alkylene oxide added can be arbitrarily changed, but the main chain is fixed to a phenol and divinylbenzene adduct.
【０００５】このように、従来の親水性オリゴマーは、
これを櫛型オリゴマーと考えた場合、櫛の歯の長さ［主
鎖と主鎖から分岐する側鎖からなる重合体の側鎖の長
さ。本発明の化合物ではアルキレンオキシドの付加モル
数が該当する］はアルキレンオキシドの付加モル数で調
節できるが、櫛の歯の間隔［主鎖と主鎖から分岐する側
鎖からなる重合体の側鎖同士の間隔。本発明の化合物で
はアルキレンオキシドを有する側鎖同士の間隔が該当す
る］の調節は制限されるため、分子構造上の自由度が少
なく、目的とする性能が十分発揮されているか懸念があ
る。As described above, the conventional hydrophilic oligomer is
When this is considered as a comb-type oligomer, the length of the teeth of the comb [the length of the side chain of the polymer composed of the main chain and the side chain branched from the main chain]. In the compound of the present invention, the addition mole number of the alkylene oxide corresponds] can be adjusted by the addition mole number of the alkylene oxide. The distance between each other. In the compound of the present invention, the distance between the side chains having an alkylene oxide corresponds), the degree of freedom in the molecular structure is small, and there is a concern that the intended performance is sufficiently exhibited.
【０００６】又、熱可塑性樹脂として例えばポリエステ
ル樹脂に溶融混練した場合は、化合物が水酸基等エステ
ル交換反応を起こす官能基を有すると、樹脂が重合度の
低下を起こして物性が低下する可能性がある。更に、ポ
リカーボネート樹脂においては、例えば特開平９−２５
３３５号公報にみられるように、本来有する樹脂の透明
性を損なわないような改質剤の検討がなされている。こ
のように、帯電防止性だけではなく種々の機能が要求さ
れ、用途に応じたきめ細かな材料対応や技術革新が求め
られている。Further, when a thermoplastic resin is melt-kneaded, for example, with a polyester resin, if the compound has a functional group which causes a transesterification reaction such as a hydroxyl group, the degree of polymerization of the resin may be reduced and the physical properties may be reduced. is there. Further, in the case of polycarbonate resin, for example, JP-A-9-25
As disclosed in JP-A-335, studies are being made on a modifier that does not impair the transparency of the resin that the resin originally has. As described above, not only the antistatic property but also various functions are required, and there is a demand for fine material handling and technical innovation according to the application.
【０００７】一方、高分子固体電解質の分野においては
さまざまなタイプのものが登場したが、現状ではポリエ
チレンオキシド系に集約されている。例えば、特公平８
−３２７５２号公報、同８−３２７５３号公報、同８−
３２７５４号公報、同８−３２７５５号公報にはエチレ
ンオキシド等の重合体のメタクリル酸やアクリル酸等の
エステル類を反応させた高分子が示されているが、これ
に代表されるように、分子中にエステルやウレタン結合
を有したり、芳香環は有しないものが殆どであり、加水
分解による物性低下、耐熱性、耐久性等の点で不安を残
している。On the other hand, various types have appeared in the field of polymer solid electrolytes, but are currently concentrated on polyethylene oxides. For example, Tokuho 8
JP-A-32752, JP-A-8-32753, and 8-
JP-A-32754 and JP-A-8-32755 disclose polymers obtained by reacting a polymer such as ethylene oxide with an ester such as methacrylic acid or acrylic acid. Most have no ester or urethane bond or no aromatic ring, and remain uneasy in terms of deterioration in physical properties due to hydrolysis, heat resistance, durability and the like.
【０００８】又、インキ、トナー、塗料、樹脂、ゴム、
繊維、紙、写真、フィルム等の諸分野において、強度、
剛性、接着性、耐熱性、耐候性、色調、深色性、艶消し
や白色化（隠蔽性）、触感特性、滑り性や耐磨耗性、及
び粘度特性の改良、増量によるコストダウン、導電性等
の新機能付与を目的として、シリカ、炭酸カルシウム、
二酸化チタン、タルク、フェライト、金属粉、金属繊
維、ガラス繊維等の無機微粒子や有機顔料等が使用され
ている。しかし、無機微粒子の表面は一般に水酸基のよ
うな極性基や吸着水で覆われているため親油性に乏し
く、そのままでは樹脂やゴム等の有機媒体中に均一に分
散させることは困難であり、顔料においても非水系のビ
ヒクル中で凝集して色むらや光沢を失うなど目的が十分
果たせない。In addition, ink, toner, paint, resin, rubber,
In various fields such as fiber, paper, photograph, film, etc., strength,
Rigidity, adhesion, heat resistance, weather resistance, color tone, deep color, matting and whitening (hiding), tactile characteristics, slipperiness and abrasion resistance, improvement in viscosity characteristics, cost reduction by increasing the amount, conductivity Silica, calcium carbonate,
Inorganic fine particles such as titanium dioxide, talc, ferrite, metal powder, metal fiber, and glass fiber, and organic pigments are used. However, the surface of the inorganic fine particles is generally poor in lipophilicity because it is covered with a polar group such as a hydroxyl group or adsorbed water, and as it is, it is difficult to uniformly disperse it in an organic medium such as a resin or rubber. However, the purpose cannot be sufficiently achieved, for example, by coagulation in a non-aqueous vehicle to lose color unevenness and gloss.
【０００９】そこで、無機微粒子や顔料の表面性を変化
させて分散性を向上させるため、種々のカップリング剤
で処理したり、各種界面活性剤や樹脂で被覆する方法が
行われている。例えば、特公平７−９８６５７号公報に
は特殊なシリル化剤が、特公平８−１３９３８号公報に
はアミノ酸−長鎖アミドからなる表面改質剤がそれぞれ
記載されている。これら従来の表面改質剤や分散剤は分
散性、耐熱性、経済性、マトリックス樹脂との相溶性等
において課題を残しており、特にマトリックス樹脂との
非反応性、他の添加剤や改質剤の性能を阻害しない、微
粒子が他の添加剤や改質剤を失活させるのを防ぐ等の要
求を満足するものは殆どない。In order to improve the dispersibility by changing the surface properties of the inorganic fine particles and the pigment, a method of treating with various coupling agents or coating with various surfactants or resins has been used. For example, Japanese Patent Publication No. 7-98657 describes a special silylating agent, and Japanese Patent Publication No. 8-13938 describes a surface modifier comprising an amino acid-long chain amide. These conventional surface modifiers and dispersants have problems in dispersibility, heat resistance, economy, compatibility with matrix resin, etc., especially non-reactivity with matrix resin, other additives and modification. Few satisfy the requirements such as not hindering the performance of the agent and preventing the fine particles from inactivating other additives or modifiers.
【００１０】上述の用途や課題に対して共通するポリア
ルキレンオキシド誘導体の望ましい分子構造は、親水性
基と疎水性基からなり、その量を用途や必要機能により
自由に制御できること、親水性基は多様な用途に使用可
能という見地からノニオン性のポリエチレンオキシド鎖
が適当であり、分子量は樹脂との相溶性や要求機能に合
わせて千から数万程度の間で制御できることが必要であ
る。又、疎水性基は耐熱性や樹脂改質剤用途としては想
定しているマトリックス樹脂である芳香族樹脂との親和
性を考慮して芳香環を有することが望ましい。更に、ポ
リエステル樹脂等と溶融混練時に樹脂の重合度低下を起
こして樹脂物性を低下したり、種々の併用薬剤の機能を
阻害しないため反応基を有しないことも重要である。こ
れらの項目を満足するようなポリエチレンオキシド誘導
体は知られていない。A desirable molecular structure of the polyalkylene oxide derivative which is common to the above-mentioned uses and problems is composed of a hydrophilic group and a hydrophobic group, and the amount thereof can be freely controlled according to the use and the required function. A nonionic polyethylene oxide chain is suitable from the viewpoint that it can be used for various applications, and it is necessary that the molecular weight can be controlled in the range of about 1,000 to tens of thousands in accordance with the compatibility with the resin and the required function. Further, it is desirable that the hydrophobic group has an aromatic ring in consideration of the heat resistance and the affinity with an aromatic resin which is a matrix resin assumed for use as a resin modifier. Further, it is important that the resin does not have a reactive group because the polymerization degree of the resin is lowered at the time of melt-kneading with a polyester resin or the like, thereby deteriorating the resin physical properties. A polyethylene oxide derivative satisfying these items is not known.
【００１１】本発明関連の化合物としては、Polymer Bu
lletin,16,337(1986) 及び J. Phys.Chem.,98,7891(199
4)にCompounds related to the present invention include Polymer Bu
lletin, 16, 337 (1986) and J. Phys. Chem., 98, 7891 (199).
4
【化３】 の報告がある。又、高分子論文集,43,91(1986)にはスチ
レンと上記化合物の重合体の記載があるが、反応条件、
共重合比等不明瞭であり、連鎖移動剤は使用していない
ため重合度が大きく、その制御は困難と考えられる。本
発明では重合度を制御し、低重合体を合成することが肝
要であるが、そのような報告はみられない。Embedded image There is a report. Also, in Polymers, 43, 91 (1986), there is a description of a polymer of styrene and the above compound.
The copolymerization ratio and the like are unclear, and since no chain transfer agent is used, the degree of polymerization is large, and it is considered difficult to control the degree of polymerization. In the present invention, it is important to control the degree of polymerization to synthesize a low polymer, but such reports have not been found.
【００１２】[0012]
【発明が解決しようとする課題】従って、本発明の目的
は、ノニオン性のポリアルキレンオキシドからなる親水
性基と芳香環を有する疎水性基を併せ有し、分子中に反
応基を有せずに、かつ、親水基と疎水基の間隔と分子量
を制御したスチレン系オリゴマーを提供することにあ
る。Accordingly, an object of the present invention is to provide a compound having both a hydrophilic group comprising a nonionic polyalkylene oxide and a hydrophobic group having an aromatic ring, and having no reactive group in the molecule. Another object of the present invention is to provide a styrenic oligomer in which the distance between the hydrophilic group and the hydrophobic group and the molecular weight are controlled.
【００１３】[0013]
【課題を解決するための手段】本発明者らは上記の課題
を解決すべく鋭意検討した結果、下記の一般式(１)で表
される構造を繰り返し単位として有してなるスチレン系
オリゴマーが多用な機能を有することを見出し、本発明
を完成させるに至った。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a styrene-based oligomer having a structure represented by the following general formula (1) as a repeating unit is obtained. The inventors have found that they have various functions, and have completed the present invention.
【００１４】即ち、本発明は、一般式(１)That is, the present invention provides a compound represented by the general formula (1):
【化４】 （式中、Ｒ1は炭素数２〜４のアルキレン基を表し、Ｒ2
は芳香環を含まない炭素数１〜１８の炭化水素基を表
し、ｍは１〜６の整数を表し、ｎは１〜１００の整数を
表し、ａ＞０、ｂ≧０である）で表される構造を繰り返
し単位として有してなるスチレン系オリゴマーに係る。Embedded image (Wherein, R 1 represents an alkylene group having 2 to 4 carbon atoms, R 2
Represents an aromatic ring-free hydrocarbon group having 1 to 18 carbon atoms, m represents an integer of 1 to 6, n represents an integer of 1 to 100, and a> 0 and b ≧ 0. A styrenic oligomer having the structure represented as a repeating unit.
【００１５】又、本発明は、スチレン系オリゴマーの製
造方法において、一般式(Ａ)Further, the present invention relates to a method for producing a styrene-based oligomer, the method comprising:
【化５】 （式中、Ｒ1は炭素数２〜４のアルキレン基を表し、Ｒ2
は芳香環を含まない炭素数１〜１８の炭化水素基を表
し、ｍは１〜６、ｎは１〜１００の整数を示す）で表さ
れるモノマーと；スチレンモノマーとを、重合開始剤及
び連鎖移動剤の存在下、重合させることを特徴とするス
チレン系オリゴマーの製造方法に係る。Embedded image (Wherein, R 1 represents an alkylene group having 2 to 4 carbon atoms, R 2
Represents a hydrocarbon group having 1 to 18 carbon atoms not containing an aromatic ring, m represents an integer of 1 to 6, and n represents an integer of 1 to 100) and a styrene monomer; a polymerization initiator and The present invention relates to a method for producing a styrenic oligomer, which comprises polymerizing in the presence of a chain transfer agent.
【００１６】[0016]
【発明の実施の形態】本発明のスチレン系オリゴマー
は、一般式(１)BEST MODE FOR CARRYING OUT THE INVENTION The styrenic oligomer of the present invention has the general formula (1)
【化６】 （式中、Ｒ1は炭素数２〜４のアルキレン基を表し、Ｒ2
は芳香環を含まない炭素数１〜１８の炭化水素基を表
し、ｍは１〜６、ｎは１〜１００の整数を示し、ａ＞
０、ｂ≧０である）で表される構造を繰り返し単位とし
て有してなることを特徴とする。Embedded image (Wherein, R 1 represents an alkylene group having 2 to 4 carbon atoms, R 2
Represents an aromatic ring-free hydrocarbon group having 1 to 18 carbon atoms, m represents an integer of 1 to 6, n represents an integer of 1 to 100, and a>
0, b ≧ 0) as a repeating unit.
【００１７】ここで、ａは小さくなるほど重合体の親水
性が弱くなるが、本発明のスチレン系オリゴマーの様々
な用途を考慮するとａ／(ａ＋ｂ)は１〜１／１００であ
ることが望ましい。また、平均重合度ａ＋ｂ≦４５(た
だし、ａ＝０であることはない)であるがこれよりも大
きいと樹脂等との相溶性が低下し、また、添加剤や改質
材としての性能が得られない。なお、ａとｂの最適な値
（重合比と重合度）は用途によって異なる。Here, as a becomes smaller, the hydrophilicity of the polymer becomes weaker. However, in consideration of various uses of the styrenic oligomer of the present invention, a / (a + b) is desirably 1 to 1/100. Further, the average degree of polymerization a + b ≦ 45 (however, a = 0 is not always possible), but if it is larger than this, the compatibility with the resin or the like is reduced, and the performance as an additive or a modifier is deteriorated. I can't get it. The optimum values of a and b (polymerization ratio and degree of polymerization) differ depending on the application.
【００１８】また、アルキレンオキシドの種類と付加モ
ル数も用途によって異なる。ただし、一般式(１)で表さ
れる繰り返し単位部分の平均分子量は５万以下であるこ
とが望ましい。Further, the kind of alkylene oxide and the number of moles to be added also vary depending on the use. However, the average molecular weight of the repeating unit represented by the general formula (1) is desirably 50,000 or less.
【００１９】アルキレンオキシドの種類については、エ
チレンオキシドは親水性基として含んでなることが好ま
しい。プロピレンオキシドやブチレンオキシド等も疎水
性付与、流動性や結晶性変化の変化等の目的で適宜組み
入れることができるが、必ずしも含んでなる必要はな
い。Regarding the type of alkylene oxide, it is preferable that ethylene oxide is included as a hydrophilic group. Propylene oxide, butylene oxide, and the like can be appropriately incorporated for the purpose of imparting hydrophobicity, change in fluidity or change in crystallinity, but need not necessarily be included.
【００２０】ところで、本発明のスチレン系オリゴマー
は基本的に水酸基、アミノ基、エステル結合、ウレタン
結合等の反応性に富む官能基は有さない。そのため、ポ
リエステル樹脂等と溶融混練しても、樹脂物性を低下さ
せたり、種々の併用薬剤の機能を阻害したり、着色する
ことはない。耐熱性もポリエチレンオキシド誘導体とし
ては良好である。Incidentally, the styrene oligomer of the present invention basically does not have a highly reactive functional group such as a hydroxyl group, an amino group, an ester bond or a urethane bond. Therefore, even when melt-kneaded with a polyester resin or the like, the resin physical properties are not reduced, the functions of various concomitant drugs are not inhibited, and no coloring is caused. Heat resistance is also good as a polyethylene oxide derivative.
【００２１】本発明のスチレン系オリゴマーを製造する
方法としては、 一般式(Ａ)The method for producing the styrenic oligomer of the present invention is represented by the general formula (A)
【化７】 （式中、同一符号は前記と同義）で表されるモノマー
と、スチレンモノマーとを重合させる方法； ヒドロキシスチレン又はヒドロキシアルキルスチレン
とスチレンモノマーとの共重合体に、アルキレンオキシ
ドを付加重合させ、次いで末端の水酸基をWilliamson法
によりアルキルエーテル化する方法がある。Embedded image (Wherein the same symbols are as defined above) and a styrene monomer; a method of polymerizing hydroxystyrene or a copolymer of hydroxyalkylstyrene and a styrene monomer with an alkylene oxide, followed by addition polymerization. There is a method in which a terminal hydroxyl group is alkyl-etherified by the Williamson method.
【００２２】一般式(Ａ)で表されるモノマーは、例え
ば、ハロアルキルスチレンとポリオキシアルキレンア
ルキルエーテル等からWilliamson法によりエーテル化し
て合成する方法、又はヒドロキシスチレン或いはヒド
ロキシアルキルスチレンにアルキレンオキシドを付加重
合後、末端水酸基をWilliamson法によりアルキルエーテ
ル等エーテル化する方法により得ることができる。例え
ば、アルキレンオキシド付加物をナトリウムメチラート
によりアルコラート化し、ハロアルキルスチレン等のハ
ロゲン化物を加えて合成することができる。副生する食
塩等は水を加えて溶解させポリアルキレンオキシド誘導
体と２層分離・濾過或いは吸着剤処理等により分離する
ことで除去する。また、食塩等はトルエン等の溶媒で希
釈し、濾別して分離することもできる。The monomer represented by the general formula (A) can be synthesized, for example, by etherifying a haloalkylstyrene and a polyoxyalkylenealkyl ether or the like by the Williamson method, or by adding alkylene oxide to hydroxystyrene or hydroxyalkylstyrene. Thereafter, the terminal hydroxyl group can be obtained by a method of etherifying an alkyl ether or the like by the Williamson method. For example, the alkylene oxide adduct can be alcoholated with sodium methylate and synthesized by adding a halide such as haloalkylstyrene. By-produced salt and the like are removed by adding water to dissolve and separating the polyalkylene oxide derivative from the polyalkylene oxide derivative by two-layer separation / filtration or adsorbent treatment. Further, salt and the like can be diluted with a solvent such as toluene and separated by filtration.
【００２３】一般にポリアルキレンオキシド誘導体はア
ルカリ性で加熱し、特に、空気との接触があると着色す
る。これはポリアルキレンオキシド誘導体中にアルデヒ
ド等の酸化生成物が存在するためと考えられるが、あら
かじめナトリウムボロハイドライド処理などにより還元
処理をし、反応中は空気との接触を避けることにより改
善できる。Generally, the polyalkylene oxide derivative is heated under alkaline conditions, and in particular, becomes colored when it comes into contact with air. This is considered to be due to the presence of an oxidation product such as an aldehyde in the polyalkylene oxide derivative, but it can be improved by performing a reduction treatment in advance by sodium borohydride treatment or the like and avoiding contact with air during the reaction.
【００２４】アルキレンオキシドを付加させる際は、酸
触媒又はアルカリ触媒のような触媒の存在下、好ましく
は加圧下、高温（例えば８０〜２００℃、好ましくは１
００〜１８０℃）で既知の方法によってこれを行うこと
ができる。触媒は、酸触媒、例えば三フッ化ホウ素また
は塩化アルミニウムのようなルイス酸であることもでき
るが、さらに好ましくは、アルカリ触媒、例えばアルカ
リ金属またはアルカリ土類金属のアルコラート、水酸化
物、酸化物、炭酸塩、水素化物またはアミドである。特
に好ましい触媒はナトリウムまたはカリウムのアルコラ
ート（例えばメチラートまたはエチラート）及び水酸化
物である。触媒は通常、最終生成物に対して０.０５〜
３重量％、好ましくは０.１〜１重量％の量で使用す
る。反応終了後、触媒は必要に応じて中和、濾過、吸着
剤処理等により除去する。When the alkylene oxide is added, the reaction is carried out in the presence of a catalyst such as an acid catalyst or an alkali catalyst, preferably under pressure, at a high temperature (for example, 80 to 200 ° C., preferably 1 to 100 ° C.).
(00-180 ° C.) by known methods. The catalyst can be an acid catalyst, for example a Lewis acid such as boron trifluoride or aluminum chloride, but more preferably an alkali catalyst, for example an alkali metal or alkaline earth metal alcoholate, hydroxide, oxide. , Carbonates, hydrides or amides. Particularly preferred catalysts are sodium or potassium alcoholates (eg methylates or ethylates) and hydroxides. The catalyst is typically used in an amount of from 0.05 to
It is used in an amount of 3% by weight, preferably 0.1-1% by weight. After completion of the reaction, the catalyst is removed by neutralization, filtration, treatment with an adsorbent or the like as necessary.
【００２５】アルキレンオキシドの種類については、エ
チレンオキシドは親水性基として含んでなることが好ま
しい。プロピレンオキシドやブチレンオキシド等も疎水
性付与、流動性や結晶性変化の変化等の目的で適宜組み
入れることができるが、必ずしも含んでなる必要はな
い。With regard to the type of alkylene oxide, it is preferable that ethylene oxide is contained as a hydrophilic group. Propylene oxide, butylene oxide, and the like can be appropriately incorporated for the purpose of imparting hydrophobicity, change in fluidity or change in crystallinity, but need not necessarily be included.
【００２６】使用する出発物質は活性水素を有する化合
物なら使用可能であり、メタノール、エタノール、高級
アルコール等の一価アルコール類、エチレングリコー
ル、プロピレングリコール、グリセリン等の多価アルコ
ール類、アミン類、メルカプタン類等が上げられる。The starting materials used may be any compounds having active hydrogen, such as monohydric alcohols such as methanol, ethanol and higher alcohols, polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin, amines and mercaptans. And so on.
【００２７】ビニル単量体の重合方法としては、ラジカ
ル重合法、アニオン重合法、カチオン重合法等がある
が、工業的には一般にラジカル重合法が用いられ、ラジ
カル重合法においてもその重合法としては塊状重合、溶
液重合、懸濁重合、乳化重合、気相重合、固相重合法等
がある。本発明ではいずれの方法でも用いることができ
る。As the polymerization method of the vinyl monomer, there are a radical polymerization method, an anion polymerization method, a cationic polymerization method and the like. In general, a radical polymerization method is industrially used, and the polymerization method is also used in the radical polymerization method. Examples include bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, gas phase polymerization, and solid phase polymerization. In the present invention, any method can be used.
【００２８】なお、本発明では、一般式(Ａ)で表される
モノマーと、スチレンモノマーとの重合度をラジカル重
合法としては小さく制御するのがポイントであり、それ
により通常の高分子化合物とは物性が異なり、添加剤や
改質剤等の性能が得られる。そのように低分子重合体を
得る方法としては、連鎖移動剤を用いることが必須であ
り、用いる連鎖移動剤の量や連鎖移動定数を適切に選択
することで低分子重合体を得ることができる。また、あ
わせて、一般的な方法、例えば、溶液重合法で溶媒を多
くする、開始剤を多くする、又は連鎖移動定数の大きい
溶媒、開始剤を使用する、或いは反応温度を上昇させる
方法等が併用できる。In the present invention, the point is that the degree of polymerization of the monomer represented by the general formula (A) and the styrene monomer is controlled to be small as a radical polymerization method. Have different physical properties, and the performance of additives and modifiers can be obtained. As a method for obtaining such a low-molecular polymer, it is essential to use a chain transfer agent, and a low-molecular polymer can be obtained by appropriately selecting the amount and chain transfer constant of the chain transfer agent to be used. . In addition, a general method, for example, a method of increasing the amount of a solvent by a solution polymerization method, increasing the amount of an initiator, or a solvent having a large chain transfer constant, using an initiator, or a method of increasing the reaction temperature, or the like. Can be used together.
【００２９】なお、連鎖移動剤を用いない方法、或いは
その他方法の併用では所望のオリゴマーを合成すること
は困難である。It should be noted that it is difficult to synthesize a desired oligomer by a method without using a chain transfer agent, or by a combination of other methods.
【００３０】また、重合物の櫛の歯の間隔は、一般式
(Ａ)で表されるモノマーと、スチレンモノマーの仕込み
量によって制御できる。これは、一般式(Ａ)で表される
モノマーと、スチレンモノマーとは反応性がほぼ等しい
ことによる。このように櫛の歯の間隔を制御できること
は本発明の大きな特徴である。The distance between the comb teeth of the polymer is represented by the general formula
It can be controlled by the charged amount of the monomer represented by (A) and the styrene monomer. This is because the monomer represented by the general formula (A) and the styrene monomer have almost the same reactivity. The ability to control the spacing between the comb teeth is a major feature of the present invention.
【００３１】なお、疎水基と親水基のバランスや表面エ
ネルギーの大きさは、一般式(Ａ)で表されるモノマー
と、スチレンモノマーの共重合比の他、一般式(Ａ)で表
されるモノマー中のポリエチレンオキシドの付加モル数
によっても制御することができる。The balance between the hydrophobic group and the hydrophilic group and the magnitude of the surface energy are represented by the general formula (A) in addition to the copolymerization ratio of the monomer represented by the general formula (A) and the styrene monomer. It can also be controlled by the number of added moles of polyethylene oxide in the monomer.
【００３２】このように一般式(Ａ)で表されるモノマー
と、スチレンモノマーの最適な間隔と重合度、アルキレ
ンオキシドの種類と付加モル数は用途によって異なる
が、本発明では それらを任意に制御できる。As described above, the optimum interval and the degree of polymerization of the monomer represented by the general formula (A) and the styrene monomer, the kind of the alkylene oxide and the number of moles added are different depending on the application. it can.
【００３３】重合開始剤としては例えば、有機過酸化物
［ベンゾイルパーオキシド、ｔ−ブチルパーオキシベン
ゾエート、ジクミルパーオキシド、ｔ−ブチルクミルパ
ーオキシド、ジーｔ−ブチルパーオキシド、ｔ−ブチル
ハイドロパーオキシド等］、無機過酸化物［過硫酸ナト
リウム、過硫酸カリウム、過硫酸アンモニウム等］、ア
ゾ化合物［２，２’−アゾビスイソブチロニトリル（以
降AIBNと記す）、２，２’−アゾビス（２ーアミジノプ
ロパン）二塩酸塩等］、レドックス重合開始剤［過硫酸
塩−酸性亜硫酸ナトリウム、クメンハイドロパーオキシ
ド−第一鉄塩、ベンゾイルパーオキシド−Ｎ，Ｎ−ジメ
チルアニリン等］が用いられる。本発明の場合、スチレ
ンモノマーは非極性物質に対して溶解性があり、一般式
(Ａ)で表されるモノマーは、アルキレンオキシドの付加
モル数によるが、界面活性剤的作用を有し多くの物質を
可溶化、分散・乳化するので開始剤の選択に際して溶解
性による制約は少なく、比較的広範な開始剤が使用でき
る。Examples of the polymerization initiator include organic peroxides [benzoyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, t-butyl cumyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide. Oxides, etc.], inorganic peroxides [sodium persulfate, potassium persulfate, ammonium persulfate, etc.], azo compounds [2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN), 2,2'-azobis ( 2-amidinopropane) dihydrochloride, etc.], and a redox polymerization initiator [persulfate-sodium acid sulfite, cumene hydroperoxide-ferrous salt, benzoyl peroxide-N, N-dimethylaniline, etc.]. In the case of the present invention, the styrene monomer is soluble in non-polar substances and has the general formula
The monomer represented by (A) depends on the number of moles of the alkylene oxide added, but has a surfactant-like effect and solubilizes, disperses, and emulsifies many substances. A relatively wide range of initiators can be used.
【００３４】連鎖移動剤は、基本的には連鎖移動定数の
大きいものが効果的でありそのようなものならば制限は
なく、ポリハロゲン化メタンやハロゲン化炭化水素、メ
ルカプタン類、αメチルスチレンダイマー、アルコール
等の活性水素化合物、２，４−ジフェニル−４−メチル
−１−ペンテン等の２，２−二置換オレフィン等が使用
できるが、用途や重合体の物性に与える有用性と制約、
経済性等を考慮して選択する。使用量は連鎖移動剤とし
ての効果、目標重合度等によって異なるが、モノマーに
対して０.０１〜０.５モル比が望ましい。As the chain transfer agent, one having a large chain transfer constant is basically effective, and there is no limitation as long as it is such. Polyhalogenated methane, halogenated hydrocarbons, mercaptans, α-methylstyrene dimer , Active hydrogen compounds such as alcohols, and 2,2-disubstituted olefins such as 2,4-diphenyl-4-methyl-1-pentene can be used.
Select in consideration of economic efficiency. The amount used depends on the effect as a chain transfer agent, the target degree of polymerization, and the like, but is preferably 0.01 to 0.5 mole ratio to the monomer.
【００３５】反応溶媒は水（乳化重合）から非極性溶媒
まで使用可能であるが、一般式(Ａ)で表されるモノマー
が溶媒的作用を有することや、経済的見地等から無溶媒
系又は水系が望ましい。重合反応は通常窒素等の不活性
気体の雰囲気下で常圧又は加圧下で行う。重合温度は開
始剤の種類等によって異なり適宜設定する。The reaction solvent can be used from water (emulsion polymerization) to non-polar solvent. However, from the viewpoint that the monomer represented by the general formula (A) has a solvating effect, economical viewpoint, etc. A water system is preferred. The polymerization reaction is usually carried out under an atmosphere of an inert gas such as nitrogen under normal pressure or pressure. The polymerization temperature varies depending on the type of the initiator and the like, and is appropriately set.
【００３６】本発明の場合、比較的多量の連鎖移動剤を
使用し、連鎖移動剤を使用すると反応速度が低下するの
で、反応温度が高い方が反応時間が短縮化されモノマー
転化率も向上し、工業的には有利である。しかし、反応
温度を上昇させると開始剤の分解速度は増大するが反応
に利用される割合が減少し、重合体の収率が低下する。
従って、適当な反応速度で進行するような温度範囲の開
始剤を選ぶ必要がある。一般に６０〜２２０℃が望まし
い範囲である。反応時間は通常１〜５０時間、好ましく
は２〜２０時間である。In the present invention, if a relatively large amount of the chain transfer agent is used, and if the chain transfer agent is used, the reaction rate is reduced. Therefore, the higher the reaction temperature, the shorter the reaction time and the higher the monomer conversion rate. It is industrially advantageous. However, when the reaction temperature is increased, the decomposition rate of the initiator is increased, but the ratio used in the reaction is reduced, and the polymer yield is reduced.
Therefore, it is necessary to select an initiator in a temperature range that proceeds at an appropriate reaction rate. Generally, 60-220 ° C. is a desirable range. The reaction time is generally 1 to 50 hours, preferably 2 to 20 hours.
【００３７】本発明のスチレン系オリゴマーは、本発明
の効果を損なわない限り、スチレン系、アクリル酸系、
メタクリル酸系、マレイン酸系等の他のラジカル重合性
モノマーを含んでもよい。又、他のラジカル重合性モノ
マーはポリエチレンオキシド等の非イオン系、スルホン
酸（塩）等のアニオン系、四級アンモニウム塩等のカチ
オン系のいずれも併用可能である。The styrene-based oligomer of the present invention may be a styrene-based, acrylic acid-based or styrene-based oligomer unless the effects of the present invention are impaired.
It may contain other radically polymerizable monomers such as methacrylic acid type and maleic acid type. As the other radical polymerizable monomer, any of a nonionic type such as polyethylene oxide, an anionic type such as sulfonic acid (salt), and a cationic type such as quaternary ammonium salt can be used in combination.
【００３８】本発明のスチレン系オリゴマーは櫛型構造
を広範かつ任意に設計が可能であることから用途は多岐
に渡る。用途により最適構造、即ち、櫛の歯の長さ［主
鎖と主鎖から分岐する側鎖からなる重合体の側鎖の長
さ。本発明の化合物ではアルキレンオキシドの付加モル
数］、櫛の歯の間隔［主鎖と主鎖から分岐する側鎖から
なる重合体の側鎖同士の間隔。本発明の化合物ではアル
キレンオキシドを有する側鎖同士の間隔］は異なる。用
途は特に限定されないが、例えば、ミクロ相分離構造、
両親媒性、界面活性等の物性・機能の複合化が要求され
る分野がまず上げられ、樹脂等の帯電防止剤・親水化剤
・可塑剤・融液の粘度低下剤・相溶化剤・接着剤、無機
微粒子の分散剤・表面処理剤、高分子固体電解質等があ
る。又、耐熱性、酸化安定性に優れた潤滑油基油、界面
活性剤等が挙げられる。The styrenic oligomer of the present invention has a wide variety of uses since the comb-shaped structure can be designed widely and arbitrarily. Optimal structure depending on the application, that is, the length of the teeth of the comb [the length of the side chain of the polymer composed of the main chain and the side chain branched from the main chain. In the compound of the present invention, the number of moles of added alkylene oxide], the distance between the teeth of the comb [the distance between the side chains of the polymer composed of the main chain and the side chain branched from the main chain]. In the compound of the present invention, the distance between the side chains having the alkylene oxide is different. The application is not particularly limited, for example, micro phase separation structure,
The fields where compounding of physical properties and functions such as amphiphilicity and surface activity are required are first raised, and antistatic agents such as resins, hydrophilizing agents, plasticizers, melt viscosity reducing agents, compatibilizing agents, and adhesion Agents, dispersants and surface treatment agents for inorganic fine particles, solid polymer electrolytes, and the like. Further, lubricating base oils and surfactants which are excellent in heat resistance and oxidation stability are exemplified.
【００３９】[0039]
【実施例】以下、実施例を挙げて本発明を更に説明する
が、本発明はその要旨を越えない限り以下の実施例に限
定されるものではないことを理解されたい。なお、実施
例中の「部」は全て重量によるものである。 一般式(Ａ)で表される化合物の製造例１ オートクレーブにメタノール６４部、水酸化カリウム
１.８部を仕込み、窒素置換して溶解後、エチレンオキ
シド９００部を徐々に注入した。反応温度は９０℃から
１２０℃に反応の進行と共に昇温した。エチレンオキシ
ド注入終了後、１時間熟成し、メタノール・１０ＥＯ付
加物を合成した。このメタノール・１０ＥＯ付加物５０
０部にＳＷＳ（野村事務所、１２% ナトリウムボロハイ
ドライドのアルカリ水溶液) を２.０部仕込み８０℃で
１時間攪拌後、２８％ナトリウムメチラート２４５部を
仕込み減圧下９５〜１１５℃でメタノールを除去した。
窒素にて大気圧に戻し４０℃に冷却してｔ−ブタノール
１００部を加えてからｐ−ビニルベンジルクロライド１
７９部を滴下した。その後、徐々に昇温し７０℃で２時
間反応した。次いで、水を２２０部加えリン酸でｐＨ６
に中和後静置し、下層の水層及び塩化ナトリウムを除去
した。減圧下で揮発分を除去してから、吸着剤キョワー
ド６００Ｓ（協和化学工業製）を５部加えて１００℃に
て処理後、吸着剤を濾過して除き生成物( 以下ＶＢ／１
０ＥＯ／Ｍｅと略記）を得た。生成物の構造と、1Ｈ−
ＮＭＲシグナルの帰属 (δ値) を以下に示す。なお、1
Ｈ−ＮＭＲは日本電子製ＪＮＭ−ＬＡ４００型ＦＴ−Ｎ
ＭＲ装置を用いて測定した。EXAMPLES Hereinafter, the present invention will be further described with reference to Examples, but it should be understood that the present invention is not limited to the following Examples unless it exceeds the gist thereof. The “parts” in the examples are all based on weight. Production Example 1 of Compound Represented by Formula (A) 64 parts of methanol and 1.8 parts of potassium hydroxide were charged into an autoclave, and after displacing with nitrogen, 900 parts of ethylene oxide was gradually injected. The reaction temperature was raised from 90 ° C. to 120 ° C. as the reaction progressed. After completion of the injection of ethylene oxide, the mixture was aged for 1 hour to synthesize a methanol / 10EO adduct. This methanol / 10EO adduct 50
In 0 parts, 2.0 parts of SWS (Nomura office, 12% aqueous solution of sodium borohydride) was added, stirred at 80 ° C. for 1 hour, 245 parts of 28% sodium methylate was added, and methanol was added at 95 to 115 ° C. under reduced pressure. Removed.
After returning to atmospheric pressure with nitrogen and cooling to 40 ° C., 100 parts of t-butanol was added, and p-vinylbenzyl chloride 1 was added.
79 parts were added dropwise. Thereafter, the temperature was gradually raised and the reaction was carried out at 70 ° C. for 2 hours. Then, 220 parts of water was added, and the pH was adjusted to 6 with phosphoric acid.
After neutralization, the mixture was allowed to stand, and the lower aqueous layer and sodium chloride were removed. After removing volatile components under reduced pressure, 5 parts of adsorbent Kyoward 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and the mixture was treated at 100 ° C., and the adsorbent was removed by filtration to remove the product (hereinafter referred to as VB / 1).
OEO / Me). Product structure and 1 H-
The assignment (δ value) of the NMR signal is shown below. Note that 1
H-NMR is JNM-LA400 type FT-N manufactured by JEOL
The measurement was performed using an MR device.
【化８】 Embedded image
【００４０】一般式(Ａ)で表される化合物の製造例２〜
３ エチレンオキシドの量を変化させた他は上記製造例１に
準じて、以下のＶＢ／ｎＥＯ／Ｍｅモノマーを合成し
た。 製造例２・ｎ＝１８ 製造例３・ｎ＝２５Production Examples 2 to 2 of the compound represented by the general formula (A)
3 The following VB / nEO / Me monomer was synthesized according to Production Example 1 except that the amount of ethylene oxide was changed. Production Example 2 · n = 18 Production Example 3 · n = 25
【００４１】実施例１ 上記製造例１で得たＶＢ／１０ＥＯ／Ｍｅモノマー２９
４部とスチレンモノマー５２部を混合し、開始剤として
ＡＩＢＮ３３部及び連鎖移動剤としてαメチルスチレン
ダイマー４７部を加え７０〜１１０℃にて窒素雰囲気下
で８時間反応した。反応液は３０分毎にサンプリングし
て経時変化を調べた。分析はＧＰＣ（東ソー製ＨＬＣ−
８０２０型ＧＰＣ装置）及び1Ｈ−ＮＭＲを用い、各モ
ノマーの残存量はＧＰＣ及び1Ｈ−ＮＭＲにより求め
た。平均重合度はＧＰＣより求めた平均分子量から各モ
ノマーの仕込み量に応じて共重合しているとして算出し
た。なお、ＶＢ／１０ＥＯ／Ｍｅモノマーとスチレンモ
ノマーは残存量が２０〜３０％まではほぼ同じ割合で減
少し、それ以降はスチレンモノマーの方が減少速度がや
や速いことが判明した。減少分は重合体に取り込まれて
いると考えると２種のモノマーの反応性は殆ど同じであ
り、２種のモノマーはランダム共重合していると考えら
れる。反応終了後のＶＢ／１０ＥＯ／Ｍｅモノマーの残
存量は仕込時の１０％、スチレンモノマーは３％であっ
た。又、平均重合度は２種のモノマーがランダム共重合
しているとして算出すると各モノマーについては４.８
であった。反応終了後１１０℃、１０ｍｍＨｇにて１時
間スチレンモノマー等の低沸点化合物を除去した。最終
生成物の1Ｈ−ＮＭＲにおいてはＶＢ／１０ＥＯ／Ｍｅ
モノマーで観測された芳香環に結合したビニル基のシグ
ナル強度は上記の残存量に応じて減少し、メチレン基の
シグナルはブロード化した。ポリエチレンオキシド鎖と
末端メチル基のシグナルは出現した。連鎖移動剤として
使用したαメチルスチレンダイマーに由来するシグナル
も認められた。Example 1 VB / 10EO / Me monomer 29 obtained in Production Example 1 above
4 parts and 52 parts of a styrene monomer were mixed, 33 parts of AIBN as an initiator and 47 parts of α-methylstyrene dimer as a chain transfer agent were added, and the mixture was reacted at 70 to 110 ° C. under a nitrogen atmosphere for 8 hours. The reaction solution was sampled every 30 minutes and the change with time was examined. The analysis was performed by GPC (Tosoh HLC-
8020 type GPC apparatus) and 1 H-NMR, and the remaining amount of each monomer was determined by GPC and 1 H-NMR. The average degree of polymerization was calculated from the average molecular weight determined by GPC assuming that the copolymerization was carried out in accordance with the charged amounts of the respective monomers. It was found that the VB / 10EO / Me monomer and the styrene monomer decreased at substantially the same rate until the residual amount was 20 to 30%, and thereafter, the reduction rate of the styrene monomer was slightly faster. Considering that the reduced amount is taken into the polymer, the reactivity of the two monomers is almost the same, and it is considered that the two monomers are randomly copolymerized. After the reaction, the residual amount of the VB / 10EO / Me monomer was 10% at the time of charging, and the styrene monomer was 3%. The average degree of polymerization is calculated as 4.8 for each monomer, assuming that two kinds of monomers are randomly copolymerized.
Met. After completion of the reaction, low boiling compounds such as styrene monomer were removed at 110 ° C. and 10 mmHg for 1 hour. In 1 H-NMR of the final product, VB / 10EO / Me
The signal intensity of the vinyl group bonded to the aromatic ring observed in the monomer decreased according to the residual amount, and the signal of the methylene group was broadened. The signal of polyethylene oxide chain and terminal methyl group appeared. A signal derived from the α-methylstyrene dimer used as a chain transfer agent was also observed.
【００４２】実施例２ 重合調整剤としてｔ−ドデシルメルカプタン４０部を用
い、７０〜１１０℃で６時間反応した以外は実施例１に
準じて合成した。反応終了後のＶＢ／１０ＥＯ／Ｍｅモ
ノマーの残存量は仕込時の１４％、スチレンモノマーは
６％であった。又、平均重合度は２種のモノマーがラン
ダム共重合しているとすると各モノマーについて３.０
であった。Example 2 Synthesis was carried out in the same manner as in Example 1 except that 40 parts of t-dodecyl mercaptan was used as a polymerization regulator and the reaction was carried out at 70 to 110 ° C. for 6 hours. After the reaction was completed, the residual amount of VB / 10EO / Me monomer was 14% at the time of charging, and the styrene monomer was 6%. The average degree of polymerization is 3.0 for each monomer, assuming that two types of monomers are randomly copolymerized.
Met.
【００４３】実施例３ 重合調整剤として２−ナフタレンチオール３２部を用
い、７０〜１１０℃で７時間反応した以外は実施例４に
準じて合成した。反応終了後のＶＢ／１０ＥＯ／Ｍｅモ
ノマーの残存量は仕込時の７％、スチレンモノマーは２
％以下であった。又、平均重合度は２つのモノマーがラ
ンダム共重合しているとすると各モノマーについて１７
であった。Example 3 Synthesis was carried out in the same manner as in Example 4 except that 32 parts of 2-naphthalene diol was used as a polymerization regulator and the reaction was carried out at 70 to 110 ° C. for 7 hours. After the completion of the reaction, the residual amount of the VB / 10EO / Me monomer was 7% at the time of preparation, and
% Or less. The average polymerization degree is 17 assuming that two monomers are randomly copolymerized.
Met.
【００４４】実施例４ 上記製造例２で得たＶＢ／１８ＥＯ／Ｍｅモノマー４７
０部を用い、８０〜１２０℃で６時間反応した以外は実
施例１に準じて合成した。反応終了後のＶＢ／１８ＥＯ
／Ｍｅモノマーの残存量は仕込時の９％、スチレンモノ
マーは２％以下であった。又、平均重合度は２種のモノ
マーがランダム共重合しているとすると各モノマーにつ
いて５.３であった。Example 4 VB / 18EO / Me monomer 47 obtained in Production Example 2 above
It synthesized according to Example 1 except having reacted at 80-120 degreeC for 6 hours using 0 part. VB / 18EO after completion of reaction
The residual amount of / Me monomer was 9% at the time of charging, and the styrene monomer was 2% or less. The average degree of polymerization was 5.3 for each monomer, assuming that two types of monomers were randomly copolymerized.
【００４５】実施例５ 上記製造例２で得たＶＢ／１８ＥＯ／Ｍｅモノマー１８
８部とスチレンモノマー８３部を用い、７０〜１１０℃
で６時間反応した以外は実施例１に準じて合成した。反
応終了後のＶＢ／１８ＥＯ／Ｍｅモノマーの残存量は仕
込時の１６％、スチレンモノマーは３％であった。又、
平均重合度は各モノマーの仕込量に応じて共重合してい
るとするとＶＢ／１８ＥＯ／Ｍｅモノマーでは２.３、
スチレンモノマーでは９.４であった。Example 5 VB / 18EO / Me monomer 18 obtained in Production Example 2 above
70-110 ° C using 8 parts and 83 parts of styrene monomer
Except that the reaction was performed for 6 hours. After the reaction was completed, the remaining amount of the VB / 18EO / Me monomer was 16% at the time of charging, and the styrene monomer was 3%. or,
Assuming that the average degree of polymerization is copolymerized according to the charged amount of each monomer, VB / 18EO / Me monomer is 2.3,
It was 9.4 for the styrene monomer.
【００４６】実施例６ 上記製造例２で得たＶＢ／１８ＥＯ／Ｍｅモノマー７５
２部とスチレンモノマー２１部を用い、７０〜１１０℃
で６時間反応した以外は実施例１に準じて合成した。反
応終了後のＶＢ／１８ＥＯ／Ｍｅモノマーの残存量は仕
込時の７％、スチレンモノマーは５％以下であった。
又、平均重合度は各モノマーの仕込量に応じて共重合し
ているとするとＶＢ／１８ＥＯ／Ｍｅモノマーでは７.
１、スチレンモノマーでは１.８であった。Example 6 VB / 18EO / Me monomer 75 obtained in Production Example 2 above
70 to 110 ° C using 2 parts and 21 parts of styrene monomer
Except that the reaction was performed for 6 hours. The residual amount of VB / 18EO / Me monomer after the completion of the reaction was 7% at the time of charging, and the styrene monomer content was 5% or less.
If the average degree of polymerization is assumed to be copolymerized according to the charged amount of each monomer, the average degree of polymerization is 7.7 for VB / 18EO / Me monomer.
1, 1.8 for styrene monomer.
【００４７】実施例７ 上記製造例３で得たＶＢ／２５ＥＯ／Ｍｅモノマー６２
４部を用い、８０〜１２０℃で８時間反応した以外は実
施例１に準じて合成した。反応終了後のＶＢ／２５ＥＯ
／Ｍｅモノマー残存量は仕込時の１１％、スチレンモノ
マーは２％以下であった。又、平均重合度は２つのモノ
マーがランダム共重合しているとすると各モノマーにつ
いて５.３であった。Example 7 VB / 25EO / Me monomer 62 obtained in Production Example 3 above
The synthesis was carried out according to Example 1 except that 4 parts were used and reacted at 80 to 120 ° C. for 8 hours. VB / 25EO after completion of reaction
The residual amount of / Me monomer was 11% at the time of charging, and the content of styrene monomer was 2% or less. The average degree of polymerization was 5.3 for each monomer, assuming that the two monomers were randomly copolymerized.
【００４８】実施例８ ｐ−ｔ−ブトキシスチレン３００部、スチレン３０部、
ＡＩＢＮ６６部及びα−メチルスチレンダイマー９４部
をジオキサン３３０部に溶解し７０〜１１０℃にて窒素
雰囲気下で６時間反応させた。反応後、再沈処理を行い
未反応モノマーを除去しポリ（ｐ−ｔ−ブトキシスチレ
ン−スチレン）共重合体を得た。引き続きこの共重合体
を酸により加水分解し分子量が約８００のポリ（ｐ−ヒ
ドロキシスチレン−スチレン）共重合体を得た。1Ｈ−
ＮＭＲで共重合比を求めたところｐ−ヒドロキシスチレ
ン：スチレン＝８５：１５（モル比）であった。この共
重合体をオートクレーブに移し水酸化カリウムを仕込
み、窒素置換して溶解後、エチレンオキシド６００部を
１２０〜１３０℃で徐々に注入した。エチレンオキシド
注入終了後、１時間熟成し、ポリ（ｐ−ヒドロキシスチ
レン−スチレン）共重合体へのＥＯ付加を物を合成し
た。1Ｈ−ＮＭＲによるとヒドロキシスチレンモノマー
１モルに対するＥＯ付加量は１０モルであった。このＥ
Ｏ付加物５００部に２８％ナトリウムメチラート１８５
部を仕込み減圧下９５〜１２０℃にてメタノールを除去
した。次いで、塩化メチル５０部を５０〜８５℃で注入
し末端メチルエーテル化した。副生成物の除去及び精製
は製造例１に準じて行った。Example 8 300 parts of pt-butoxystyrene, 30 parts of styrene,
66 parts of AIBN and 94 parts of α-methylstyrene dimer were dissolved in 330 parts of dioxane and reacted at 70 to 110 ° C. under a nitrogen atmosphere for 6 hours. After the reaction, a reprecipitation treatment was performed to remove unreacted monomers to obtain a poly (pt-butoxystyrene-styrene) copolymer. Subsequently, the copolymer was hydrolyzed with an acid to obtain a poly (p-hydroxystyrene-styrene) copolymer having a molecular weight of about 800. 1 H-
The copolymerization ratio determined by NMR was p-hydroxystyrene: styrene = 85: 15 (molar ratio). The copolymer was transferred to an autoclave, charged with potassium hydroxide, and dissolved by substituting with nitrogen. After that, 600 parts of ethylene oxide was gradually injected at 120 to 130 ° C. After completion of the injection of ethylene oxide, the mixture was aged for 1 hour to synthesize EO addition to the poly (p-hydroxystyrene-styrene) copolymer. According to 1 H-NMR, the amount of EO added was 1 mol per 1 mol of the hydroxystyrene monomer. This E
O adduct 500 parts, 28% sodium methylate 185
The methanol was removed at 95 to 120 ° C under reduced pressure. Then, 50 parts of methyl chloride was injected at 50 to 85 ° C. to perform methyl ether etherification. Removal and purification of by-products were performed according to Production Example 1.
【００４９】比較例１ 製造例１で得たＶＢ／１０ＥＯ／Ｍｅモノマー２９４
部、開始剤としてＡＩＢＮ３３部を加え７０〜１１０℃
で６時間反応した。反応終了後のＶＢ／１０ＥＯ／Ｍｅ
モノマーの残存量は仕込時の５％以下であった。又、平
均重合度は４８であった。Comparative Example 1 VB / 10EO / Me monomer 294 obtained in Production Example 1
Parts, 33 parts of AIBN as an initiator and 70-110 ° C
For 6 hours. VB / 10EO / Me after completion of the reaction
The residual amount of the monomer was 5% or less at the time of charging. The average degree of polymerization was 48.
【００５０】比較例２ スチレンモノマー５２部、ポリエチレングリコール(１
０００)のジメチルエーテル化合物を２９４部、開始剤
としてＡＩＢＮ３３部を加え７０〜１１０℃で６時間反
応した。反応終了後のスチレンモノマーの残存量は仕込
時の２％以下であった。又、平均重合度は１５０以上で
あった。Comparative Example 2 52 parts of styrene monomer, polyethylene glycol (1
000) and 33 parts of AIBN as an initiator, and reacted at 70 to 110 ° C. for 6 hours. The residual amount of the styrene monomer after the reaction was 2% or less of the charged amount. The average degree of polymerization was 150 or more.
【００５１】比較例３ 製造例２で得たＶＢ／１８ＥＯ／Ｍｅモノマー４７０部
とスチレンモノマー５２部を混合し、開始剤としてＡＩ
ＢＮ３３部を加え７０〜１２０℃で６時間反応した。反
応終了後のＶＢ／１８ＥＯ／Ｍｅモノマーの残存量は仕
込時の５％以下、スチレンモノマーは２％以下であっ
た。又、平均重合度は２つのモノマーがランダム共重合
しているとすると両モノマーの合計で５０以上であっ
た。Comparative Example 3 470 parts of the VB / 18EO / Me monomer obtained in Production Example 2 and 52 parts of a styrene monomer were mixed, and AI was used as an initiator.
33 parts of BN were added and reacted at 70 to 120 ° C. for 6 hours. The residual amount of VB / 18EO / Me monomer after the reaction was 5% or less at the time of charging, and the styrene monomer was 2% or less. The average degree of polymerization was 50 or more in total assuming that the two monomers were randomly copolymerized.
【００５２】[0052]
【発明の効果】本発明により、主鎖がポリスチレン骨
格、側鎖はポリエチレンオキシド鎖から構成される新規
櫛型スチレン系オリゴマーが提供される。本発明のスチ
レン系オリゴマーは、分子設計の自由度が大きく、櫛の
間隔、疎水基や親水基のバランス、分子量が任意に制御
可能できるため、用途や要求物性にあった任意の構造の
ポリアルキレンオキシド誘導体を得ることが可能とな
る。According to the present invention, there is provided a novel comb-type styrene-based oligomer having a main chain composed of a polystyrene skeleton and a side chain composed of a polyethylene oxide chain. The styrenic oligomer of the present invention has a high degree of freedom in molecular design, and can control the distance between combs, the balance between hydrophobic groups and hydrophilic groups, and the molecular weight arbitrarily. It becomes possible to obtain an oxide derivative.
Claims (4)
は芳香環を含まない炭素数１〜１８の炭化水素基を表
し、ｍは１〜６の整数を表し、ｎは１〜１００の整数を
表し、ａ＞０、ｂ≧０である）で表される構造を繰り返
し単位として有してなるスチレン系オリゴマー。1. A compound of the general formula (1) (Wherein, R 1 represents an alkylene group having 2 to 4 carbon atoms, R 2
Represents an aromatic ring-free hydrocarbon group having 1 to 18 carbon atoms, m represents an integer of 1 to 6, n represents an integer of 1 to 100, and a> 0 and b ≧ 0. A styrenic oligomer having the structure represented as a repeating unit.
る、請求項１記載のスチレン系オリゴマー。2. The styrenic oligomer according to claim 1, wherein a + b ≦ 45 in the general formula (1).
ゴマーの製造方法において、一般式(Ａ) 【化２】 （式中、Ｒ1は炭素数２〜４のアルキレン基を表し、Ｒ2
は芳香環を含まない炭素数１〜１８の炭化水素基を表
し、ｍは１〜６、ｎは１〜１００の整数を示す）で表さ
れるモノマーと；スチレンモノマーとを、重合開始剤及
び連鎖移動剤の存在下、重合させることを特徴とするス
チレン系オリゴマーの製造方法。3. The method for producing a styrenic oligomer according to claim 1 or 2, wherein the compound represented by the general formula (A): (Wherein, R 1 represents an alkylene group having 2 to 4 carbon atoms, R 2
Represents a hydrocarbon group having 1 to 18 carbon atoms not containing an aromatic ring, m represents an integer of 1 to 6, and n represents an integer of 1 to 100) and a styrene monomer; a polymerization initiator and A method for producing a styrenic oligomer, comprising polymerizing in the presence of a chain transfer agent.
オキシアルキレンアルキルエーテルと、ハロアルキルス
チレンとの反応生成物である、請求項３記載のスチレン
系オリゴマーの製造方法。4. The method for producing a styrene oligomer according to claim 3, wherein the monomer represented by the general formula (A) is a reaction product of a polyoxyalkylene alkyl ether and a haloalkylstyrene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30198297A JPH11140133A (en) | 1997-11-04 | 1997-11-04 | Styrene oligomer and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30198297A JPH11140133A (en) | 1997-11-04 | 1997-11-04 | Styrene oligomer and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11140133A true JPH11140133A (en) | 1999-05-25 |
Family
ID=17903472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30198297A Pending JPH11140133A (en) | 1997-11-04 | 1997-11-04 | Styrene oligomer and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11140133A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001098173A (en) * | 1999-09-29 | 2001-04-10 | Asahi Denka Kogyo Kk | Resin modifier |
| US6525133B1 (en) * | 2000-03-29 | 2003-02-25 | The Goodyear Tire & Rubber Company | Tire with tread which utilizes an alpha-methyl styrene oligomer |
| WO2005097857A1 (en) * | 2004-04-09 | 2005-10-20 | Shiseido Company, Ltd. | Brush-form alternative copolymer and process for producing the same |
| JP2005344248A (en) * | 2004-06-03 | 2005-12-15 | Kao Corp | Wrinkle-removing agent |
| JP2007519786A (en) * | 2004-01-27 | 2007-07-19 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Use of statistical copolymers |
-
1997
- 1997-11-04 JP JP30198297A patent/JPH11140133A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001098173A (en) * | 1999-09-29 | 2001-04-10 | Asahi Denka Kogyo Kk | Resin modifier |
| US6525133B1 (en) * | 2000-03-29 | 2003-02-25 | The Goodyear Tire & Rubber Company | Tire with tread which utilizes an alpha-methyl styrene oligomer |
| JP2007519786A (en) * | 2004-01-27 | 2007-07-19 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Use of statistical copolymers |
| WO2005097857A1 (en) * | 2004-04-09 | 2005-10-20 | Shiseido Company, Ltd. | Brush-form alternative copolymer and process for producing the same |
| JP2005344248A (en) * | 2004-06-03 | 2005-12-15 | Kao Corp | Wrinkle-removing agent |
| JP4481088B2 (en) * | 2004-06-03 | 2010-06-16 | 花王株式会社 | Wrinkle remover |
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