JP4136886B2 - Polymers of novel alicyclic vinyl ethers - Google Patents
Polymers of novel alicyclic vinyl ethers Download PDFInfo
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Description
本発明は、新規な脂環式ビニルエーテル重合体に関し、更に詳しくは、光学材料、電気・電子材料用樹脂に好適な、側鎖に脂環骨格を有する新規な脂環式ビニルエーテル重合体に関するものである。 The present invention relates to a novel alicyclic vinyl ether polymer, and more particularly to a novel alicyclic vinyl ether polymer having an alicyclic skeleton in the side chain, which is suitable for optical materials and resins for electrical and electronic materials. is there.
近年、ジシクロペンタジエンの誘導体としてのアクリレート類やエポキシ類について、光学材料分野においては透明性樹脂、接着剤、コーティグ及び光導波路用樹脂として、又、レジスト分野においてはエッチング性が高く、微細なパターンを精度良く形成できるフォトレジスト用樹脂として、その用途が検討されている。 In recent years, acrylates and epoxies as derivatives of dicyclopentadiene are used as transparent resins, adhesives, coatings and optical waveguide resins in the field of optical materials, and in the resist field, they have high etching properties and fine patterns. Is being studied as a photoresist resin that can be accurately formed.
一般に、ジシクロペンタジエンの誘導体としてのアクリレート類は、脂環骨格を有するために剛直な構造や透明性を有しており、このようなアクリレート類については、例えば特許文献１や特許文献２に、トリシクロペンタデカンジメタノールとアクリル酸及びメタアクリル酸のエステル化物であるジメチロールトリシクロペンタデカンジ（メタ）アクリレートのラジカル重合体やその製造方法が記載されている。 In general, acrylates as derivatives of dicyclopentadiene have a rigid structure and transparency because they have an alicyclic skeleton, and for such acrylates, for example, in Patent Document 1 and Patent Document 2, A radical polymer of dimethylol tricyclopentadecane di (meth) acrylate, which is an esterified product of tricyclopentadecane dimethanol with acrylic acid and methacrylic acid, and a method for producing the same are described.
又、上記のジメチロールトリシクロペンタデカンジ（メタ）アクリレートのラジカル重合体の用途としては、例えば特許文献３に、寸法安定性、耐熱性、透明性に優れる成型品を製造可能な光硬化性樹脂組成物が記載されている。 Moreover, as a use of the above-mentioned radical polymer of dimethylol tricyclopentadecane di (meth) acrylate, for example, Patent Document 3 discloses a photocurable resin capable of producing a molded product having excellent dimensional stability, heat resistance, and transparency. A composition is described.
しかしながら、上記のようなアクリル系モノマーに関しては、皮膚刺激性や臭気性が強く、作業性、環境上の問題があること、及び、アクリル系化合物は吸湿性を有するために、樹脂材料として使用する際には寸法安定性に問題あることがますます指摘されるようになり、このようなアクリル系化合物の欠点を改善しようとする中で、ビニルエーテル系化合物及びこれらの重合体が注目されるようになった。 However, the acrylic monomers as described above have strong skin irritation and odor properties, have workability and environmental problems, and acrylic compounds have hygroscopic properties, so they are used as resin materials. In some cases, it is increasingly pointed out that there is a problem in dimensional stability, and vinyl ether compounds and polymers thereof are attracting attention in an attempt to improve the drawbacks of such acrylic compounds. became.
例えば、ビニルエーテル系化合物の重合体としては、特許文献４に、光学用成型品として、ポリ（ネオペンチルビニルエーテル）、或いは、このポリマーと、側鎖に環状飽和炭化水素、例えばノルボルニル基、ジメタノデカヒドロナフチル基等の基本骨格を有するビニルエーテルポリマーとのブレンド品が、ガラス転移点がそれぞれ１２５℃、１４０℃近くあり、複屈折が極めて低く、光透過性に優れ、且つ、吸水率が低いことが記載されている。 For example, as a polymer of a vinyl ether compound, Patent Document 4 discloses, as an optical molded product, poly (neopentyl vinyl ether), or this polymer, and a cyclic saturated hydrocarbon such as norbornyl group, dimethanodeca on the side chain. A blended product with a vinyl ether polymer having a basic skeleton such as a hydronaphthyl group has glass transition points of 125 ° C. and 140 ° C., respectively, extremely low birefringence, excellent light transmittance, and low water absorption. Are listed.
又、特許文献５には、光学用成型品として、例えば側鎖に環状飽和炭化水素、例えばノルボルニル基、ジメタノデカヒドロナフチル基等の基本骨格を有するビニルエーテルポリマーが、ガラス転移点が１０５℃乃至１６２℃近くあり、複屈折が極めて低く、光透過性に優れ、且つ、吸水率が低いことが開示されている。 Further, in Patent Document 5, as an optical molded article, for example, a vinyl ether polymer having a basic skeleton such as a cyclic saturated hydrocarbon such as a norbornyl group or a dimethanodecahydronaphthyl group in a side chain has a glass transition point of 105 ° C. to It is disclosed that the temperature is close to 162 ° C., the birefringence is extremely low, the light transmittance is excellent, and the water absorption is low.
更に、特許文献６には、脂環式炭化水素、例えばアダマンタン環、ノルボルナン環、トリシクロデカン環等を有するビニルエーテル化合物を単独重合して得られる、耐エッチング性に優れ、微細なパターンを精度良く形成できるフォトレジスト用高分子化合物が開示されている。 Furthermore, Patent Document 6 discloses that a fine pattern is obtained with excellent etching resistance and a fine pattern obtained by homopolymerizing a vinyl ether compound having an alicyclic hydrocarbon such as an adamantane ring, a norbornane ring, a tricyclodecane ring or the like. Polymer compounds for photoresist that can be formed are disclosed.
ところが、側鎖にノルボルナン、トリシクロデカン等の基本骨格を有する上記のビニルエーテルポリマーは、ガラス転移点が高いため、光透明性を有する光学材料に用いられているが、近年の光学材料分野における波長の短波長への変遷と透明性への要求、或いは、電気・電子材料分野における高速化と高密度化に対応するには、更に、単分散に近いポリマー等への改良が望まれている。
本発明は、上記のような従来技術の難点を解消し、光学材料分野における波長の短波長への変遷と透明性への要求、或いは、電気・電子材料分野における高速化と高密度化への要求に対応し、側鎖に新規な脂環骨格を導入した新たなビニルエーテル重合体を提供することを目的とする。 The present invention solves the problems of the prior art as described above, and shifts the wavelength to a short wavelength in the optical material field and demands for transparency, or increases the speed and density in the electric / electronic material field. An object of the present invention is to provide a new vinyl ether polymer in which a new alicyclic skeleton is introduced into a side chain in response to the demand.
本発明者は、上記の課題を解決すべく鋭意検討した結果、側鎖に新規な脂環骨格、即ち、特定のトリシクロデカン或いはペンタシクロペンタデカン骨格を有するビニルエーテル重合体が、疎水性が高いため、吸湿性が低く、寸法安定性に優れ、又、その嵩高さから、耐熱性、ビニルエーテル基による金属等への優れた密着性が期待でき、且つ、単分散に近い樹脂であることを見い出し、更に研究を重ねて新規な脂環式ビニルエーテル重合体を開発し、本発明を完成させた。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a novel alicyclic skeleton, that is, a vinyl ether polymer having a specific tricyclodecane or pentacyclopentadecane skeleton is highly hydrophobic. , Low hygroscopicity, excellent dimensional stability, and from its bulkiness, heat resistance, excellent adhesion to metals by vinyl ether groups can be expected, and found to be a resin close to monodispersion, Further research was conducted to develop a novel alicyclic vinyl ether polymer, thereby completing the present invention.
即ち、本発明は、式［１］ That is, the present invention provides the formula [1]
（mは０又は１を示し、nは１０〜１０,０００の整数を示す。）
で表され、リビングカチオン重合法により重合されたことを特徴とする新規な脂環式ビニルエーテル重合体を提供する。
(M represents 0 or 1, and n represents an integer of 10 to 10,000.)
And a novel alicyclic vinyl ether polymer characterized by being polymerized by a living cationic polymerization method .
又、本発明は、式［２］ The present invention also provides the formula [2]
で表されることを特徴とする新規な脂環式ビニルエーテル重合体を提供する。
The alicyclic vinyl ether polymer characterized by these is provided.
更に又、本発明は、式［３］ Furthermore, the present invention provides the formula [3]
（mは０又は１を示し、ｐ、ｑは０以上の整数を示し、ｐ＋ｑ＝１０〜１０,０００である。）
で表され、リビングカチオン重合法により重合されたことを特徴とする新規な脂環式ビニルエーテル重合体を提供する。
(M represents 0 or 1, p, q represents an integer of 0 or more, and p + q = 10 to 10,000.)
And a novel alicyclic vinyl ether polymer characterized by being polymerized by a living cationic polymerization method .
本発明により、光学、電気・電子材料用樹脂として有用な、側鎖に特定のトリシクロデカン、及びペンタシクロペンタデカン骨格を有する新たな脂環式ビニルエーテルを重合して新規な脂環式ビニルエーテル重合体を提供することが可能となる。 According to the present invention, a novel alicyclic vinyl ether polymer obtained by polymerizing a new alicyclic vinyl ether having a specific tricyclodecane and pentacyclopentadecane skeleton in the side chain, which is useful as a resin for optical and electrical / electronic materials. Can be provided.
式［１］〜［３］で表される本発明の脂環式ビニルエーテル重合体のためのモノマーとなる脂環式ビニルエーテル類としては、特に制限はなく、ビニル基交換等、公知の合成方法により得られるものを採用することができるが、例えば下式で示されるものが用いられる。 The alicyclic vinyl ethers that are monomers for the alicyclic vinyl ether polymer of the present invention represented by the formulas [1] to [3] are not particularly limited, and may be obtained by a known synthesis method such as vinyl group exchange. Although what is obtained can be adopted, for example, one represented by the following formula is used.
更に具体的には、上記の脂環式ビニルエーテル類のうち、例えば、式［４］で表されるトリシクロデカンビニルエーテルは、式［９］に示されるトリシクロデカンモノオールと無置換のアセチレンにより、以下のようにして製造することができる。 More specifically, among the above alicyclic vinyl ethers, for example, tricyclodecane vinyl ether represented by the formula [4] is represented by tricyclodecane monool represented by the formula [9] and unsubstituted acetylene. It can be manufactured as follows.
例えば、公知のビニルエーテル重合体の製造法に準じて、対応するビニルエーテルモノマーを不活性雰囲気中で硫酸等のプレンステツド酸や三フツ化ホウ素、四塩化チタン等のルイス酸を開始剤とする、通常のカチオン重合により高分子量化させることができる。重合の反応溶媒としては、通常のカチオン重合に用いられる溶媒、例えばトルエンや塩化メチレン或いは塩化メチレン／ヘキサン混合溶媒等が用いられる。 For example, in accordance with a known method for producing a vinyl ether polymer, a corresponding vinyl ether monomer is used in an inert atmosphere as a starter acid such as sulfuric acid or other prested acid, boron trifluoride, titanium tetrachloride or other Lewis acid as an initiator. High molecular weight can be achieved by cationic polymerization. As a polymerization reaction solvent, a solvent used for normal cationic polymerization, for example, toluene, methylene chloride, a methylene chloride / hexane mixed solvent, or the like is used.
反応温度は、通常−１００℃程度から３０℃の範囲であるが、高分子量の脂環式ビニルエーテル重合体を得るためには、開始剤濃度を下げ、−３０℃以下の低温で重合させるのが良い。尚、カチオン共重合の場合には、第３のコモノマーとして、更に炭素数４以下の低級アルキルビニルエーテルを添加することができる。 The reaction temperature is usually in the range of about −100 ° C. to 30 ° C., but in order to obtain a high molecular weight alicyclic vinyl ether polymer, the initiator concentration is lowered and the polymerization is carried out at a low temperature of −30 ° C. or lower. good. In the case of cationic copolymerization, a lower alkyl vinyl ether having 4 or less carbon atoms can be added as the third comonomer.
上記重合反応により、重合体は塊状若しくは溶媒に溶解或いは分散した形で得られるが、必要に応じてメタノール等の貧溶媒に注ぐことによって、未反応のモノマーや、低重合度のオリゴマー、分散剤等を除去することができる。 By the above polymerization reaction, the polymer is obtained in the form of a mass or dissolved or dispersed in a solvent, but if necessary, by pouring it into a poor solvent such as methanol, an unreacted monomer, an oligomer with a low polymerization degree, a dispersing agent Etc. can be removed.
具体的には、例えば、上記の原料（脂環式ビニルエーテル類）にトルエンを加えて、系内の温度が−３０℃に達した時点で、塩化水素のトルエン溶液及び塩化亜鉛のジエチルエーテル溶液を添加し、重合を開始し、分子量を時間の経過に応じてゲルパーミエーションクロマトグラフィー（ＧＰＣ）でモニタリングし、最後に系内にアンモニア／メタノール溶液を加えて、重合を停止させる。反応後は混合溶液中にトルエンを加え希釈し、食塩水溶液で洗浄し、溶媒を除去させ、その後に残留物をＴＨＦ（テトラヒドロフラン）に溶解させ、メタノール溶液中に再沈澱させ、濾過し、減圧乾燥させて、目的とする重合体が得ることができるのである。 Specifically, for example, when toluene is added to the above raw materials (alicyclic vinyl ethers) and the temperature in the system reaches −30 ° C., a toluene solution of hydrogen chloride and a diethyl ether solution of zinc chloride are added. The polymerization is started, the molecular weight is monitored by gel permeation chromatography (GPC) as time passes, and finally, an ammonia / methanol solution is added to the system to stop the polymerization. After the reaction, toluene is added to the mixed solution to dilute, washed with brine solution to remove the solvent, and then the residue is dissolved in THF (tetrahydrofuran), reprecipitated in methanol solution, filtered and dried under reduced pressure. Thus, the desired polymer can be obtained.
以下に実施例を挙げて詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例に限定されるものではない。
下記の実施例中、「数平均分子量（以下、Ｍｎと略す）」及び「分子量分布（重量平均分子量と数平均分子量の比、以下、Ｍｗ／Ｍｎと略す）」は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いた標準ポリスチレン換算法により算出した。
Examples will be described in detail below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
In the following examples, “number average molecular weight (hereinafter abbreviated as Mn)” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight, hereinafter abbreviated as Mw / Mn)” are gel permeation chromatography ( It was calculated by a standard polystyrene conversion method using GPC).
参考例１
トリシクロデカンモノメチルビニルエーテルの合成
ガラス製フラスコにトリシクロデカンモノメタノール２０５.６６ｇ（１.２４mol）、水酸化カリウム７.５６ｇ（１０mol%）、１,３−ジメチルイミダゾリジノン（ＤＭＩ） ４５４.３５ｇを導入し、減圧下（１２mmHg）、１２０℃で反応させた。この反応液をステンレス製オートクレーブに導入し、０.０２ＭＰaのアセチレン雰囲気下、１４０℃で５時間反応させた。反応液を回収、溶媒を留去した後、残渣をヘキサン／メタノール／水で抽出し、ヘキサン相を回収した。ヘキサン相を無水硫酸ナトリウムで乾燥、濾別し、減圧乾燥することにより粗トリシクロデカンモノメチルビニルエーテル１６０.０１ｇを得た。更に、蒸留精製を行って、目的のトリシクロデカンモノメチルビニルエーテル１３９.８９ｇを得た。
Reference example 1
Synthesis of tricyclodecane monomethyl vinyl ether In a glass flask, 205.66 g (1.24 mol) of tricyclodecane monomethanol, 7.56 g (10 mol%) of potassium hydroxide, 454.35 g of 1,3-dimethylimidazolidinone (DMI) Was allowed to react at 120 ° C. under reduced pressure (12 mmHg). This reaction solution was introduced into a stainless steel autoclave and allowed to react at 140 ° C. for 5 hours in an acetylene atmosphere of 0.02 MPa. After the reaction solution was recovered and the solvent was distilled off, the residue was extracted with hexane / methanol / water to recover the hexane phase. The hexane phase was dried over anhydrous sodium sulfate, filtered, and dried under reduced pressure to obtain 160.01 g of crude tricyclodecane monomethyl vinyl ether. Furthermore, distillation purification was performed to obtain 139.89 g of the desired tricyclodecane monomethyl vinyl ether.
参考例２
トリシクロデカンビニルエーテルの合成
ガラス製フラスコにトリシクロデカンモノオール１３７.００ｇ（０.９０mol）、水酸化カリウム５.５ｇ（１０mol%）、１,３−ジメチルイミダゾリジノン（ＤＭＩ）５００ｇを導入し、減圧下（４０mmHg）、１２０℃で反応させた。この反応液をステンレス製オートクレーブに導入し、０.０２ＭＰaのアセチレン雰囲気下、１４０℃で５時間反応させた。反応液を回収、溶媒を留去した後、残渣をトルエン／水で抽出し、トルエン相を回収した。トルエン相を無水硫酸ナトリウムで乾燥、濾別し、減圧乾燥することにより粗トリシクロデカンビニルエーテル１４３.８０ｇを得た。更に、蒸留精製を行って、目的のトリシクロデカンビニルエーテル１１６.７０ｇを得た。
Reference example 2
Synthesis of tricyclodecane vinyl ether Into a glass flask, 137.00 g (0.90 mol) of tricyclodecane monool, 5.5 g (10 mol%) of potassium hydroxide, and 500 g of 1,3-dimethylimidazolidinone (DMI) were introduced. The reaction was carried out at 120 ° C. under reduced pressure (40 mmHg). This reaction solution was introduced into a stainless steel autoclave and allowed to react at 140 ° C. for 5 hours in an acetylene atmosphere of 0.02 MPa. After the reaction solution was recovered and the solvent was distilled off, the residue was extracted with toluene / water to recover the toluene phase. The toluene phase was dried over anhydrous sodium sulfate, filtered, and dried under reduced pressure to obtain 143.80 g of crude tricyclodecane vinyl ether. Furthermore, distillation purification was performed to obtain 116.70 g of the target tricyclodecane vinyl ether.
参考例３
トリシクロデセンビニルエーテルの合成
ガラス製フラスコにトリシクロデセンモノオール２００.００ｇ（１.３３mol）、水酸化カリウム７.２ｇ（１０mol%）、１,３−ジメチルイミダゾリジノン（ＤＭＩ）５００ｇを導入し、減圧下（４０mmHg）、１２０℃で反応させた。この反応液をステンレス製オートクレーブに導入し、０.０２ＭＰaのアセチレン雰囲気下、１４０℃で６時間反応させた。反応液を回収、溶媒を留去した後、残渣をヘキサン／水で抽出し、ヘキサン相を回収した。ヘキサン相を無水硫酸ナトリウムで乾燥、濾別し、減圧乾燥することにより粗トリシクロデセンビニルエーテル２１１.００ｇを得た。更に、蒸留精製を行って、目的のトリシクロデセンビニルエーテル１７０.５０ｇを得た。
Reference example 3
Synthesis of tricyclodecene vinyl ether Into a glass flask was introduced 200.00 g (1.33 mol) of tricyclodecene monool, 7.2 g (10 mol%) of potassium hydroxide, and 500 g of 1,3-dimethylimidazolidinone (DMI). The reaction was carried out at 120 ° C. under reduced pressure (40 mmHg). This reaction solution was introduced into a stainless steel autoclave and allowed to react at 140 ° C. for 6 hours in an acetylene atmosphere of 0.02 MPa. After the reaction solution was recovered and the solvent was distilled off, the residue was extracted with hexane / water to recover the hexane phase. The hexane phase was dried over anhydrous sodium sulfate, filtered and dried under reduced pressure to obtain 211.00 g of crude tricyclodecene vinyl ether. Furthermore, distillation purification was performed to obtain 170.50 g of the desired tricyclodecene vinyl ether.
参考例４
ペンタシクロペンタデカンモノビニルエーテルの合成
ガラス製フラスコにペンタシクロペンタモノオール１８５.００ｇ（０.８５mol）、水酸化カリウム４.７６ｇ（１０mol%）、Ｎ−メチルピロリドン（ＮＭＰ） ５００ｇを導入し、減圧下（４０mmHg）、１２０℃で反応させた。この反応液をステンレス製オートクレーブに導入し、０.０２ＭＰaのアセチレン雰囲気下、１４５℃で５時間反応させた。反応液を回収、溶媒を留去した後、残渣をヘキサン／メタノール／水で抽出し、ヘキサン相を回収した。ヘキサン相を無水硫酸ナトリウムで乾燥、濾別し、減圧乾燥することにより粗ペンタシクロペンタデカンモノビニルエーテル３９.０６ｇを得た。更に、蒸留精製を行って、目的のペンタシクロペンタデカンモノビニルエーテル２０.２８ｇを得た。
Reference example 4
Synthesis of pentacyclopentadecane monovinyl ether 185.00 g (0.85 mol) of pentacyclopentamonool, 4.76 g (10 mol%) of potassium hydroxide and 500 g of N-methylpyrrolidone (NMP) were introduced into a glass flask under reduced pressure. (40 mmHg), the reaction was performed at 120 ° C. This reaction solution was introduced into a stainless steel autoclave and allowed to react at 145 ° C. for 5 hours in an acetylene atmosphere of 0.02 MPa. After the reaction solution was recovered and the solvent was distilled off, the residue was extracted with hexane / methanol / water to recover the hexane phase. The hexane phase was dried over anhydrous sodium sulfate, filtered and dried under reduced pressure to obtain 39.06 g of crude pentacyclopentadecane monovinyl ether. Furthermore, distillation purification was performed to obtain 20.28 g of the intended pentacyclopentadecane monovinyl ether.
トリシクロデカンモノメチルビニルエーテル重合体の合成
三方活栓を取り付けたガラス容器内を窒素置換した後、窒素ガス雰囲気下で加熱することにより、ガラス容器内の吸着水を除去した。系を室温に戻した後、トリシクロデカンモノメチルビニルエーテル５．０mmol及びトルエン５．０mlを加え、系中の温度が−３０℃に達したところで塩化水素（２．５×１０−２mmol）のトルエン溶液及び塩化亜鉛（２．５×１０−３mmol）のジエチルエーテル溶液を添加して重合を開始した。分子量を時間の経過に応じてＧＰＣを用いてモニタリングし、系中に３．０wt％のアンモニア／メタノール溶液を加えることにより重合反応の停止を行った。反応を終えた混合溶液中にトルエンを加え希釈し、１０wt%食塩水溶液で３回洗浄し溶媒を除去した。その後残留物をテトラヒドロフラン（ＴＨＦ）に溶解させ、メタノール溶液中で再沈殿したものを濾過し、減圧乾燥させて目的物であるトリシクロデカンモノメチルビニルエーテル重合体０．８ｇを得た。
Synthesis of tricyclodecane monomethyl vinyl ether polymer The inside of a glass container equipped with a three-way stopcock was purged with nitrogen, and then the adsorbed water in the glass container was removed by heating in a nitrogen gas atmosphere. After returning the system to room temperature, 5.0 mmol of tricyclodecane monomethyl vinyl ether and 5.0 ml of toluene were added, and when the temperature in the system reached −30 ° C., toluene of hydrogen chloride (2.5 × 10 −2 mmol). The solution and a solution of zinc chloride (2.5 × 10 −3 mmol) in diethyl ether were added to initiate the polymerization. The molecular weight was monitored using GPC over time, and the polymerization reaction was stopped by adding a 3.0 wt% ammonia / methanol solution to the system. Toluene was added to the mixed solution after the reaction to dilute, and the mixture was washed 3 times with a 10 wt% saline solution to remove the solvent. Thereafter, the residue was dissolved in tetrahydrofuran (THF), and the re-precipitated product in a methanol solution was filtered and dried under reduced pressure to obtain 0.8 g of the target tricyclodecane monomethyl vinyl ether polymer.
回収した重合体のＭｎは２.２×１０4 、Ｍｗ／Ｍｎは１.１であり、Ｔｇは６５℃であった。又、トリシクロデカンモノメチルビニルエーテルの1H−ＮＭＲ分析において６.４ｐｐｍに観察されるエーテル酸素に隣接したビニル水素のシグナルが重合後消失することから、トリシクロデカンモノメチルビニルエーテル重合体が生成していることが支持された。 The recovered polymer had Mn of 2.2 × 10 4 , Mw / Mn of 1.1, and Tg of 65 ° C. Moreover, since the signal of vinyl hydrogen adjacent to ether oxygen observed at 6.4 ppm in 1 H-NMR analysis of tricyclodecane monomethyl vinyl ether disappears after polymerization, a tricyclodecane monomethyl vinyl ether polymer is formed. It was supported.
トリシクロデカンビニルエーテル重合体の合成
三方活栓を取り付けたガラス容器内を窒素置換した後、窒素ガス雰囲気下で加熱することにより、ガラス容器内の吸着水を除去した。系を室温に戻した後、トリシクロデカンビニルエーテル５６．１mmol及びトルエン５５．０mlを加え、系中の温度が−３０℃に達したところで塩化水素（３．０×１０−２mmol）のトルエン溶液及び塩化亜鉛（７．０×１０−３mmol）のジエチルエーテル溶液を添加して重合を開始した。分子量を時間の経過に応じてＧＰＣを用いてモニタリングし、系中に３．０wt％のアンモニア／メタノール溶液を加える事により重合反応の停止を行った。反応を終えた混合溶液中にトルエンを加え希釈し、１０wt%食塩水溶液で３回洗浄し溶媒を除去した。その後残留物をTHFに溶解させ、メタノール溶液中で再沈殿したものを濾過し、減圧乾燥させて目的物であるトリシクロデカンビニルエーテル重合体８．４ｇを得た。
Synthesis of Tricyclodecane Vinyl Ether Polymer The inside of a glass container equipped with a three-way cock was replaced with nitrogen, and then heated in a nitrogen gas atmosphere to remove adsorbed water in the glass container. After returning the system to room temperature, 56.1 mmol of tricyclodecane vinyl ether and 55.0 ml of toluene were added. When the temperature in the system reached −30 ° C., a toluene solution of hydrogen chloride (3.0 × 10 −2 mmol). And a diethyl ether solution of zinc chloride (7.0 × 10 −3 mmol) was added to initiate the polymerization. The molecular weight was monitored using GPC over time, and the polymerization reaction was stopped by adding a 3.0 wt% ammonia / methanol solution to the system. Toluene was added to the mixed solution after the reaction to dilute, and the mixture was washed 3 times with a 10 wt% saline solution to remove the solvent. Thereafter, the residue was dissolved in THF, and the re-precipitated product in methanol solution was filtered and dried under reduced pressure to obtain 8.4 g of the target tricyclodecane vinyl ether polymer.
回収した重合体のＭｎは１.８×１０５ 、Ｍｗ／Ｍｎは１.２であり、Ｔｇは１０８℃であった。又、トリシクロデカンビニルエーテルの1H−ＮＭＲ分析において６.４ｐｐｍに観察されるエーテル酸素に隣接したビニル水素のシグナルが重合後消失することから、トリシクロデカンビニルエーテル重合体が生成していることが支持された。 The recovered polymer had Mn of 1.8 × 10 5 , Mw / Mn of 1.2, and Tg of 108 ° C. Moreover, since the signal of vinyl hydrogen adjacent to ether oxygen observed at 6.4 ppm in 1 H-NMR analysis of tricyclodecane vinyl ether disappears after polymerization, a tricyclodecane vinyl ether polymer is formed. Supported.
トリシクロデセンビニルエーテル重合体の合成
三方活栓を取り付けたガラス容器内を窒素置換した後、窒素ガス雰囲気下で加熱することにより、ガラス容器内の吸着水を除去した。系を室温に戻した後、トリシクロデセンビニルエーテル８．０mmol及びトルエン８．０mlを加え、系中の温度が−３０℃に達したところで塩化水素（４．０×１０−２mmol）のトルエン溶液及び塩化亜鉛（４．０×１０−３mmol）のジエチルエーテル溶液を添加して重合を開始した。分子量を時間の経過に応じてＧＰＣを用いてモニタリングし、系中に３．０wt%のアンモニア／メタノール溶液を加える事により重合反応の停止を行った。反応を終えた混合溶液中にトルエンを加え希釈し、１０wt%食塩水溶液で３回洗浄し溶媒を除去した。その後残留物をTHFに溶解させ、メタノール溶液中で再沈殿したものを濾過し、減圧乾燥させて目的物であるトリシクロデセンビニルエーテル重合体１．１ｇを得た。
Synthesis of Tricyclodecene Vinyl Ether Polymer After the inside of a glass container equipped with a three-way cock was replaced with nitrogen, the adsorbed water in the glass container was removed by heating in a nitrogen gas atmosphere. After returning the system to room temperature, 8.0 mmol of tricyclodecene vinyl ether and 8.0 ml of toluene were added, and when the temperature in the system reached −30 ° C., a toluene solution of hydrogen chloride (4.0 × 10 −2 mmol). And a diethyl ether solution of zinc chloride (4.0 × 10 −3 mmol) was added to initiate the polymerization. The molecular weight was monitored with GPC over time, and the polymerization reaction was stopped by adding 3.0 wt% ammonia / methanol solution to the system. Toluene was added to the mixed solution after the reaction to dilute, and the mixture was washed 3 times with a 10 wt% saline solution to remove the solvent. Thereafter, the residue was dissolved in THF, and reprecipitated in a methanol solution was filtered and dried under reduced pressure to obtain 1.1 g of the target tricyclodecene vinyl ether polymer.
回収した重合体のＭｎは２.２×１０4、Ｍｗ／Ｍｎは１.１であり、Ｔｇは１００℃であった。又、トリシクロデセンビニルエーテルの1H−ＮＭＲ分析において６.３ｐｐｍに観察されるエーテル酸素に隣接したビニル水素のシグナルが重合後消失することから、トリシクロデセンビニルエーテル重合体が生成していることが支持された。 The recovered polymer had Mn of 2.2 × 10 4 , Mw / Mn of 1.1, and Tg of 100 ° C. Further, since the signal of vinyl hydrogens adjacent to an ether oxygen are observed 6.3ppm in of 1 H-NMR analysis tricycloalkyl decene vinyl disappears after polymerization, be tricycloalkyl decene vinyl polymer is produced Supported.
ペンタシクロペンタデカンモノビニルエーテル重合体の合成
三方活栓を取り付けたガラス容器内を窒素置換した後、窒素ガス雰囲気下で加熱することにより、ガラス容器内の吸着水を除去した。系を室温に戻した後、ペンタシクロペンタデカンモノビニルエーテル３．９mmol及びトルエン３mlを加え、系中の温度が−３０℃に達したところで塩化水素（２．０×１０−２mmol）のトルエン溶液及び塩化亜鉛（２．０×１０−３mmol）のジエチルエーテル溶液を添加して重合を開始した。ＧＰＣを用いてモニタリングし、系中に３wt%のアンモニア／メタノール溶液を加える事により重合反応の停止を行った。反応を終えた混合溶液中にトルエンを加え希釈し、１０wt%食塩水溶液で３回洗浄し溶媒を除去した。その後残留物をTHFに溶解させ、メタノール溶液中で再沈殿したものを濾過し、減圧乾燥させて目的物であるペンタシクロペンタデカンモノビニルエーテル重合体０．８ｇを得た。
Synthesis of Pentacyclopentadecane Monovinyl Ether Polymer The inside of a glass container equipped with a three-way stopcock was purged with nitrogen, and then heated in a nitrogen gas atmosphere to remove adsorbed water in the glass container. After returning the system to room temperature, 3.9 mmol of pentacyclopentadecane monovinyl ether and 3 ml of toluene were added. When the temperature in the system reached −30 ° C., a toluene solution of hydrogen chloride (2.0 × 10 −2 mmol) and Polymerization was initiated by adding a diethyl ether solution of zinc chloride (2.0 × 10 −3 mmol). Monitoring was performed using GPC, and the polymerization reaction was stopped by adding a 3 wt% ammonia / methanol solution to the system. Toluene was added to the mixed solution after the reaction to dilute, and the mixture was washed 3 times with a 10 wt% saline solution to remove the solvent. Thereafter, the residue was dissolved in THF, and reprecipitated in a methanol solution was filtered and dried under reduced pressure to obtain 0.8 g of the target pentacyclopentadecane monovinyl ether polymer.
回収した重合体のＭｎは１.５×１０4、Ｍｗ／Ｍｎは１.５であり、Ｔｇは１６０℃であった。又、ペンタシクロペンタデカンモノビニルエーテルの1H−ＮＭＲ分析において６.２ｐｐｍに観察されるエーテル酸素に隣接したビニル水素のシグナルが重合後消失することから、ペンタシクロペンタデカンモノビニルエーテル重合体が生成していることが支持された。 The recovered polymer had Mn of 1.5 × 10 4 , Mw / Mn of 1.5, and Tg of 160 ° C. Moreover, since the signal of vinyl hydrogen adjacent to ether oxygen observed at 6.2 ppm in 1 H-NMR analysis of pentacyclopentadecane monovinyl ether disappears after polymerization, a pentacyclopentadecane monovinyl ether polymer is formed. It was supported.
本発明のビニルエーテル重合体は、側鎖に特定のトリシクロデカン或いはペンタシクロペンタデカン骨格を有し、疎水性が高いため、吸湿性が低く、寸法安定性に優れ、又、その嵩高さから、耐熱性、ビニルエーテル基による金属等への優れた密着性が期待でき、且つ、単分散に近い樹脂であるという優れたものである。 The vinyl ether polymer of the present invention has a specific tricyclodecane or pentacyclopentadecane skeleton in the side chain, and since it has high hydrophobicity, it has low hygroscopicity, excellent dimensional stability, and its bulkiness makes it heat resistant. And excellent adhesion to a metal or the like due to vinyl ether groups, and an excellent resin that is close to monodispersion.
Claims (3)
（mは０又は１を示し、nは１０〜１０,０００の整数を示す。）
で表され、リビングカチオン重合法により重合されたことを特徴とする新規な脂環式ビニルエーテル重合体。 Formula [1]
(M represents 0 or 1, and n represents an integer of 10 to 10,000.)
And a novel alicyclic vinyl ether polymer characterized by being polymerized by a living cationic polymerization method .
（ｐ及びｑは０以上の整数を示し、ｐ＋ｑ＝１０〜１０,０００である。）
で表されることを特徴とする新規な脂環式ビニルエーテル重合体。 Formula [2]
(P and q represent an integer of 0 or more, and p + q = 10 to 10,000.)
A novel alicyclic vinyl ether polymer characterized by the following:
（mは０又は１を示し、ｐ、ｑは０以上の整数を示し、ｐ＋ｑ＝１０〜１０,０００である。）
で表され、リビングカチオン重合法により重合されたことを特徴とする新規な脂環式ビニルエーテル重合体。 Formula [3]
(M represents 0 or 1, p, q represents an integer of 0 or more, and p + q = 10 to 10,000.)
And a novel alicyclic vinyl ether polymer characterized by being polymerized by a living cationic polymerization method .
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