JPH0441684B2 - - Google Patents
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- Publication number
- JPH0441684B2 JPH0441684B2 JP9119285A JP9119285A JPH0441684B2 JP H0441684 B2 JPH0441684 B2 JP H0441684B2 JP 9119285 A JP9119285 A JP 9119285A JP 9119285 A JP9119285 A JP 9119285A JP H0441684 B2 JPH0441684 B2 JP H0441684B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- anionic polymerization
- compound
- polymerization initiator
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 229920000642 polymer Polymers 0.000 claims description 25
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 18
- 239000003505 polymerization initiator Substances 0.000 description 17
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 13
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 8
- -1 acrylic acid compound Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003708 ampul Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229920001002 functional polymer Polymers 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IJJSYKQZFFGIEE-UHFFFAOYSA-N naphthalene;potassium Chemical compound [K].C1=CC=CC2=CC=CC=C21 IJJSYKQZFFGIEE-UHFFFAOYSA-N 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
産業上の利用分野
本発明は、アクリル酸系化合物のリビングポリ
マーに関する。
従来の技術
分子中に反応性基を持つビニルモノマーから
は、反応性基中の活性水素のため、直接それらビ
ニルモノマーのマニオンリビングポリマーは得ら
れていない。
本発明者らは、先に水酸基、アミノ基等の反応
性基を持つ芳香族系ビニルモノマーの反応性基
を、予め置換シリル基で保護した後、アニオン重
合開始剤を作用させることにより、置換シリル基
で保護された芳香族系ビニルモノマーのアニオン
リビングポリマーが得られることを見出した（特
開昭59−53509号公報）。
発明が解決しようとする問題点
本発明はアクリル酸系化合物、特にメタクリル
酸誘導体のアニオンリビングポリマーを合成する
ことを目的とする。
問題を解決するための手段
発明の要旨
本発明者らは、鋭意研究を行つた結果、反応性
基を持つアクリル酸系化合物を予めヒドカルビル
シリル基（以下、置換シリル基という。）で保護
した後、アニオン重合開始剤を使用させることに
より、置換シリル基で保護した上記アクリル酸系
化合物のリビングポリマーが生成することを見出
して本発明を完成した。
すなわち、本発明は
一般式
〔式中、Ｒはメチル基、Ｚは（CH2）n・
OSiR1R2R3を示し、ｍは１〜６の数、R1〜R3は
炭素数１〜６個の同一のアルキル基を示す。〕の
繰り返し単位からなり、数平均分子量500〜
500000の新規リビングポリマー（）を要旨とす
る。
リビングポリマーの製造法
本発明のリビングポリマー（）は、例えば、
一般式
〔式中、Ｒはメチル基を、Ｘは（CH2）nOH基を
示す、ｍは１〜６の数を示す。〕で表されるメタ
クリル酸系化合物（）を、式（R1R2R3Si）oＬ、
〔式中、R1〜R3は同一の炭素数１〜６個のアルキ
ル基、Ｌ及びＭはハロゲン原子又はNH基、ｎは
Ｌがハロゲン原子の場合は１でありNH基の場合
は２である。〕で表わされる置換シリル基含有化
合物と接触させ、得られる置換シリル基置換体
を、アニオン重合開始剤の存在下で重合させるこ
とによつて得られる。
上記化合物（）の具体例としては、CH2＝Ｃ
（CH3）CO・OCH2OH、OH2＝Ｃ（CH3）CO・
Ｏ（CH2）2OH、CH2＝Ｃ（CH3）CO・Ｏ
（CH2）4OH等が挙げられる。
化合物（）の反応性を保護するために用いら
れる置換シリル基含有化合物の具体例としては、
〔（CH3）3Si〕2NH、〔（C2H5）3Si〕2NH、〔（ｉ−
C3H7）3Si〕2NH、〔（ｔ−C4H9）2CH3Si〕2NH、
（CH3）3SiCl、（C2H5）3SiCl、ｔ−C4H9
（CH3）2SiCl、CH3（C2H5）2SiCl、（ｎ−
C4H9）3SiCl、等を挙げることができる。これら
の化合物は、一種に限らず二種以上同時に用いて
もよい。
化合物（）と置換シリル基含有化合物との接
触は、室温若しくは加温下で、通常0.5〜50時間
行なわれる。接触は、溶媒中で行つてもよく、又
窒素ガス等の不活性ガス雰囲気下で行つてもよ
い。適当な溶媒としては、DMF（ジメチルホルム
アミド）、THF（テトラヒドロフラ）、NMP（Ｎ−
メチルピロリドン）、スルフオラン、DMSO（ジ
メチルスルホキシド）、クロロホルム、四塩化炭
素、ジクロルエタン等が挙げられる。なお、置換
シリル基含有化合物がR1R2R3Si・ハロゲン原子
の場合は、置換シリル基含有化合物に対して等モ
ルの第三級アミン、例えばトリエチルアミン、ト
リブチルアミン等、を併用する必要があり、その
際に存在させることができる溶媒としては、ベン
ゼン、ジエチルエーテル、ヘキサン等の方が望ま
しい。
化合物（）と置換シリル基含有化合物との接
触は、二段以上で行つてもよい。両者の接触割合
は、化合物（）に対して置換シリル基含有化合
物が１倍モル以上、望ましくは等モル〜10倍モル
である。
かくすることにより、化合物（）の反応性基
中の活性水素は、置換シリル基と置換され、化合
物（）の置換体となるが、該置換体は次いでア
ニオン重合開始剤の存在下、アニオン重合するこ
とにより、該置換体のリビングポリマー（）が
得られる。
適当なアニオン重合開始剤としては、ｎ−ブチ
ルリチウム、ナフタレンリチウム塩、ナフタレン
ナトリウム塩、ナフタレンカリウム塩、（α−メ
チルスチレンオリゴマー）ナトリウム塩等を挙げ
ることができるが、これら重合開始剤にジフエニ
ルエチレンを組み合せるとより効果的である。特
に一般のビニル系モノマーのアニオン重合開始剤
として通常用いられるｎ−ブチルリチウムを用い
た場合、本発明のリビングポリマーは生成しない
のに対して、ジフエニルエチレンを併用すること
により、ｎ−ブチルリチウムの活性を抑え、カル
ボニルへの攻撃を防ぐことができ、リビング重合
が可能となる。ジフエニルエチレンは該重合開始
剤に対して通常２〜５倍モル用いられる。
アニオン重合は、室温で行つてもよいが、望ま
しくは、−30℃以下の低温、特に望ましくは−50
℃〜−100℃の低温で、0.1〜20時間、望ましくは
溶媒の存在下、で行なわれる。適当な溶媒として
は、THF、トルエン、ヘキサン、シクロヘキサ
ン等が挙げられる。それらは二種以上用いてもよ
い。又、重合反応は、不活性ガス雰囲気中、減圧
下、特に望ましくは高真空下で行うのが望まし
い。
リビングポリマー（）の分子量は、該置換
体／アニオン重合開始剤比を変えることにより制
御することができ、その比を上げることにより分
子量を増加することができる。又、アニオン重合
開始剤の種類又は重合温度を変えることによつて
も分子量の調節は可能である。
かくして得られたリビングポリマー（）は、
500〜500000、望ましくは2000〜200000、更に望
ましくは5000〜100000の数平均分子量を持ち、比
較的低温において安定な性質を有する。
本発明のリビングポリマー（）は、他のモノ
マーとの（リビング）ブロツク共重合体の合成原
料として有用であり、又メタノール、エタノー
ル、フエノール、塩酸、硫酸等のプロトン供与体
と接触させることにより、保護基である置換シリ
ル基が容易に脱離し、化合物（）のポリマーを
製造することができる。この方法によれば公知の
化合物（）のラジカル重合法による化合物
（）のポリマー製造法に比べ、分子量の調節が
容易であり、任意の分子量でかつ狭い分子量分布
を持つポリマーを容易に製造することができると
いう特徴を有する。
かくして得られる保護基を外したポリマーは、
機能性ポリマーとして利用でき、その反応性置換
基を他の極性基と置換した新らたな機能性ポリマ
ーの合成原料としても有用である。
以下、本発明を実施例により詳細に説明する
が、本発明は、その主旨に反しない限り、これら
実施例に限定されるものではない。
実験は、高真空ラインに接続した複数のアニオ
ン重合開始剤溶液及びモノマー溶液を凍結、脱気
して封入したブレーカブルシールを持つアンプル
並びに系内を洗浄した廃アニオン重合開始剤及び
リビングポリマーの一部を取り出すスペアーの枝
管と接続されたフラスコからなる図面に示す装置
を用い、次の方法で行つた。
まず、フラスコ１を10-6mmHgに５時間保つて
脱気し、真空ライン８からＡ点で封じ切り、次い
で一つのアニオン重合開始剤の入つたアンプル３
のシールを破り、フラスコ１を含む系内に導び
き、系内を十分に洗浄し、スペアーの枝管７に導
びき、その枝管７をＣ点で封じ切り、系から取り
除き、しかる後、所定の温度に冷却し、所定の温
度に冷却された第２のアニオン重合開始剤溶液が
入つたアンプル２のシールを破り、フラスコ１に
アニオン重合開始剤を導き、次いで第１のモノマ
ーをアンプル４から同様にしてフラスコ１に導入
して所定時間反応させた後、一部の溶液を枝管６
に導入して封じ切り、リビングポリマーのキヤラ
クタリゼーシヨンに供した。
実施例
〔HEMA−Siの合成及び固定〕
反応器にヒドロキシエチルメタクリレート
及びHEMAに対して等モルの〔（CH3）3Si〕2NH
を入れ、窒素ガス雰囲気下室温で10時間撹拌を行
つた。得られた生成物を減圧蒸溜して、
を得、更にカルシウムジハイドライドを加えて真
空蒸溜することにより、80％の収率で精製した
HEMA−Siを得た。このHEMA−Siは61〜62
℃／３mmHgの沸点を有していた。
HEMA−Siを1H NMR（60MHz、CCl4中、
TMS基準）分析し、そのケミカルシフト値（下
記）からHEMA−Siは上記構造式からなるもの
であることが確認された。
0.16ppm（ｓ、9H、Si−CH3）、0.19ppm（ｍ、
3H、Ｃ−CH3）、3.6〜4.4ppm（ｍ、4H、Ｏ−
CH2）、5.60ppm（ｍ、1H、H3C−Ｃ＝CH cis）、
6.15ppm〔ｍ、1H、
INDUSTRIAL APPLICATION FIELD The present invention relates to living polymers of acrylic acid compounds. PRIOR ART Manion-living polymers of vinyl monomers having reactive groups in their molecules have not been directly obtained due to the active hydrogen in the reactive groups. The present inventors first protected the reactive group of an aromatic vinyl monomer having a reactive group such as a hydroxyl group or an amino group with a substituted silyl group, and then treated it with an anionic polymerization initiator. It has been found that an anionic living polymer of an aromatic vinyl monomer protected with a silyl group can be obtained (Japanese Patent Application Laid-Open No. 59-53509). Problems to be Solved by the Invention The present invention aims to synthesize anionic living polymers of acrylic acid compounds, particularly methacrylic acid derivatives. Means to Solve the Problem Summary of the Invention As a result of intensive research, the present inventors have discovered that an acrylic acid compound having a reactive group is protected in advance with a hydrocarbylsilyl group (hereinafter referred to as a substituted silyl group). After that, they discovered that by using an anionic polymerization initiator, a living polymer of the above-mentioned acrylic acid compound protected with a substituted silyl group was produced, and the present invention was completed. That is, the present invention has the general formula [In the formula, R is a methyl group, Z is (CH 2 ) n .
OSiR 1 R 2 R 3 is shown, m is a number of 1 to 6, and R 1 to R 3 are the same alkyl group having 1 to 6 carbon atoms. ] and has a number average molecular weight of 500~
Abstracts include 500,000 new living polymers (). Method for producing living polymer The living polymer () of the present invention is, for example,
general formula [In the formula, R represents a methyl group, X represents a (CH 2 ) n OH group, and m represents a number from 1 to 6. ] The methacrylic acid compound () represented by the formula (R 1 R 2 R 3 Si) o L,
[In the formula, R 1 to R 3 are the same alkyl groups having 1 to 6 carbon atoms, L and M are halogen atoms or NH groups, and n is 1 when L is a halogen atom and 2 when L is an NH group. It is. It is obtained by contacting with a substituted silyl group-containing compound represented by ] and polymerizing the resulting substituted silyl group-substituted product in the presence of an anionic polymerization initiator. Specific examples of the above compound () include CH 2 =C
(CH 3 )CO・OCH 2 OH, OH 2 =C(CH 3 )CO・
O(CH 2 ) 2 OH, CH 2 =C(CH 3 )CO・O
( CH2 ) 4OH etc. are mentioned. Specific examples of substituted silyl group-containing compounds used to protect the reactivity of compound () include:
[(CH 3 ) 3 Si] 2 NH, [(C 2 H 5 ) 3 Si] 2 NH, [(i-
C 3 H 7 ) 3 Si〕 2 NH, [(t-C 4 H 9 ) 2 CH 3 Si〕 2 NH,
( CH3 ) 3SiCl , ( C2H5 ) 3SiCl , t- C4H9
(CH 3 ) 2 SiCl, CH 3 (C 2 H 5 ) 2 SiCl, (n-
Examples include C 4 H 9 ) 3 SiCl, and the like. These compounds are not limited to one type, and two or more types may be used simultaneously. The contact between the compound () and the substituted silyl group-containing compound is usually carried out at room temperature or under heating for 0.5 to 50 hours. The contact may be performed in a solvent or under an inert gas atmosphere such as nitrogen gas. Suitable solvents include DMF (dimethylformamide), THF (tetrahydrofura), NMP (N-
Examples include methylpyrrolidone), sulforane, DMSO (dimethylsulfoxide), chloroform, carbon tetrachloride, dichloroethane, and the like. In addition, when the substituted silyl group-containing compound is R 1 R 2 R 3 Si/halogen atom, it is necessary to use an equimolar amount of tertiary amine, such as triethylamine, tributylamine, etc., with respect to the substituted silyl group-containing compound. As the solvent that can be present at that time, benzene, diethyl ether, hexane, etc. are preferable. The contact between the compound () and the substituted silyl group-containing compound may be carried out in two or more stages. The contact ratio between the two is such that the amount of the substituted silyl group-containing compound is at least 1 mole, preferably equimolar to 10 times the mole of the compound (). By doing so, the active hydrogen in the reactive group of compound () is substituted with a substituted silyl group, resulting in a substituted product of compound (), which is then subjected to anionic polymerization in the presence of an anionic polymerization initiator. By doing so, a living polymer () of the substituted product is obtained. Suitable anionic polymerization initiators include n-butyllithium, naphthalene lithium salt, naphthalene sodium salt, naphthalene potassium salt, (α-methylstyrene oligomer) sodium salt, etc.; It is more effective when combined with ethylene. In particular, when n-butyllithium, which is commonly used as an anionic polymerization initiator for general vinyl monomers, is used, the living polymer of the present invention is not produced. activity and prevent attack on carbonyls, making living polymerization possible. Diphenylethylene is usually used in a molar amount 2 to 5 times the amount of the polymerization initiator. The anionic polymerization may be carried out at room temperature, but preferably at a low temperature of -30°C or lower, particularly preferably at -50°C.
The reaction is carried out at a low temperature of 0.degree. C. to -100.degree. C. for 0.1 to 20 hours, preferably in the presence of a solvent. Suitable solvents include THF, toluene, hexane, cyclohexane, and the like. Two or more kinds of them may be used. Further, the polymerization reaction is desirably carried out in an inert gas atmosphere under reduced pressure, particularly preferably under high vacuum. The molecular weight of the living polymer () can be controlled by changing the ratio of the substituent/anionic polymerization initiator, and the molecular weight can be increased by increasing the ratio. The molecular weight can also be controlled by changing the type of anionic polymerization initiator or the polymerization temperature. The living polymer () thus obtained is
It has a number average molecular weight of 500 to 500,000, preferably 2,000 to 200,000, and more preferably 5,000 to 100,000, and is stable at relatively low temperatures. The living polymer () of the present invention is useful as a raw material for the synthesis of (living) block copolymers with other monomers, and can also be used by contacting it with a proton donor such as methanol, ethanol, phenol, hydrochloric acid, or sulfuric acid. The substituted silyl group, which is a protecting group, is easily removed, and a polymer of compound () can be produced. According to this method, the molecular weight can be easily controlled compared to the known method of producing a polymer of compound () by radical polymerization of compound (), and a polymer having an arbitrary molecular weight and a narrow molecular weight distribution can be easily produced. It has the characteristic of being able to The thus obtained deprotected polymer is
It can be used as a functional polymer, and is also useful as a raw material for the synthesis of new functional polymers whose reactive substituents are replaced with other polar groups. EXAMPLES Hereinafter, the present invention will be explained in detail with reference to examples, but the present invention is not limited to these examples unless it goes against the gist thereof. The experiment consisted of an ampoule with a breakable seal in which multiple anionic polymerization initiator solutions and monomer solutions were frozen and degassed, which were connected to a high vacuum line, and a sample of the waste anionic polymerization initiator and living polymer that had been cleaned inside the system. Using the apparatus shown in the drawing, which consists of a flask connected to a spare branch pipe for taking out the sample, the following method was used. First, the flask 1 was kept at 10 -6 mmHg for 5 hours to degas it, the vacuum line 8 was sealed off at point A, and then the ampoule 3 containing one anionic polymerization initiator was
break the seal, introduce it into the system containing the flask 1, thoroughly wash the inside of the system, guide it to a spare branch pipe 7, seal off the branch pipe 7 at point C, remove it from the system, and then, Cool to a predetermined temperature, break the seal of the ampoule 2 containing the second anionic polymerization initiator solution cooled to the predetermined temperature, introduce the anionic polymerization initiator into the flask 1, and then introduce the first monomer into the ampoule 4. After introducing the solution into flask 1 in the same manner and allowing it to react for a predetermined period of time, a portion of the solution was introduced into branch pipe 6.
The polymer was introduced into a container, sealed, and subjected to the characterization of a living polymer. Example [Synthesis and fixation of HEMA-Si] Hydroxyethyl methacrylate in the reactor and equimolar [(CH 3 ) 3 Si] 2 NH with respect to HEMA
was added and stirred at room temperature under a nitrogen gas atmosphere for 10 hours. The obtained product was distilled under reduced pressure, was purified with a yield of 80% by further adding calcium dihydride and vacuum distillation.
HEMA-Si was obtained. This HEMA−Si is 61 to 62
It had a boiling point of °C/3 mmHg. HEMA−Si by 1H NMR (60MHz, in CCl4 ,
(TMS standard) analysis, and it was confirmed from the chemical shift value (below) that HEMA-Si has the above structural formula. 0.16ppm (s, 9H, Si-CH 3 ), 0.19ppm (m,
3H, C-CH 3 ), 3.6-4.4ppm (m, 4H, O-
CH2 ), 5.60ppm (m, 1H, H3C -C=CHcis),
6.15ppm [m, 1H,
得られたHEMA−Siを第１表に示す各種のア
ニオン重合開始剤の存在下、THF中−78℃で重
合した。
結果を第１表に示すが、収量はアニオン重合開
始剤がｔ−C4H9OKの場合を除いてほぼ定量的で
あつた。得られたリビングポリマー
は、室温で不安定のため、以下の処理を行つた後
キヤラクタリゼーシヨンを行つた。
このリビングポリマーを室温でTHF−H2O溶
媒中、希薄HCl−メタノール溶液にて１分間処理
することにより、保護基のトリメチルシリル基は
離脱し、ポリ（ヒドロキシエチルメタクリレー
ト）（PHEMA）が得られた。PHEMAは、
DMF、ピリジン、メタノール、エタノールに可
溶であり、ベンゼン、四塩化炭素、エーテル、
THF、１，４−ジオキサン、アセトン、メチル
エチルケトン、酢酸エチル、ブタノール、水等に
不溶であつた。
PHEMAはIRスペクトル分析及び1H HMR分
析の結果、トリメチルシリル基の存在による吸収
は認められず、従つて、PHEMAは
の構造式を持つことが確認された。
PHEMAはTHFに溶解しないため、その−
OH基を安息香酸無水物によりベンゾイル化した
後、GPC又はVPO（Vapor Pressure
Osmometer）で数平均分子量（ｎ）を測定し、
PHEMA中の−OH基が総てベンゾイル化された
として計算したｎと共にその結果を第１表に示
す。両者はかなりよく一致していることが分る。
又、このベンゾイル化PHEMAは極めて狭い分
子量分布（ｗ／ｎ＝1.1〜1.3）を持つポリマ
ーであることが確認された。
The obtained HEMA-Si was polymerized at -78°C in THF in the presence of various anionic polymerization initiators shown in Table 1. The results are shown in Table 1, and the yields were almost quantitative except when the anionic polymerization initiator was t-C 4 H 9 OK. Living polymer obtained Because it is unstable at room temperature, characterization was performed after the following treatment. By treating this living polymer with dilute HCl-methanol solution in THF- H2O solvent for 1 minute at room temperature, the trimethylsilyl protecting group was removed and poly(hydroxyethyl methacrylate) (PHEMA) was obtained. . PHEMA is
Soluble in DMF, pyridine, methanol, ethanol, benzene, carbon tetrachloride, ether,
It was insoluble in THF, 1,4-dioxane, acetone, methyl ethyl ketone, ethyl acetate, butanol, water, etc. As a result of IR spectrum analysis and 1 H HMR analysis of PHEMA, no absorption due to the presence of trimethylsilyl group was observed, therefore, PHEMA It was confirmed that it has the structural formula. Since PHEMA does not dissolve in THF, its −
After benzoylating the OH group with benzoic anhydride, GPC or VPO (Vapor Pressure
Measure the number average molecular weight (n) with an Osmometer),
The results are shown in Table 1 along with n, which was calculated assuming that all -OH groups in PHEMA were benzoylated. It can be seen that the two agree quite well.
It was also confirmed that this benzoylated PHEMA is a polymer with an extremely narrow molecular weight distribution (w/n=1.1 to 1.3).
図面は本発明におけるアニオン重合を行う装置
の一例の概念図を示す。
１……フラスコ、２，３……アニオン重合開始
剤封入アンプル、４，５……モノマー封入アンプ
ル、６，７……枝管、８……真空ライン、９……
コツク、１０……マグネツト。
The drawing shows a conceptual diagram of an example of an apparatus for carrying out anionic polymerization in the present invention. 1... Flask, 2, 3... Ampoule filled with anionic polymerization initiator, 4, 5... Ampoule filled with monomer, 6, 7... Branch pipe, 8... Vacuum line, 9...
Kotsuku, 10... Magnet.
Claims (1)
OSiR1R2R3を示し、ｍは１〜６の数、R1〜R3は
炭素数１〜６個の同一のアルキル基を示す。〕の
繰り返し単位からなり、数平均分子量500〜
500000のリビングポリマー。[Claims] 1. General formula [In the formula, R is a methyl group, Z is (CH 2 ) n .
OSiR 1 R 2 R 3 is shown, m is a number of 1 to 6, and R 1 to R 3 are the same alkyl group having 1 to 6 carbon atoms. ] and has a number average molecular weight of 500~
500000 living polymers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9119285A JPS61250011A (en) | 1985-04-30 | 1985-04-30 | Living polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9119285A JPS61250011A (en) | 1985-04-30 | 1985-04-30 | Living polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61250011A JPS61250011A (en) | 1986-11-07 |
| JPH0441684B2 true JPH0441684B2 (en) | 1992-07-09 |
Family
ID=14019574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9119285A Granted JPS61250011A (en) | 1985-04-30 | 1985-04-30 | Living polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61250011A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5081191A (en) * | 1989-01-18 | 1992-01-14 | The Dow Chemical Company | Functionalized polymers prepared by anionic polymerization |
| US4975491A (en) * | 1989-01-18 | 1990-12-04 | The Dow Chemical Company | Functionalized polymers prepared by anionic polymerization |
| EP0976767A4 (en) | 1997-04-14 | 2001-07-11 | Nanocarrier Co Ltd | Methacrylic polymer having terminal functional group and composition thereof |
-
1985
- 1985-04-30 JP JP9119285A patent/JPS61250011A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61250011A (en) | 1986-11-07 |
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