JPH09176152A - Polymerization of cyclic carbonate compound - Google Patents
Polymerization of cyclic carbonate compoundInfo
- Publication number
- JPH09176152A JPH09176152A JP34252195A JP34252195A JPH09176152A JP H09176152 A JPH09176152 A JP H09176152A JP 34252195 A JP34252195 A JP 34252195A JP 34252195 A JP34252195 A JP 34252195A JP H09176152 A JPH09176152 A JP H09176152A
- Authority
- JP
- Japan
- Prior art keywords
- cyclic carbonate
- carbonate compound
- amine
- opening polymerization
- cyclic
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、特定の一般式で示
される環状カーボナート化合物をアミン系アニオン開環
重合開始剤を用いて重合することを特徴とする重合方法
に関する。本発明における環状カーボナート化合物は、
重合時に体積膨張を示し、寸法精度や密着性等が要求さ
れる成形材料、複合材料、注型材料、封止材料、塗料お
よび接着剤等の原料として有用である。TECHNICAL FIELD The present invention relates to a polymerization method characterized in that a cyclic carbonate compound represented by a specific general formula is polymerized using an amine-based anionic ring-opening polymerization initiator. The cyclic carbonate compound in the present invention is
It is useful as a raw material for molding materials, composite materials, casting materials, sealing materials, paints, adhesives, etc., which exhibit volume expansion during polymerization and are required to have dimensional accuracy and adhesion.
【０００２】[0002]
【従来の技術】一般にスチレンやメタクリル酸メチル等
のビニルモノマーが重合する際大きな収縮を伴うことは
良く知られている。また、エポキシ樹脂、フェノール樹
脂、不飽和ポリエステル樹脂のような熱硬化性樹脂も硬
化する際、体積収縮を発生する。これら収縮は、硬化物
の物性に大きな影響を及ぼし、ボイド、クラック、外観
不良等の発生あるいは接着強度の低下等種々の問題を引
き起こすため、注型材料、封止材料、接着材料等の分野
で大きな問題となっている。もし、重合時に非収縮性を
示す材料が出来れば、寸法精度の向上やそり、歪み、剥
離発生の低減による精密な成形、内部応力の低減による
材料強度や接着力の向上等が期待できる。上記、問題を
解決するため、環状カーボナート化合物は、開環重合時
に体積が増大する現象が報告され、前記の各種用途への
応用が注目されている。例えばトリフルオロメタンスル
ホン酸メチルや三フッ化ホウ素エーテル錯体等のルイス
酸系カチオン重合開始剤およびナトリウムメトキシド等
のアルコキサイド系やｎ−ブチルリチウム、ｓｅｃ−ブ
チルリチウム等のアルキルリチウム系をアニオン重合開
始剤として開環重合し、体積膨張を示すことが知られて
いる（マクロモレキュールズ(Macromolecules),Vol.24,
No.15,4229-4235(1991)、日本化学会第６５春季年会講
演予稿集２７１項（１９９３年）、第４３回高分子学会
年次大会予稿集２９４項（１９９４年））。2. Description of the Related Art It is well known that vinyl monomers such as styrene and methyl methacrylate generally undergo large shrinkage during polymerization. Further, when a thermosetting resin such as an epoxy resin, a phenol resin, or an unsaturated polyester resin is cured, volume contraction occurs. These shrinkages have a large effect on the physical properties of the cured product, and cause various problems such as the occurrence of voids, cracks, poor appearance, etc., or a decrease in adhesive strength.Therefore, in the fields of casting materials, sealing materials, adhesive materials, etc. It is a big problem. If a material exhibiting non-shrinkage during polymerization can be obtained, improvement in dimensional accuracy, precise molding by reducing warpage, distortion, and peeling, and improvement in material strength and adhesion by reducing internal stress can be expected. In order to solve the above problems, it has been reported that the cyclic carbonate compound increases its volume during ring-opening polymerization, and attention has been paid to its application to the above-mentioned various applications. For example, Lewis acid cationic polymerization initiators such as methyl trifluoromethanesulfonate and boron trifluoride ether complex and alkoxides such as sodium methoxide and n-butyllithium, and alkyllithiums such as sec-butyllithium as anionic polymerization initiators It is known that it undergoes ring-opening polymerization and exhibits volume expansion (Macromolecules, Vol. 24,
No. 15,4229-4235 (1991), Proceedings of the 65th Annual Meeting of the Chemical Society of Japan, 271 (1993), Proceedings of the 43rd Annual Meeting of the Society of Polymer Science, 294 (1994)).
【０００３】[0003]
【発明が解決しようとする課題】ルイス酸系カチオン重
合開始剤を用いた環状カーボナート化合物の開環重合
は、トリフルオロメタンスルホン酸メチルや三フッ化ホ
ウ素エーテル錯体等の強酸であるルイス酸を用いるため
重合時の取り扱いが困難であり、また、水分による影響
が大きいため作業性が悪かった。さらに、酸成分が存在
するため金属が腐食する等の問題が生じ、電子材料用と
しては用いることができなかった。また、ナトリウムメ
トキシド等のアルコキサイド系やｎ−ブチルリチウム、
ｓｅｃ−ブチルリチウム等のアルキルリチウム系開始剤
を用いるアニオン重合による環状カーボナート化合物の
開環重合法は、水分により開始剤の活性が低下し、開環
重合への影響が著しく大きい、またナトリウムイオン、
リチウムイオン等のイオン性不純物が存在するため、電
子材料用としては用いることが出来ず、工業的に有用な
用途が見出されるに至っていなかった。The ring-opening polymerization of a cyclic carbonate compound using a Lewis acid-based cationic polymerization initiator involves the use of a Lewis acid which is a strong acid such as methyl trifluoromethanesulfonate or a boron trifluoride etherate complex. Handling at the time of polymerization was difficult, and the workability was poor due to the large influence of moisture. Furthermore, the presence of an acid component causes problems such as corrosion of the metal, and cannot be used for electronic materials. Also, alkoxides such as sodium methoxide and n-butyllithium,
In the ring-opening polymerization method of a cyclic carbonate compound by anionic polymerization using an alkyl lithium-based initiator such as sec-butyl lithium, the activity of the initiator is reduced by moisture, the influence on the ring-opening polymerization is remarkably large, and sodium ion,
Since ionic impurities such as lithium ions are present, they cannot be used for electronic materials, and have not found industrially useful uses.
【０００４】[0004]
【課題を解決するための手段】本発明者らは上記問題を
解決するために、環状カーボナート化合物を工業的に容
易な開始剤により開環重合させる方法について、開発を
行った結果、下記で示される環状カーボナート化合物が
アミン系アニオン重合開始剤により開環重合し、体積膨
張を示すことを見出し本発明を完成するに至った。In order to solve the above problems, the present inventors have developed a method for ring-opening polymerization of a cyclic carbonate compound with an industrially easy initiator. The present inventors have completed the present invention by discovering that the cyclic carbonate compound described above undergoes ring-opening polymerization with an amine-based anionic polymerization initiator and exhibits volume expansion.
【０００５】即ち、本発明は、一般式（１）又は一般式
（２）で示される環状カーボナート化合物をアミン系ア
ニオン開環重合開始剤を用いて重合することを特徴とす
る環状カーボナート化合物の重合方法であり、That is, the present invention is characterized in that the cyclic carbonate compound represented by the general formula (1) or (2) is polymerized by using an amine type anionic ring-opening polymerization initiator. Is the way
【化１】 （式中、ｘ、ｙは、０から３までの整数、Ｒ1、Ｒ2 は１
５以下の炭素数を含むアルキル基、フェニル、ナフチル
等の芳香族基、又はアリル基を示す）Embedded image (In the formula, x and y are integers from 0 to 3, and R 1 and R 2 are 1
Indicates an alkyl group containing 5 or less carbon atoms, an aromatic group such as phenyl or naphthyl, or an allyl group)
【化２】 （式中、ｘ、ｙは、０から３までの整数、Ｒ3、Ｒ4 は環
状化合物を示す）また、アミン系アニオン開環重合開始
剤が環状アミン化合物である前記の環状カーボナート化
合物の重合方法であり、また、環状アミン系開環重合開
始剤が１,８−ジアザビシクロ[５,４,０]ウンデク−７
−エン（以下ＤＢＵと略す）、４−ジメチルアミノピリ
ジン、トリエチレンジアミンである前記の環状カーボナ
ート化合物の重合方法である。Embedded image (In the formula, x and y are integers from 0 to 3, and R 3 and R 4 are cyclic compounds.) Further, the polymerization of the cyclic carbonate compound in which the amine-based anionic ring-opening polymerization initiator is a cyclic amine compound. And the cyclic amine ring-opening polymerization initiator is 1,8-diazabicyclo [5,4,0] undec-7.
It is a method for polymerizing the above cyclic carbonate compounds which are -ene (hereinafter abbreviated as DBU), 4-dimethylaminopyridine and triethylenediamine.
【０００６】本発明における環状カーボナート化合物の
好ましい例として次の化合物が挙げられる。Preferred examples of the cyclic carbonate compound in the present invention include the following compounds.
【化３】 Embedded image
【０００７】なお、本発明における環状カーボナート化
合物は一種の化合物だけでなく、二種以上の化合物の混
合物として用いてもよい。環状カーボナート化合物の製
造方法は、公知の方法（第３９回高分子学会年次大会予
稿集２８４頁（１９９０年）によって得られたもの使用
することができる。本発明で用いられるアミン系開環重
合開始剤としては、ジエチレントリアミン、トリエチレ
ンテトラミン、テトラエチレンペンタミン、ジエチルア
ミノプロピルアミン、ベンジルジメチルアミン、２−
（ジメチルアミノメチル）フェノール、２,４,６−トリ
ス（ジアミノメチル）フェノール、トリエチルアミン、
ジエチルアミン、エチルアミン、アニリン、テトラメチ
ルグアニジン、アルキルｔｅｒｔモノアミン等が挙げら
れる。特に、アミン系開環重合開始剤が環状アミン化合
物である開始剤としては、２−メチルイミダゾール、２
−エチル−４−メチルイミダゾール、２−ウンデシルイ
ミダゾール、２−ヘプタデシルイミダゾール、２−フェ
ニルイミダゾール、１−ベンジル−２−メチルイミダゾ
ール、１−シアノエチル−２−メチルイミダゾール、
２,４−ジアミノ−６−[２−メチルイミダゾリル−
(１)]−エチルＳ−トリアジン、ピペリジン、Ｎ,Ｎ’−
ジメチルピペラジン、ピリジン、ピコリン 等が挙げら
れる。環状アミン化合物中、特に、１,８−ジアザビシ
クロ[５,４,０]ウンデク−７−エン、トリエチレンジア
ミン、４−ジメチルアミノピリジンは一般式（１）およ
び一般式（２）で示される環状カーボナート化合物との
反応が著しく速く、また分子量、収率が高い。The cyclic carbonate compound in the present invention may be used not only as one compound but also as a mixture of two or more compounds. The cyclic carbonate compound may be produced by a known method (obtained by the 39th Annual Meeting of the Polymer Society of Japan, Proceedings pp. 284 (1990). Amine ring-opening polymerization used in the present invention. As the initiator, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, benzyldimethylamine, 2-
(Dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, triethylamine,
Examples thereof include diethylamine, ethylamine, aniline, tetramethylguanidine, alkyl tert-monoamine and the like. Particularly, as the initiator in which the amine-based ring-opening polymerization initiator is a cyclic amine compound, 2-methylimidazole, 2
-Ethyl-4-methyl imidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 2-phenyl imidazole, 1-benzyl-2-methyl imidazole, 1-cyanoethyl-2-methyl imidazole,
2,4-diamino-6- [2-methylimidazolyl-
(1)]-Ethyl S-triazine, piperidine, N, N'-
Dimethylpiperazine, pyridine, picoline and the like. Among the cyclic amine compounds, 1,8-diazabicyclo [5,4,0] undec-7-ene, triethylenediamine and 4-dimethylaminopyridine are cyclic carbonates represented by the general formula (1) and the general formula (2). The reaction with the compound is extremely fast, and the molecular weight and yield are high.
【０００８】前記のアミン系アニオン開始剤は、一般式
（１）および一般式（２）で示される環状カーボナート
化合物に対して、０.０１〜１５モル％、好ましくは、
０.１〜５モル％の範囲内で用いられる。０.０１モル％
未満では、重合は進行するものの、長時間を必要とする
ため好ましくない。一方、１０モル％を超える濃度で
は、低分子量体が生じ易くなるため好ましくない。これ
ら重合反応の条件は、硬化促進剤の種類、量により異な
るが、通常、室温〜２００℃、好ましくは、５０〜１８
０℃の範囲である。本発明の化合物は、必要に応じて、
充填材、染料、顔料等の添加剤を配合することができ
る。充填材としては、木粉、パルプ粉、各種織物粉砕
物、熱硬化樹脂積層板および成形品の粉砕物等の有機質
のもの、シリカ、ガラス、タルク、アルミナ、炭酸カル
シウム、カーボン等の無機粉末、ガラス繊維、カーボン
繊維、マイカ等の無機繊維等を選ぶことができる。The above-mentioned amine-based anion initiator is 0.01 to 15 mol%, preferably 0.1 to 15 mol% with respect to the cyclic carbonate compound represented by the general formula (1) or (2).
It is used within the range of 0.1 to 5 mol%. 0.01 mol%
If it is less than 1, the polymerization will proceed, but it requires a long time, which is not preferable. On the other hand, if the concentration exceeds 10 mol%, a low molecular weight product is likely to be formed, which is not preferable. The conditions of these polymerization reactions vary depending on the kind and amount of the curing accelerator, but are usually room temperature to 200 ° C., preferably 50 to 18
It is in the range of 0 ° C. The compound of the present invention, if necessary,
Additives such as fillers, dyes and pigments can be added. Examples of the filler include organic powders such as wood powder, pulp powder, various crushed textiles, crushed thermosetting resin laminates and molded products, and inorganic powders such as silica, glass, talc, alumina, calcium carbonate, and carbon; Inorganic fibers such as glass fiber, carbon fiber, and mica can be selected.
【０００９】[0009]
【実施例】以下、実施例および比較例に基づいて、本発
明を具体的に説明する。1Ｈ−ＮＭＲスペクトルはＴＭ
Ｓを内部標準として、日本電子社製ＥＸ−９０型を用い
て測定し、赤外線吸収スペクトルは、日本分光工業社製
ＦＴ／ＩＲ−３型を用いて測定した。数平均分子量は、
東ソー社製ＧＰＣ−８０００システム測定装置を用いて
測定し、ポリスチレン換算によって算出した。密度は、
柴山科学器械製作所社製密度勾配管法比重測定装置Ａ型
で臭化カリウム、または、臭化カルシウム水溶液２５℃
中で測定した。The present invention will be specifically described below based on examples and comparative examples. 1 H-NMR spectrum is TM
Using S as an internal standard, an EX-90 type manufactured by JEOL Ltd. was used, and an infrared absorption spectrum was measured using an FT / IR-3 type manufactured by JASCO Corporation. The number average molecular weight is
It measured using the GPC-8000 system measuring device by Tosoh Corporation, and calculated by polystyrene conversion. The density is
Shibayama Scientific Instruments Co., Ltd. Density Gradient Tube Method Specific Gravity Measuring Device Type A, potassium bromide or calcium bromide aqueous solution 25 ° C
Measured in
【００１０】［実施例１］化学式（４）で示される１,
３−ジオキサン−２−オン １.０２ｇ、[Example 1] 1, represented by the chemical formula (4),
3-dioxan-2-one 1.02 g,
【化４】 ＤＢＵ ０.０４ｇを、あらかじめ攪拌子を装填した試
験管に仕込み、１２０℃、１０分間加熱攪拌を行い、塩
化メチレン／酢酸１０ｍｌを添加して、重合を終了及
び、重合物を溶解させ、メタノール２００ｍｌ中に再沈
殿して濾過後回収し、白色固形物０.８０ｇを得た。該
生成物の数平均分子量は１００００であった。該生成物
の1Ｈ-ＮＭＲスペクトルを測定したところ、４.２４お
よび２.０５ｐｐｍに開環重合したことを示すメチレン
のピークが観測された。該生成物のＩＲスペクトルを観
測したところ、２９７０、１７５０、１４７０、１２４
０ｃｍ-1にピークが観測された。これらの結果から、該
生成物は下記の化学式（５）の繰り返し単位からなる、
１,３−ジオキサン−２−オンが開環重合した構造のポ
リマーであると確認された。Embedded image DBU (0.04 g) was placed in a test tube pre-loaded with a stirrer, heated and stirred at 120 ° C. for 10 minutes, and 10 ml of methylene chloride / acetic acid was added to terminate the polymerization and dissolve the polymer to obtain 200 ml of methanol. The precipitate was reprecipitated in the solution, collected after filtration, and 0.80 g of a white solid product was obtained. The number average molecular weight of the product was 10,000. When the 1 H-NMR spectrum of the product was measured, a methylene peak indicating ring-opening polymerization at 4.24 and 2.05 ppm was observed. When the IR spectrum of the product was observed, it was 2970, 1750, 1470, 124.
A peak was observed at 0 cm -1 . From these results, the product is composed of repeating units of the following chemical formula (5):
It was confirmed to be a polymer having a structure in which 1,3-dioxan-2-one was subjected to ring-opening polymerization.
【化５】 該ポリマーの密度を測定したところ、１.２０であり、
モノマーの密度１.２５から計算した体積膨張率は、４.
１％であった。Embedded image When the density of the polymer was measured, it was 1.20,
The volume expansion coefficient calculated from the monomer density of 1.25 is 4.
1%.
【００１１】［実施例２］実施例１において、１,３−
ジオキサン−２−オン １.０２ｇに代えて化学式
（６）で示されるノルボルネン環状カーボナート １.
８０ｇ を用い、[Second Embodiment] In the first embodiment, 1,3-
Norbornene cyclic carbonate represented by the chemical formula (6) in place of 1.02 g of dioxan-2-one 1.
Using 80 g,
【化６】 反応時間を３０分にした以外は実施例１と同様にして重
合を行い、白色固形物１.２０ｇを得た。該生成物の数
平均分子量は８０００であった。該生成物は1Ｈ-ＮＭＲ
スペクトル、ＩＲスペクトルからノルボルネン環状カー
ボナートが開環重合した構造のポリマーであることが確
認された。[Chemical 6] Polymerization was performed in the same manner as in Example 1 except that the reaction time was 30 minutes to obtain 1.20 g of a white solid. The number average molecular weight of the product was 8,000. The product is 1 H-NMR
From the spectrum and IR spectrum, it was confirmed that the norbornene cyclic carbonate was a polymer having a structure obtained by ring-opening polymerization.
【００１２】［実施例３］実施例１においてＤＢＵ
０.０４ｇに代えてジメチルアミノピリジン ０.０３ｇ
を用い、反応時間を１時間にした以外は 実施例１と同
様にして重合を行い、白色固形物 ０.７５ｇを得た。
該生成物の数平均分子量は９０００であった。該生成物
は1Ｈ-ＮＭＲスペクトル、ＩＲスペクトルから１,３−
ジオキサン−２−オンが開環重合した構造のポリマーで
あることが確認された。[Embodiment 3] DBU in Embodiment 1
Dimethylaminopyridine 0.03 g instead of 0.04 g
Polymerization was conducted in the same manner as in Example 1 except that the reaction time was 1 hour to obtain 0.75 g of a white solid.
The number average molecular weight of the product was 9000. The product was analyzed by 1 H-NMR spectrum and IR spectrum to give 1,3-
It was confirmed that dioxan-2-one was a polymer having a structure obtained by ring-opening polymerization.
【００１３】［比較例１］実施例１においてＤＢＵ
０.０４ｇに代えてトリフルオロメタンスルホン酸メチ
ル ０.０４ｇを用い、反応時間を１時間にした以外は
実施例１と同様にして重合を行い、白色固形物 ０.１
０ｇを得た。該生成物の数平均分子量は５００であっ
た。該生成物は1Ｈ-ＮＭＲスペクトル、ＩＲスペクトル
から１,３−ジオキサン−２−オンが開環重合した構造
のポリマーであることが確認された。Comparative Example 1 DBU in Example 1
Methyl trifluoromethanesulfonate (0.04 g) was used instead of 0.04 g, and the reaction time was changed to 1 hour.
Polymerization was carried out in the same manner as in Example 1 to give a white solid 0.1
0 g was obtained. The number average molecular weight of the product was 500. From the 1 H-NMR spectrum and IR spectrum, it was confirmed that the product was a polymer having a structure in which 1,3-dioxan-2-one was subjected to ring-opening polymerization.
【００１４】［比較例２］比較例１においてＤＢＵ
０.０４ｇに代えてｓｅｃ−ブチルリチウム ０.０４ｇ
を用い、１,３−ジオキサン−２−オン １.０２ｇに代
えてノルボルネン環状カーボナート ２.１０ｇ反応時
間を１時間にした以外は 実施例１と同様にして重合を
行い、白色固形物 ０.２０ｇを得た。該生成物の数平
均分子量は８００であった。該生成物は1Ｈ-ＮＭＲスペ
クトル、ＩＲスペクトルからノルボルネン環状カーボナ
ートが開環重合した構造のポリマーであることが確認さ
れた。Comparative Example 2 DBU in Comparative Example 1
Sec-Butyllithium 0.04 g instead of 0.04 g
Was used in place of 1.02 g of 1,3-dioxan-2-one, 2.10 g of norbornene cyclic carbonate was polymerized in the same manner as in Example 1 except that the reaction time was 1 hour. Got The number average molecular weight of the product was 800. From the 1 H-NMR spectrum and IR spectrum, it was confirmed that the product was a polymer having a structure in which a norbornene cyclic carbonate was subjected to ring-opening polymerization.
【００１５】[0015]
【発明の効果】環状カーボナートは、アミン系アニオン
開環重合開始剤により、収率良く、高分子量な重合物が
得られ、体積膨張を示す。従って、注型材料、封止材
料、接着材料等の工業材料の用途に有用である。INDUSTRIAL APPLICABILITY The cyclic carbonate gives a high yield and high molecular weight polymer by the amine type anionic ring-opening polymerization initiator, and exhibits volume expansion. Therefore, it is useful for applications of industrial materials such as casting materials, sealing materials, and adhesive materials.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｄ 321/10 Ｃ０７Ｄ 321/10 487/04 １５０ 487/04 １５０ Ｃ０８Ｇ 64/30 ＮＰＵ Ｃ０８Ｇ 64/30 ＮＰＵ // Ｃ０７Ｄ 213/74 Ｃ０７Ｄ 213/74 Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI Technical display location C07D 321/10 C07D 321/10 487/04 150 487/04 150 C08G 64/30 NPU C08G 64/30 NPU // C07D 213/74 C07D 213/74
Claims (3)
る環状カーボナート化合物をアミン系アニオン開環重合
開始剤を用いて重合することを特徴とする環状カーボナ
ート化合物の重合方法。 【化１】 （式中、ｘ、ｙは、０から３までの整数、Ｒ1、Ｒ2 は１
５以下の炭素数を含むアルキル基、フェニル、ナフチル
等の芳香族基、又はアリル基を示す） 【化２】 （式中、ｘ、ｙは、０から３までの整数、Ｒ3、Ｒ4 は環
状化合物を示す）1. A method for polymerizing a cyclic carbonate compound, which comprises polymerizing the cyclic carbonate compound represented by the general formula (1) or (2) using an amine-based anionic ring-opening polymerization initiator. Embedded image (In the formula, x and y are integers from 0 to 3, and R 1 and R 2 are 1
Indicates an alkyl group containing 5 or less carbon atoms, an aromatic group such as phenyl or naphthyl, or an allyl group) (In the formula, x and y are integers from 0 to 3, and R 3 and R 4 are cyclic compounds.)
アミン化合物である請求項１記載の環状カーボナート化
合物の重合方法。2. The method for polymerizing a cyclic carbonate compound according to claim 1, wherein the amine-based anionic ring-opening polymerization initiator is a cyclic amine compound.
ジアザビシクロ[５,４,０]ウンデク−７−エン、４−ジ
メチルアミノピリジン、トリエチレンジアミンである請
求項１記載の環状カーボナート化合物の重合方法。3. A cyclic amine ring-opening polymerization initiator is 1,8-
The method for polymerizing a cyclic carbonate compound according to claim 1, which is diazabicyclo [5,4,0] undec-7-ene, 4-dimethylaminopyridine, or triethylenediamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34252195A JPH09176152A (en) | 1995-12-28 | 1995-12-28 | Polymerization of cyclic carbonate compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34252195A JPH09176152A (en) | 1995-12-28 | 1995-12-28 | Polymerization of cyclic carbonate compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09176152A true JPH09176152A (en) | 1997-07-08 |
Family
ID=18354395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34252195A Pending JPH09176152A (en) | 1995-12-28 | 1995-12-28 | Polymerization of cyclic carbonate compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09176152A (en) |
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|---|---|---|---|---|
| JP2006077150A (en) * | 2004-09-10 | 2006-03-23 | Jsr Corp | Cyclic olefine-based ring-opened polymer, method for producing the same, crosslinked polymer of the same and method for producing the crosslinked polymer |
| JP2007071921A (en) * | 2005-09-02 | 2007-03-22 | Daicel Chem Ind Ltd | Volume hologram recording photosensitive composition |
| JP2010043290A (en) * | 2009-11-26 | 2010-02-25 | Jsr Corp | Cyclic olefin-based ring-opened polymer, method for producing the same, crosslinked polymer of the same and method for producing the crosslinked polymer |
| JP2011021206A (en) * | 2010-10-29 | 2011-02-03 | Jsr Corp | Method of producing cycloolefin-based ring-opened polymer |
| JP2011505468A (en) * | 2007-11-30 | 2011-02-24 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Solvent-free process for the polymerization of trimethylene carbonate to poly (trimethylene glycol carbonate trimethylene glycol ether) diol |
| JP2011505467A (en) * | 2007-11-30 | 2011-02-24 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Process for producing poly (trimethylene carbonate) glycol |
| JP2011046958A (en) * | 2010-10-29 | 2011-03-10 | Jsr Corp | Method for producing cyclic olefin ring-opened polymer |
-
1995
- 1995-12-28 JP JP34252195A patent/JPH09176152A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006077150A (en) * | 2004-09-10 | 2006-03-23 | Jsr Corp | Cyclic olefine-based ring-opened polymer, method for producing the same, crosslinked polymer of the same and method for producing the crosslinked polymer |
| JP2007071921A (en) * | 2005-09-02 | 2007-03-22 | Daicel Chem Ind Ltd | Volume hologram recording photosensitive composition |
| JP4636469B2 (en) * | 2005-09-02 | 2011-02-23 | ダイセル化学工業株式会社 | Photosensitive composition for volume hologram recording |
| JP2011505468A (en) * | 2007-11-30 | 2011-02-24 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Solvent-free process for the polymerization of trimethylene carbonate to poly (trimethylene glycol carbonate trimethylene glycol ether) diol |
| JP2011505467A (en) * | 2007-11-30 | 2011-02-24 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Process for producing poly (trimethylene carbonate) glycol |
| JP2010043290A (en) * | 2009-11-26 | 2010-02-25 | Jsr Corp | Cyclic olefin-based ring-opened polymer, method for producing the same, crosslinked polymer of the same and method for producing the crosslinked polymer |
| JP2011021206A (en) * | 2010-10-29 | 2011-02-03 | Jsr Corp | Method of producing cycloolefin-based ring-opened polymer |
| JP2011046958A (en) * | 2010-10-29 | 2011-03-10 | Jsr Corp | Method for producing cyclic olefin ring-opened polymer |
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