JP4124586B2 - Photopolymerization / dissociation reversible telechelic oligomer, polymer thereof, and production method thereof - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、光重合／解離可逆性テレケリックオリゴマーに関する。さらに詳しくは、片末端または両末端に官能性の基を有するオレフィン・オリゴマーを出発物質とする光重合／解離可逆性テレケリックオリゴマーおよびその重合体ならびにそれらの製造方法に関する。
【０００２】
【従来の技術】
本発明者らは、ポリプロピレン、ポリスチレンなどのポリオレフィンの高度制御熱分解により、片末端または両末端に官能性のビニリデン二重結合を有するオレフィン・オリゴマーが得られることをMacromolechles, 28, 7973(1995)で報告した。また、末端ビニリデン二重結合をヒドロキシル化やマレイン化してより反応性の基に修飾できることを高分子学会予稿集，47, (7), 1255(1998)で報告した。一方、アントラセンまたはウラシル、チミンなどのピリミジン塩基は、照射光の波長を選択することにより二量化と解離とが可逆的に生起することが、Macromolechles, 12, 848, 853(1979)に報告されている。
【０００３】
【発明が解決しようとする課題】
ポリオレフィンの高度制御熱分解によって得られるオレフィン・オリゴマーは、環境問題となっている漂着ペレットなどの廃オレフィンを原料にでき、しかも末端に官能性の基を有することから、これらを利用した新しい材料の創設が期待され、提案されている。しかしながら、提案された材料のほとんどは未だ実用の段階に至っていない。その有効な利用技術の確立が期待されている。
【０００４】
本発明は、片末端または両末端に官能性基を有するオレフィン・オリゴマーを出発物質とする新規な光重合／解離可逆性テレケリックオリゴマーおよびその製造方法を提供することを目的とする。
別の本発明は上記テレケリックオリゴマーを重合させたリサイクル可能な重合体およびその製造方法を提供することを目的とする。
【０００５】
本発明者らは、アントラセンの二量化と解離とが照射する活性光線の波長により可逆的に生起することに着目し、本発明を完成した。
【０００６】
本発明は、一般式（１）
【化７】
【０００７】
別の本発明は、一般式（４）
【化８】
【０００８】
【発明実施の形態】
本発明の前記一般式（１）で表される光重合／解離可逆性テレケリックオリゴマーは、式中のＲは炭素数１〜３のアルキル基、たとえばメチル、エチル、プロピルまたはフェニル基である。すなわち（ ）内はポリオレフィン鎖、たとえばポリプロピレン、ポリ１−ブテン、ポリ１−ペンテンなどの脂肪族ポリオレフィン鎖、またはポリスチレンなどの芳香族ポリオレフィン鎖のモノマー単位を表し、ｎはその繰返し数を表す。ｎは１〜１００、好ましくは１０〜５０である。
【０００９】
R1は３００nm以上の長波長の活性光線の露光により二量化し得る光官能性基、たとえばアントラニル基、ピリミジン塩基たとえばウラシル、チミジルなどである。
R2は上記光官能性基であるか、または−R3基、すなわち光に対して非官能性の基である。すなわちR3は水素、ヒドロキシ基、炭素数１〜８のアルキル基、たとえばメチル、エチル、プロピル、ブチル、ｔ−ブチル、ペンチル、ヘキシル、シクロヘキシル、ヘプチル、ノニル基など、アルコキシ基、たとえばメトキシ、エトキシ、プロポキシ、ブトキシなど、またはアルケニル基、たとえばビニル、アリルなどである。
【００１０】
上記光重合／解離可逆性テレケリックオリゴマーは、一般式（２）
【化９】
【００１１】
上記一般式（２）で表される末端ヒドロキシ基含有オレフィン・オリゴマーは、片末端または両末端にビニリデン二重結合を有するオレフィン・オリゴマーをヒドロホウ素化した後、酸化してヒドロキシル化することにより合成することができる。片末端または両末端にビニリデン二重結合を有するオレフィン・オリゴマーは、工業的に生産されているポリオレフィンを高度制御熱分解して製造することが好ましい。このポリオレフィンの高度制御熱分解で得られるオレフィン・オリゴマー、たとえばプロピレン・オリゴマーは、熱分解前のポリプロピレンの立体規則性を極めて良く維持しているので、それらの立体構造に依存した特性をも維持している。
【００１２】
本発明のテレケリックオリゴマー重合体は、下記一般式（４）
【化１０】
【００１３】
前記一般式（４）で表される重合体は、前記一般式（１）で表されるテレケリックオリゴマーを、適当な溶媒中において、要すれば増感剤の存在下に、３００nm未満の波長の光をフィルターでカットした３００nm以上の活性光線に露光して光重合させることにより製造することがでる。また、テレケリックオリゴマーの溶液を基体上に塗布して溶媒を除去した後、３００nm以上の活性光線に露光してテレケリックオリゴマーを光重合させて製造することもできる。
【００１４】
この重合体は、テレケリックオリゴマーの主鎖を構成するオレフィン・オリゴマーの特性を良く継承し、実質的にポリオレフィンと同等の特性を有する。したがって、種々の成形品の製造にベース樹脂として使用できる。また、光重合性を利用した感光性ポリマーとしての利用も期待できる。
【００１５】
【実施例】
本発明を実施例によりさらに詳細に説明する。
実施例１
両末端ヒドロキシ基含有プロピレン・オリゴマー(ｉＰＰｖ−ＯＨ)の合成
アイソタクチック・ポリプロピレンの高度制御熱分解によって得られた数平均分子量１.４３×１０3、分子量分布の分散度１.１１の両末端ビニリデン基含有プロピレン・オリゴマー(ｎ＝３４)をテトラヒドロフラン（ＴＨＦ）に分散させた中に、ＢＨ3・ＴＨＦ錯体のＴＨＦ溶液を滴下して両末端ビニリデン基含有プロピレン・オリゴマーをヒドロホウ素化した後、水酸化ナトリウム水溶液および過酸化水素水を添加して両末端のビニリデン基を酸化し、両末端ヒドロキシ基含有プロピレン・オリゴマー(ｉＰＰｖ−ＯＨ)を合成した。
【００１６】
アントラセン末端テレケリックオリゴマー(ｉＰＰｖ−ＡＴ)の合成
ｉＰＰｖ−ＯＨ／トリエチルアミンのＴＨＦ分散液に、窒素雰囲気下、室温でアントロン酸塩化物のＴＨＦ分散液を滴下し、さらに２時間反応を熟成させた。次いで、反応液からＴＨＦを留去し、キシレンを加えて還流下に溶解し、熱濾過してメタノール中に滴下して沈殿させ濾過回収した。沈殿物の収率は約９０重量％であった。得られた沈殿物の1Ｈ−ＮＭＲスペクトルはｉＰＰｖ−ＯＨのスペクトルに認められるメチレンプロトンに帰属するピークが完全に消失し、代わりにアントロン酸エステル構造の各プロトンに帰属するシグナルが明瞭に出現したことから、この沈殿物はｉＰＰｖ−ＡＴであることが確認された。
ｉＰＰｖ−ＡＴおよびｉＰＰｖ−ＯＨの1Ｈ−ＮＭＲスペクトルを図１に示す。
【００１７】
実施例２
ｉＰＰｖ−ＡＴの光重合
１０mlのＴＨＦに０.２ｇのｉＰＰｖ−ＡＴを溶解した溶液に、高圧水銀灯を用いて３００nm未満の光をナフタレン／ヘキサン溶液によるフィルターを介してカットした３００nm以上の波長の光を照射し、ｉＰＰｖ−ＡＴを重合させた。
反応液は、時間の経過に伴って白濁したが、追加のＴＨＦの添加により透明になった。
反応混合物のＧＰＣ曲線を図２に示す。図２から明らかなように時間の経過に従って、モノマーのピークが低くなり、代わりにダイマー、トリマー、テトラマーの生成を示すピークが出現する。光照射１８時間後の面積比から求めた重合反応率は８６％であった。
【００１８】
実施例３
ｉＰＰｖ−ＡＴ重合体の光解離
実施例２において光重合反応時間経過後に得られたｉＰＰｖ−ＡＴ重合体の溶液に、高圧水銀灯を用いて３００nm以上の光を光学フィルターを介してカットした３００nm未満の波長の光を照射して重合体を解離させた。
この溶液のＧＰＣ曲線は、モノマーのピークのみを示した。
【００１９】
実施例４
両末端ヒドロキシ基含有プロピレン・オリゴマー(ｓＰＰｖ−ＯＨ)の合成
シンジオタクチック・ポリプロピレンの高度制御熱分解によって得られた数平均分子量４.８４×１０3（ポリスチレン換算）、分子量分布の分散度１.４３、一分子当たりの末端ビニリデン（ＴＶＤ）の平均数約１.７３の両末端ビニリデン基含有プロピレン・オリゴマーをテトラヒドロフラン（ＴＨＦ）に分散させた中に、ＢＨ3・ＴＨＦ錯体のＴＨＦ溶液を滴下して両末端ビニリデン基含有プロピレン・オリゴマーをヒドロホウ素化した後、水酸化ナトリウム水溶液および過酸化水素水を添加して両末端のビニリデン基を酸化し、両末端ヒドロキシ基含有プロピレン・オリゴマー(ｓＰＰｖ−ＯＨ)を合成した。
【００２０】
アントラセン末端テレケリックオリゴマー(ｓＰＰｖ−ＡＴ)の合成
ｓＰＰｖ−ＯＨ／トリエチルアミンのＴＨＦ分散液に、窒素雰囲気下、室温でアントロン酸塩化物のＴＨＦ分散液を滴下し、さらに２時間反応を熟成させた。次いで、反応液からＴＨＦを留去し、キシレンを加えて還流下に溶解し、熱濾過してメタノール中に滴下して沈殿させ濾過回収した。沈殿物の収率は約９０重量％であった。得られた沈殿物の1Ｈ−ＮＭＲスペクトルはｓＰＰｖ−ＯＨのスペクトルに認められるメチレンプロトンに帰属するピークが完全に消失し、代わりにアントロン酸エステル構造の各プロトンに帰属するシグナルが明瞭に出現したことから、この沈殿物はｓＰＰｖ−ＡＴであることが確認された。
【００２１】
実施例５
ｓＰＰｖ−ＡＴの光重合
１０mlのＴＨＦに０.２ｇのｓＰＰｖ−ＡＴを溶解した溶液に、高圧水銀灯を用いて３００nm未満の光をナフタレン／ヘキサン溶液によるフィルターを介してカットした３００nm以上の波長の光を照射し、ｓＰＰｖ−ＡＴを重合させた。
反応液は、時間の経過に伴って白濁したが、追加のＴＨＦの添加により透明になった。
反応混合物のＧＰＣ曲線を図３に示す。反応時間の増加とともに分子量が徐々に増大し、１２時間以上の光照射ではｓＰＰｖ−ＡＴの分子量分布は変化しなくなり、光逐次重合は止まった。０時間と１２時間で得た逐次重合体のピークトップ、数平均分子量を比較すると、ピークトップでは約６倍、数平均分子量では約３倍になっている。このことから、ｓＰＰｖ−ＡＴの両末端のアントラセン基が光により逐次重合していることが明らかとなった。
【００２２】
実施例６
ｓＰＰｖ−ＡＴ重合体の熱解離
図４は１８時間光逐次重合したｓＰＰｖ−ＡＴを重合管に取り、窒素封管した物を１４０℃で２時間加熱した時のＧＰＣ曲線を示している。図から、光逐次重合体は熱により完全にｓＰＰｖ−ＡＴに解離していることを示している。
【００２３】
【発明の効果】
上記実施例に示したように、本発明のテレケリックオリゴマーは、光重合／解離可逆性である。したがって、このテレケリックオリゴマーの重合体は、使用後に解離させることにより原料のテレケリックオリゴマーを再生することが可能なリサイクル型ポリマー、特定的にはリサイクル型ポリオレフィンである。
【００２４】
さらに出発原料の一つ片末端または両末端にヒドロキシ基を含有するオレフィンオリゴマーは、環境問題となっている漂着ペレットなど廃ポリマーの高度制御熱分解によって容易に製造することができる。
本発明は、廃ポリマーの処理およびリサイクル型ポリマーを提供することから、ポリマー分野はもちろんのこと、環境分野における意義はきわめて大きい。
【図面の簡単な説明】
【図１】実施例１で合成されたテレケリックプロピレンオリゴマーおよびその合成に使用した両末端ヒドロキシ基含有プロピレンオリゴマーの1Ｈ−ＮＭＲスペクトル。
【図２】実施例２で得られたテレケリックプロピレンオリゴマー重合体のＧＰＣ曲線
【図３】実施例５で得られた反応混合物のＧＰＣ曲線。
【図４】実施例６で得られた反応混合物のＧＰＣ曲線。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photopolymerization / dissociation reversible telechelic oligomer. More specifically, the present invention relates to a photopolymerization / dissociation reversible telechelic oligomer starting from an olefin oligomer having a functional group at one or both ends, a polymer thereof, and a production method thereof.
[0002]
[Prior art]
Macromolechles, 28, 7973 (1995) that the present inventors can obtain an olefin oligomer having a functional vinylidene double bond at one or both ends by highly controlled pyrolysis of polyolefins such as polypropylene and polystyrene. Reported on. In addition, we reported in Polymer Science Society Proceedings, 47, (7), 1255 (1998) that a terminal vinylidene double bond can be modified to a more reactive group by hydroxylation or maleation. On the other hand, it is reported in Macromolechles, 12, 848, 853 (1979) that pyrimidine bases such as anthracene, uracil, and thymine reversibly cause dimerization and dissociation by selecting the wavelength of irradiation light. Yes.
[0003]
[Problems to be solved by the invention]
Olefin oligomers obtained by highly controlled pyrolysis of polyolefins can be made from waste olefins such as floating pellets, which are environmental problems, and have functional groups at the ends. Founding is expected and proposed. However, most of the proposed materials have not yet reached a practical stage. The establishment of effective utilization technology is expected.
[0004]
An object of the present invention is to provide a novel photopolymerization / dissociation reversible telechelic oligomer starting from an olefin oligomer having a functional group at one or both ends and a method for producing the same.
Another object of the present invention is to provide a recyclable polymer obtained by polymerizing the telechelic oligomer and a method for producing the same.
[0005]
The present inventors have completed the present invention by paying attention to the fact that dimerization and dissociation of anthracene occur reversibly depending on the wavelength of actinic rays irradiated.
[0006]
The present invention relates to a general formula (1)
[Chemical 7]
[0007]
Another aspect of the present invention is a compound of the general formula (4)
[Chemical 8]
[0008]
DETAILED DESCRIPTION OF THE INVENTION
In the photopolymerization / dissociation reversible telechelic oligomer represented by the general formula (1) of the present invention, R in the formula is an alkyl group having 1 to 3 carbon atoms, for example, a methyl, ethyl, propyl or phenyl group. That is, () represents a monomer unit of a polyolefin chain, for example, an aliphatic polyolefin chain such as polypropylene, poly 1-butene, poly 1-pentene, or an aromatic polyolefin chain such as polystyrene, and n represents the number of repetitions thereof. n is 1 to 100, preferably 10 to 50.
[0009]
R 1 is a photofunctional group that can be dimerized by exposure to actinic rays having a long wavelength of 300 nm or longer, such as an anthranyl group, a pyrimidine base such as uracil, thymidyl, and the like.
R 2 is the above-mentioned photofunctional group or —R 3 group, that is, a non-functional group with respect to light. That is, R 3 is hydrogen, hydroxy group, alkyl group having 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, nonyl group, etc., alkoxy groups such as methoxy, ethoxy , Propoxy, butoxy and the like, or alkenyl groups such as vinyl, allyl and the like.
[0010]
The photopolymerization / dissociation reversible telechelic oligomer has the general formula (2)
[Chemical 9]
[0011]
The terminal hydroxy group-containing olefin oligomer represented by the general formula (2) is synthesized by hydroborating an olefin oligomer having a vinylidene double bond at one end or both ends, and then oxidizing and hydroxylating. can do. The olefin / oligomer having a vinylidene double bond at one or both ends is preferably produced by highly controlled pyrolysis of an industrially produced polyolefin. Olefin oligomers obtained by highly controlled pyrolysis of polyolefins, such as propylene oligomers, maintain the stereoregularity of polypropylene before pyrolysis very well, so that the properties depending on their stereostructure are also maintained. ing.
[0012]
The telechelic oligomer polymer of the present invention has the following general formula (4)
Embedded image
[0013]
The polymer represented by the general formula (4) comprises a telechelic oligomer represented by the general formula (1) having a wavelength of less than 300 nm in an appropriate solvent, if necessary, in the presence of a sensitizer. Can be produced by exposing the light to an actinic ray of 300 nm or more cut by a filter and photopolymerizing it. Alternatively, the telechelic oligomer solution may be coated on a substrate to remove the solvent, and then exposed to actinic rays of 300 nm or more to photopolymerize the telechelic oligomer.
[0014]
This polymer inherits the characteristics of the olefin oligomer constituting the main chain of the telechelic oligomer well and has substantially the same characteristics as polyolefin. Therefore, it can be used as a base resin in the manufacture of various molded products. In addition, it can be expected to be used as a photosensitive polymer utilizing photopolymerization.
[0015]
【Example】
The invention is explained in more detail by means of examples.
Example 1
Synthesis of Propylene Oligomer Containing Both Ends Hydroxyl Group (iPPv-OH) Both Ends of Number Average Molecular Weight 1.43 × 10 3 Obtained by Highly Controlled Pyrolysis of Isotactic Polypropylene and Molecular Weight Distribution Dispersity 1.11 In a dispersion of vinylidene group-containing propylene oligomer (n = 34) in tetrahydrofuran (THF), a THF solution of BH 3 · THF complex was added dropwise to hydroborate the vinylidene group-containing propylene oligomer. A sodium hydroxide aqueous solution and a hydrogen peroxide solution were added to oxidize vinylidene groups at both ends to synthesize a propylene oligomer (iPPv-OH) containing hydroxy groups at both ends.
[0016]
Synthesis of anthracene-terminated telechelic oligomer (iPPv-AT) To a THF dispersion of iPPv-OH / triethylamine, a THF dispersion of antron chloride was added dropwise at room temperature under a nitrogen atmosphere, and the reaction was further aged for 2 hours. Next, THF was distilled off from the reaction solution, xylene was added, and the mixture was dissolved under reflux, filtered hot, dropped into methanol, precipitated, and collected by filtration. The yield of the precipitate was about 90% by weight. In the 1 H-NMR spectrum of the obtained precipitate, the peak attributed to the methylene proton observed in the spectrum of iPPv-OH completely disappeared, and instead a signal attributed to each proton of the anthronic ester structure clearly appeared. From this, it was confirmed that this precipitate was iPPv-AT.
1 H-NMR spectra of iPPv-AT and iPPv-OH are shown in FIG.
[0017]
Example 2
Photopolymerization of iPPv-AT Light having a wavelength of 300 nm or more obtained by cutting light of less than 300 nm through a filter with a naphthalene / hexane solution into a solution of 0.2 g of iPPv-AT dissolved in 10 ml of THF using a high-pressure mercury lamp. To polymerize iPPv-AT.
The reaction solution became cloudy over time, but became clear with the addition of additional THF.
The GPC curve of the reaction mixture is shown in FIG. As apparent from FIG. 2, the monomer peak decreases with the passage of time, and instead, peaks indicating the formation of dimer, trimer, and tetramer appear. The polymerization reaction rate determined from the area ratio after 18 hours of light irradiation was 86%.
[0018]
Example 3
Photodissociation of iPPv-AT polymer In the solution of iPPv-AT polymer obtained after the photopolymerization reaction time in Example 2, light of 300 nm or more was cut through an optical filter using a high-pressure mercury lamp, and the solution was less than 300 nm. The polymer was dissociated by irradiation with light of a wavelength.
The GPC curve of this solution showed only the monomer peak.
[0019]
Example 4
Synthesis of both terminal hydroxy group-containing propylene oligomer (sPPv-OH) Number average molecular weight 4.84 × 10 3 (polystyrene conversion) obtained by highly controlled pyrolysis of syndiotactic polypropylene, dispersity of molecular weight distribution 1. 43. A bivinylidene group-containing propylene oligomer having an average number of terminal vinylidene (TVD) per molecule of about 1.73 was dispersed in tetrahydrofuran (THF), and a THF solution of BH 3 · THF complex was added dropwise. After hydroboration of the vinylidene group-containing propylene oligomer at both ends, a sodium hydroxide aqueous solution and hydrogen peroxide solution were added to oxidize the vinylidene groups at both ends to oxidize the both-end hydroxy group-containing propylene oligomer (sPPv-OH ) Was synthesized.
[0020]
Synthesis of anthracene-terminated telechelic oligomer (sPPv-AT) To a THF dispersion of sPPv-OH / triethylamine, a THF dispersion of anthronic acid chloride was added dropwise at room temperature in a nitrogen atmosphere, and the reaction was further aged for 2 hours. Next, THF was distilled off from the reaction solution, xylene was added, and the mixture was dissolved under reflux, filtered hot, dropped into methanol, precipitated, and collected by filtration. The yield of the precipitate was about 90% by weight. In the 1 H-NMR spectrum of the obtained precipitate, the peak attributed to the methylene proton found in the spectrum of sPPv-OH completely disappeared, and instead a signal attributed to each proton of the anthronic ester structure clearly appeared. From this, it was confirmed that this precipitate was sPPv-AT.
[0021]
Example 5
Photopolymerization of sPPv-AT Light having a wavelength of 300 nm or more obtained by cutting light of less than 300 nm through a filter with a naphthalene / hexane solution into a solution of 0.2 g of sPPv-AT dissolved in 10 ml of THF using a high-pressure mercury lamp. Was irradiated to polymerize sPPv-AT.
The reaction solution became cloudy over time, but became clear with the addition of additional THF.
The GPC curve of the reaction mixture is shown in FIG. As the reaction time increased, the molecular weight gradually increased, and when irradiated for 12 hours or longer, the molecular weight distribution of sPPv-AT did not change, and the photopolymerization stopped. Comparing the peak top and number average molecular weight of the sequential polymers obtained at 0 hours and 12 hours, the peak top is about 6 times, and the number average molecular weight is about 3 times. This revealed that the anthracene groups at both ends of sPPv-AT were sequentially polymerized by light.
[0022]
Example 6
Thermal Dissociation of sPPv-AT Polymer FIG. 4 shows a GPC curve when sPPv-AT photo-sequentially polymerized for 18 hours is placed in a polymerization tube and the nitrogen sealed tube is heated at 140 ° C. for 2 hours. From the figure, it is shown that the photo sequential polymer is completely dissociated into sPPv-AT by heat.
[0023]
【The invention's effect】
As shown in the above examples, the telechelic oligomer of the present invention is photopolymerization / dissociation reversible. Therefore, the polymer of the telechelic oligomer is a recyclable polymer, specifically a recyclable polyolefin, that can regenerate the raw telechelic oligomer by dissociation after use.
[0024]
Furthermore, an olefin oligomer containing a hydroxy group at one or both ends of the starting material can be easily produced by highly controlled pyrolysis of waste polymer such as floating pellets, which is an environmental problem.
Since the present invention provides a waste polymer treatment and recyclable polymer, it has great significance not only in the polymer field but also in the environmental field.
[Brief description of the drawings]
FIG. 1 is a 1 H-NMR spectrum of a telechelic propylene oligomer synthesized in Example 1 and a propylene oligomer containing both terminal hydroxy groups used in the synthesis.
2 is a GPC curve of the telechelic propylene oligomer polymer obtained in Example 2. FIG. 3 is a GPC curve of the reaction mixture obtained in Example 5.
4 is a GPC curve of the reaction mixture obtained in Example 6. FIG.
Claims (5)
ｎは、０または１〜１００の正数であり、
Ｒは、炭素数１〜３のアルキル基またはフェニル基であり、
Ｒ １ は、３００ｎｍ以上の長波長の活性光線の露光により二量化し得る光官能性基であり、
Ｒ ２ は、Ｒ １ −、Ｒ １ −（Ｏ）ＣＯ−又はＲ ３ −（ここにＲ ３ は水素、ヒドロキシ基、炭素数１〜８のアルキル基、アルコキシ基またはアルケニル基を表す）
を表し、
ｐは０または１である。
ただし、ｐが１のときＲ １ はアントラニル基であり、ｐが０のときＲ １ はピリミジル、ウラシル−イル、またはチミジル基である。）
で表される光重合／解離可逆性テレケリックオリゴマー。General formula (1)
n is 0 or a positive number from 1 to 100;
R is an alkyl group having 1 to 3 carbon atoms or a phenyl group,
R 1 is a photofunctional group that can be dimerized by exposure to actinic rays having a long wavelength of 300 nm or longer,
R 2 represents R 1 —, R 1 — (O) CO—, or R 3 — (wherein R 3 represents hydrogen, a hydroxy group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, or an alkenyl group).
Represents
p is 0 or 1;
However, when p is 1, R 1 is an anthranyl group, and when p is 0, R 1 is a pyrimidyl, uracil-yl, or thymidyl group. )
A photopolymerization / dissociation reversible telechelic oligomer represented by:
ｎは、０または１〜１００の正数であり、
Ｒは、炭素数１〜３のアルキル基またはフェニル基であり、
Ｒ １ は、３００ｎｍ以上の長波長の活性光線の露光により二量化し得る光官能性基であり、
Ｒ ２ は、Ｒ １ −、Ｒ １ −（Ｏ）ＣＯ−又はＲ ３ −（ここにＲ ３ は水素、ヒドロキシ基、炭素数１〜８のアルキル基、アルコキシ基またはアルケニル基を表す）
を表し、
ｐは０または１である。
ただし、ｐが１のときＲ １ はアントラニル基であり、ｐが０のときＲ １ はピリミジル、ウラシル−イル、またはチミジル基である。）
で表されるテレケリックオリゴマーを、要すれば光増感剤の存在下に、３００ｎｍ以上の長波長の活性光線に露光して光重合することにより得られるテレケリックオリゴマー重合体。 General formula (1)
n is 0 or a positive number from 1 to 100;
R is an alkyl group having 1 to 3 carbon atoms or a phenyl group,
R 1 is a photofunctional group that can be dimerized by exposure to actinic rays having a long wavelength of 300 nm or longer,
R 2 represents R 1 —, R 1 — (O) CO—, or R 3 — (wherein R 3 represents hydrogen, a hydroxy group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, or an alkenyl group).
Represents
p is 0 or 1;
However, when p is 1, R 1 is an anthranyl group, and when p is 0, R 1 is a pyrimidyl, uracil-yl, or thymidyl group. )
A telechelic oligomer polymer obtained by photopolymerizing the telechelic oligomer represented by the formula (1) by exposing it to actinic rays having a long wavelength of 300 nm or longer, if necessary, in the presence of a photosensitizer.
Priority Applications (15)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001331937A JP4124586B2 (en) | 2000-11-24 | 2001-10-30 | Photopolymerization / dissociation reversible telechelic oligomer, polymer thereof, and production method thereof |
| DE60143490T DE60143490D1 (en) | 2000-11-24 | 2001-11-22 | FUNCTIONAL SUBSTANCES DERIVED FROM OLIGOOLEFINS WITH FUNCTIONAL END GROUPS |
| CNB01819429XA CN100558758C (en) | 2000-11-24 | 2001-11-22 | From the lower polyolefins deutero-functional substance of functional end-group is arranged |
| EP01997195A EP1364973B1 (en) | 2000-11-24 | 2001-11-22 | Functional substances derived from oligoolefins having functional groups at the ends |
| AU2002224085A AU2002224085A1 (en) | 2000-11-24 | 2001-11-22 | Functional substances derived from oligoolefins having functional groups at the ends |
| PCT/JP2001/010244 WO2002042340A1 (en) | 2000-11-24 | 2001-11-22 | Functional substances derived from oligoolefins having functional groups at the ends |
| US10/416,615 US7125834B2 (en) | 2000-11-24 | 2001-11-22 | Functional substances derived from oligoolefins having functional groups at the ends |
| DE60137463T DE60137463D1 (en) | 2000-11-24 | 2001-11-22 | functional substances from oligoolefins with functional end groups |
| CN200810181676XA CN101486779B (en) | 2000-11-24 | 2001-11-22 | Functional substances derived from oligoolefins having functional groups at the ends |
| KR10-2003-7006981A KR100501968B1 (en) | 2000-11-24 | 2001-11-22 | Functional substances derived from oligoolefins having functional groups at the ends |
| EP07001650A EP1790669B1 (en) | 2000-11-24 | 2001-11-22 | Functional substances derived from oligoolefins having functional groups at the ends |
| HK04110142.2A HK1067135A1 (en) | 2000-11-24 | 2004-12-22 | Functional substances derived from oligoolefins having functional groups at the ends |
| HK09110762.6A HK1133025A1 (en) | 2000-11-24 | 2004-12-22 | Functional substances derived from oligoolefins having functional groups at the ends |
| US11/440,900 US7229957B2 (en) | 2000-11-24 | 2006-05-25 | Functional substances derived from oligoolefins having functional groups at the ends |
| US11/654,751 US7345017B2 (en) | 2000-11-24 | 2007-01-18 | Functional substances derived from oligoolefins having functional groups at the ends |
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| JP2001331937A JP4124586B2 (en) | 2000-11-24 | 2001-10-30 | Photopolymerization / dissociation reversible telechelic oligomer, polymer thereof, and production method thereof |
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| JP2002161111A (en) * | 2000-11-24 | 2002-06-04 | Takashi Sawaguchi | Olefin oligomer containing terminal perfluoroalkyl group and its producing method |
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| JP2008255159A (en) * | 2007-04-02 | 2008-10-23 | Sanei Kogyo:Kk | Method for synthesizing oligomer having on its one end vinylidene-type double bond and/or oligomer having on its both ends vinylidene-type double bonds |
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