JP2017066222A - Terminal modified polybutadiene - Google Patents
Terminal modified polybutadiene Download PDFInfo
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Abstract
Description
本発明は、末端変性ポリブタジエンに関する。 The present invention relates to terminal-modified polybutadiene.
ポリブタジエン鎖の末端を様々な構造で変性したポリブタジエンが提案されている。それらの末端変性ポリブタジエンは、様々な用途に応用されている（特許文献１、２）。 There have been proposed polybutadienes having terminal ends of polybutadiene chains modified with various structures. Those terminal-modified polybutadienes are applied to various uses (Patent Documents 1 and 2).
様々な用途に応用することができる新規の構造を有する末端変性ポリブタジエンが求められていた。 There has been a demand for terminally modified polybutadiene having a novel structure that can be applied to various uses.
本発明者らは上記課題を解決するために鋭意検討を重ねた。その結果、新規の構造を有する末端変性ポリブタジエンを見出した。本発明はこれらの知見に基づいて完成するに至ったものである。 The present inventors have made extensive studies to solve the above problems. As a result, a terminal-modified polybutadiene having a novel structure was found. The present invention has been completed based on these findings.
すなわち、本発明は、
（１）式〔Ｉ〕
(1) Formula [I]
本発明によれば、新規の構造を有する末端変性ポリブタジエンを提供することができる。 According to the present invention, a terminal-modified polybutadiene having a novel structure can be provided.
以下、本発明を詳細に説明する。
（末端変性ポリブタジエン）
本発明の末端変性ポリブタジエンは式〔Ｉ〕で表される。
Hereinafter, the present invention will be described in detail.
(Terminal-modified polybutadiene)
The terminal-modified polybutadiene of the present invention is represented by the formula [I].
式〔Ｉ〕中、実線と点線の二重結合部分は、単結合または二重結合を意味する。実線と点線の二重結合部分が、二重結合であるとき、シス体、トランス体、またはシス体とトランス体の混合物いずれであってもよい。 In the formula [I], the double bond part of a solid line and a dotted line means a single bond or a double bond. When the double bond portion of the solid line and the dotted line is a double bond, it may be a cis isomer, a trans isomer, or a mixture of a cis isomer and a trans isomer.
式〔Ｉ〕中、Ｒは、直鎖又は分岐鎖を有するＣ１〜Ｃ１０アルキレン基を表す。直鎖又は分岐鎖を有するＣ１〜Ｃ１０のアルキレン基としては、メチレン、エチレン、プロピレン、メチルエチレン、ブチレン、１，２−ジメチルエチレン、ペンチレン、１−メチルブチレン、２−メチルブチレン、ヘキサメチレン等が挙げられる。これらのうち、エチレンが好ましい。 In formula [I], R represents a C1-C10 alkylene group having a straight or branched chain. Examples of the C1-C10 alkylene group having a straight chain or branched chain include methylene, ethylene, propylene, methylethylene, butylene, 1,2-dimethylethylene, pentylene, 1-methylbutylene, 2-methylbutylene, hexamethylene and the like. Can be mentioned. Of these, ethylene is preferred.
式〔Ｉ〕中、ＰＢは、ポリブタジエン鎖、又は水素添加ポリブタジエン鎖を表す。
ポリブタジエン鎖とは、式〔II〕で表される１，４−結合による繰り返し単位、及び／又は、式〔III〕で表される１，２−結合による繰り返し単位を骨格として有するポリブタジエン鎖を意味する。
In the formula [I], PB represents a polybutadiene chain or a hydrogenated polybutadiene chain.
The polybutadiene chain means a polybutadiene chain having, as a skeleton, a repeating unit having a 1,4-bond represented by the formula [II] and / or a repeating unit having a 1,2-bond represented by the formula [III]. To do.
式〔II〕で表される１，４−結合による繰り返し単位と、式〔III〕で表される１，２−結合の比率は、各々０〜１００モル％である。それらのうち、式〔II〕で表される繰り返し単位と、式〔III〕で表される繰り返し単位のモル比が、３０／７０〜１／９９であるのが好ましく、２０／８０〜１／９９であるのがより好ましい。 The ratio of the repeating unit by the 1,4-bond represented by the formula [II] and the 1,2-bond represented by the formula [III] is 0 to 100 mol%. Among them, the molar ratio of the repeating unit represented by the formula [II] and the repeating unit represented by the formula [III] is preferably 30/70 to 1/99, and 20/80 to 1/99. 99 is more preferred.
水素添加ポリブタジエン鎖とは、上記で説明したポリブタジエン鎖中の式〔II〕または式〔III〕で表される繰り返し単位中の二重結合の全部あるいは一部が水素添加されているポリマー鎖を表す。二重結合が水素添加されている割合は特に限定されないが、全繰り返し単位中に含まれる二重結合の７０〜１００％が水素添加されているのが好ましく、８０〜１００％が水素添加されているのがより好ましい。 The hydrogenated polybutadiene chain represents a polymer chain in which all or part of the double bond in the repeating unit represented by the formula [II] or the formula [III] in the polybutadiene chain described above is hydrogenated. . The ratio in which the double bonds are hydrogenated is not particularly limited, but 70 to 100% of the double bonds contained in all repeating units are preferably hydrogenated, and 80 to 100% are hydrogenated. More preferably.
式〔Ｉ〕で表される末端変性ポリブタジエン中の実線と点線の二重結合部分が、二重結合である時、ＰＢは水素添加ポリブタジエン鎖であるのが好ましい。 When the solid and dotted double bonds in the end-modified polybutadiene represented by the formula [I] are double bonds, PB is preferably a hydrogenated polybutadiene chain.
式〔Ｉ〕中、ｎは、１または２を表す。 In the formula [I], n represents 1 or 2.
本発明の末端変性ポリブタジエンは、ポリスチレンを指標として用いたＧＰＣ（ゲル濾過）法によると、数平均分子量（Ｍｎ）が５００〜１０，０００であるのが好ましい。 The terminal-modified polybutadiene of the present invention preferably has a number average molecular weight (Mn) of 500 to 10,000 according to GPC (gel filtration) method using polystyrene as an index.
（末端変性ポリブタジエンの製造方法）
本発明の末端変性ポリブタジエンは、例えば下記に示す方法に従って製造することができる。
すなわち、式〔IV〕で表される末端水酸基変性ポリブタジエンと、無水マレイン酸または無水コハク酸を反応させることにより製造することができる。
(Method for producing terminal-modified polybutadiene)
The terminal-modified polybutadiene of the present invention can be produced, for example, according to the method shown below.
That is, it can be produced by reacting a terminal hydroxyl group-modified polybutadiene represented by the formula [IV] with maleic anhydride or succinic anhydride.
式〔IV〕中、Ｒ、ＰＢ、およびｎは、式〔Ｉ〕中の、Ｒ、ＰＢ、およびｎと同様である。 In formula [IV], R, PB, and n are the same as R, PB, and n in formula [I].
反応は、無溶媒で行ってもよいし、溶媒中で行ってもよい。 The reaction may be performed without a solvent or in a solvent.
反応温度は、５０℃〜２００℃で行うのが好ましく、６０℃〜１５０℃で行うのがより好ましい。 The reaction temperature is preferably 50 to 200 ° C., more preferably 60 to 150 ° C.
式〔IV〕で表される末端水酸基変性ポリブタジエンとしては、具体的に、ＮＩＳＳＯ−ＰＢ−Ｇ−１０００、ＮＩＳＳＯ−ＰＢ−Ｇ−２０００、ＮＩＳＳＯ−ＰＢ−Ｇ−３０００、ＮＩＳＳＯ−ＰＢ−ＧＩ−１０００、ＮＩＳＳＯ−ＰＢ−ＧＩ−２０００、ＮＩＳＳＯ−ＰＢ−ＧＩ−３０００などを挙げることができる。 Specific examples of the terminal hydroxyl group-modified polybutadiene represented by the formula [IV] include NISSO-PB-G-1000, NISSO-PB-G-2000, NISSO-PB-G-3000, NISSO-PB-GI-1000. , NISSO-PB-GI-2000, NISSO-PB-GI-3000, and the like.
本発明の末端変性ポリブタジエンは、各種ゴム用の添加剤などの用途に用いることができる。 The terminal-modified polybutadiene of the present invention can be used for applications such as additives for various rubbers.
以下、実施例を挙げて本発明をより具体的に説明する。なお、本発明は以下の実施例によって制限を受けるものではなく、本発明の趣旨に適合し得る範囲で適宜に変更を加えて実施することが勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。 Hereinafter, the present invention will be described more specifically with reference to examples. It should be noted that the present invention is not limited by the following examples, and can of course be implemented with appropriate modifications within a range that can be adapted to the spirit of the present invention. To be included in the scope.
実施例１
メカニカルスターラー、コンデンサー、温度計を取り付けた５００ｍＬの４つ口セパラブルフラスコに末端水酸基変性ポリブタジエン（ＧＩ−２０００、日本曹達社製、数平均分子量（Ｍｎ）：２０００、水酸基価（ＯＨＶ）：４６．３（ＫＯＨｍｇ/ｇ））３００ｇ、ジブチルヒドロキシトルエン０．３ｇおよび無水マレイン酸２３．１ｇを加え、内温を８０℃まで昇温し８０℃で４時間撹拌した。トルエン３００ｇを加え、室温まで冷却してから１時間撹拌した後に反応液を濾過して不溶物を除去した。得られた濾液を減圧濃縮で溶媒を留去し末端変性ポリブタジエンＡを３０９ｇ得た。
Example 1
A terminal hydroxyl group-modified polybutadiene (GI-2000, manufactured by Nippon Soda Co., Ltd., number average molecular weight (Mn): 2000, hydroxyl value (OHV): 46. 3 (KOH mg / g)) 300 g, dibutylhydroxytoluene 0.3 g and maleic anhydride 23.1 g were added, the internal temperature was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 4 hours. After adding 300 g of toluene and cooling to room temperature and stirring for 1 hour, the reaction solution was filtered to remove insoluble matters. The obtained filtrate was concentrated under reduced pressure to remove the solvent, and 309 g of terminal-modified polybutadiene A was obtained.
実施例２
メカニカルスターラー、コンデンサー、温度計を取り付けた５００ｍＬの４つ口セパラブルフラスコに末端水酸基変性ポリブタジエン（ＧＩ−２０００、日本曹達社製、数平均分子量（Ｍｎ）：２０００、水酸基価（ＯＨＶ）：４６．１（ＫＯＨｍｇ/ｇ））３００ｇ、ジブチルヒドロキシトルエン０．３ｇおよび無水コハク酸２３．４ｇを加え、内温を１２０℃まで昇温し１２０℃で４時間撹拌した。８０℃まで冷却した後にトルエン３００ｇを加え、室温まで冷却してから１時間撹拌した後に反応液を濾過して不溶物を除去した。得られた濾液を減圧濃縮で溶媒を留去し末端変性ポリブタジエンＢを３０４ｇ得た。
Example 2
A terminal hydroxyl group-modified polybutadiene (GI-2000, manufactured by Nippon Soda Co., Ltd., number average molecular weight (Mn): 2000, hydroxyl value (OHV): 46. 1 (KOH mg / g)) 300 g, dibutylhydroxytoluene 0.3 g and succinic anhydride 23.4 g were added, the internal temperature was raised to 120 ° C., and the mixture was stirred at 120 ° C. for 4 hours. After cooling to 80 ° C., 300 g of toluene was added, and after cooling to room temperature, the mixture was stirred for 1 hour, and then the reaction solution was filtered to remove insoluble matters. The obtained filtrate was concentrated under reduced pressure to remove the solvent, and 304 g of terminal-modified polybutadiene B was obtained.
Claims (1)
Formula [I]
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| JP2015191061A JP2017066222A (en) | 2015-09-29 | 2015-09-29 | Terminal modified polybutadiene |
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| JP2015191061A JP2017066222A (en) | 2015-09-29 | 2015-09-29 | Terminal modified polybutadiene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018180371A1 (en) | 2017-03-29 | 2018-10-04 | 三井化学株式会社 | Thermoplastic elastomer composition having excellent molding appearance and molded body thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018180371A1 (en) | 2017-03-29 | 2018-10-04 | 三井化学株式会社 | Thermoplastic elastomer composition having excellent molding appearance and molded body thereof |
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