JP5283107B2 - Functionalized linear polymer and process for producing the same - Google Patents
Functionalized linear polymer and process for producing the same Download PDFInfo
- Publication number
- JP5283107B2 JP5283107B2 JP2008118073A JP2008118073A JP5283107B2 JP 5283107 B2 JP5283107 B2 JP 5283107B2 JP 2008118073 A JP2008118073 A JP 2008118073A JP 2008118073 A JP2008118073 A JP 2008118073A JP 5283107 B2 JP5283107 B2 JP 5283107B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- group
- general formula
- nucleophilic solvent
- production method
- 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.)
- Active
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 230000000269 nucleophilic effect Effects 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims description 9
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 9
- -1 mercaptophenyl group Chemical group 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000005036 alkoxyphenyl group Chemical group 0.000 claims description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004001 thioalkyl group Chemical group 0.000 claims description 3
- 150000003573 thiols Chemical class 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 9
- 239000003930 superacid Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical class ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- 125000000524 functional group Chemical group 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- URQUNWYOBNUYJQ-UHFFFAOYSA-N diazonaphthoquinone Chemical compound C1=CC=C2C(=O)C(=[N]=[N])C=CC2=C1 URQUNWYOBNUYJQ-UHFFFAOYSA-N 0.000 description 4
- 229920006351 engineering plastic Polymers 0.000 description 4
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 4
- UVGPELGZPWDPFP-UHFFFAOYSA-N 1,4-diphenoxybenzene Chemical compound C=1C=C(OC=2C=CC=CC=2)C=CC=1OC1=CC=CC=C1 UVGPELGZPWDPFP-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KZJRKRQSDZGHEC-UHFFFAOYSA-N 2,2,2-trifluoro-1-phenylethanone Chemical compound FC(F)(F)C(=O)C1=CC=CC=C1 KZJRKRQSDZGHEC-UHFFFAOYSA-N 0.000 description 1
- 229940087189 2,2,2-trifluoroacetophenone Drugs 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- BSILAEQTGTZMIW-UHFFFAOYSA-N bis(4-phenoxyphenyl)methanone Chemical compound C=1C=C(OC=2C=CC=CC=2)C=CC=1C(=O)C(C=C1)=CC=C1OC1=CC=CC=C1 BSILAEQTGTZMIW-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
本発明は、機能化された新規直鎖状重合体及びその製造方法に関する。より詳細には、本発明は、ポリ付加縮合機構[Poly(addition−condensation) Mechanism]により、ポリ(フェニレンエーテル)の各構造単位を機能化した直鎖状重合体及びその製造方法に関する。 The present invention relates to a functionalized novel linear polymer and a method for producing the same. More specifically, the present invention relates to a linear polymer in which each structural unit of poly (phenylene ether) is functionalized by a poly addition condensation mechanism [Poly (addition-condensation) mechanism] and a method for producing the same.
2004年にKhalilovらが以下のような重合を報告した(非特許文献1)。この重合は2,2,2−トリフルオロアセトフェノンに4,4’−ジフェノキシベンゾフェノンが2回求核置換する反応で、室温で高分子量のポリマーが得られている。
本発明は、ポリ付加縮合機構(Poly(addition−condensation) Mechanism)により、ポリ(フェニレンエーテル)の各構造単位を機能化した直鎖状重合体及びその製造方法を提供することを目的とする。 An object of the present invention is to provide a linear polymer obtained by functionalizing each structural unit of poly (phenylene ether) by a poly (addition-condensation) mechanism and a method for producing the same.
本発明者らは、触媒としてトリフルオロメタンスルホン酸を用いて、4−トリフルオロアセチル−4’−フェノキシジフェノキシベンゼンを重合した結果、高分子量の直鎖状ポリフェニレンエーテルが得られることを見出した。さらに、安定なカルボカチオンの反応を利用し、重合停止に用いる溶媒を水、メタノール、アニソール、及びフェノール等に換えることによって主鎖中の1モノマー単位にヒドロキシル基、メトキシ基、メトキシフェニル基、及びヒドロキシルフェニル基等を導入できることを見出し、本発明を完成させた。 The present inventors have found that high-molecular-weight linear polyphenylene ether is obtained as a result of polymerizing 4-trifluoroacetyl-4'-phenoxydiphenoxybenzene using trifluoromethanesulfonic acid as a catalyst. Furthermore, by utilizing a stable carbocation reaction, the solvent used for terminating the polymerization is changed to water, methanol, anisole, phenol, etc., so that one monomer unit in the main chain has a hydroxyl group, a methoxy group, a methoxyphenyl group, and The present inventors have found that a hydroxylphenyl group can be introduced and completed the present invention.
即ち、本発明は下記の新規重合体及びその製造方法を提供する。
1.(A)下記一般式(2)
で示される化合物に、超強酸を加えて重合反応を行う工程、及び
(B)求核性の溶媒を添加して重合反応を停止させる工程
を含む、下記一般式(1)で示される構造単位を有する重合体の製造方法。
2.前記超強酸として、トリフルオロメタンスルホン酸(CF3SO3H)及び/又はフルオロスルホン酸(HSO3F)を用いる上記1に記載の製造方法。
3.前記求核性の溶媒として、水を用いる上記1又は2に記載の製造方法。
4.前記求核性の溶媒として、アルコール及びチオールから選ばれる少なくとも1種を用いる上記1又は2に記載の製造方法。
5.前記求核性の溶媒として、アニソールを用いる上記1又は2に記載の製造方法。
6.前記求核性の溶媒として、フェノールを用いる上記1又は2に記載の製造方法。
7.下記一般式(1)で示される構造単位を有する重合体。
8.前記一般式(1)における基−R1が、ヒドロキシル基、アルコキシ基、チオアルキル基、ヒドロキシフェニル基、メルカプトフェニル基又はアルコキシフェニル基である上記7に記載の重合体。
That is, this invention provides the following novel polymer and its manufacturing method.
1. (A) The following general formula (2)
A structural unit represented by the following general formula (1), which comprises a step of adding a super strong acid to the compound represented by the formula (1) and carrying out a polymerization reaction to stop the polymerization reaction by adding a nucleophilic solvent. The manufacturing method of the polymer which has this.
2. 2. The production method according to 1 above, wherein trifluoromethanesulfonic acid (CF 3 SO 3 H) and / or fluorosulfonic acid (HSO 3 F) is used as the super strong acid.
3. 3. The production method according to 1 or 2 above, wherein water is used as the nucleophilic solvent.
4). 3. The production method according to 1 or 2 above, wherein at least one selected from alcohol and thiol is used as the nucleophilic solvent.
5. 3. The production method according to 1 or 2 above, wherein anisole is used as the nucleophilic solvent.
6). 3. The production method according to 1 or 2 above, wherein phenol is used as the nucleophilic solvent.
7). The polymer which has a structural unit shown by following General formula (1).
8). 8. The polymer according to 7 above, wherein the group —R 1 in the general formula (1) is a hydroxyl group, an alkoxy group, a thioalkyl group, a hydroxyphenyl group, a mercaptophenyl group, or an alkoxyphenyl group.
本発明によれば、モノマー単位で機能化された新規直鎖状重合体を安定して提供することができる。
本発明の製造方法によれば、重合停止に用いる溶媒を変えることによってポリマーに様々な官能基を導入することが可能となる。
本発明の新規重合体は、官能基を有するエンジニアリングプラスチックとして好適である。例えば、ヒドロキシフェニル基を有するポリマーはジアゾナフトキノンや酸発生剤と架橋剤の組み合わせで容易に耐熱性の感光性ポリマーとして使用できる。
ADVANTAGE OF THE INVENTION According to this invention, the novel linear polymer functionalized by the monomer unit can be provided stably.
According to the production method of the present invention, it is possible to introduce various functional groups into the polymer by changing the solvent used for stopping the polymerization.
The novel polymer of the present invention is suitable as an engineering plastic having a functional group. For example, a polymer having a hydroxyphenyl group can be easily used as a heat-resistant photosensitive polymer by combining diazonaphthoquinone or an acid generator and a crosslinking agent.
以下、本発明の新規重合体及びその製造方法について具体的に説明する。 Hereinafter, the novel polymer of the present invention and the production method thereof will be specifically described.
I.重合体
本発明の重合体は、下記一般式(1)で示される構造単位を有することを特徴とする。
上記一般式(1)中、R1は、求核性溶媒の水素を除いた構造を表し、
好ましくは、ヒドロキシル基、アルコキシ基、チオアルキル基、アルコキシフェニル基、置換又は非置換のヒドロキシフェニル基、或いは、置換又は非置換のメルカプトフェニル基である。
mは0、1、又は2を表し、0又は1であることが好ましい。
In the general formula (1), R 1 represents a structure excluding hydrogen of the nucleophilic solvent,
A hydroxyl group, an alkoxy group, a thioalkyl group, an alkoxyphenyl group, a substituted or unsubstituted hydroxyphenyl group, or a substituted or unsubstituted mercaptophenyl group is preferable.
m represents 0, 1, or 2, and is preferably 0 or 1.
本発明の重合体は、分岐が制御された直鎖状の構造を有している。そして、本発明の重合体は、1モノマー単位毎にヒドロキシル基、メトキシ基、及びメトキシフェニル基、ヒドロキシフェニル基等が導入されており、官能基を有するエンジニアリングプラスチックとして有用である。例えば、ヒドロキシフェニル基を有するポリマーはジアゾナフトキノンや酸発生剤と架橋剤の組み合わせで容易に耐熱性の感光性ポリマーとして使用できる。 The polymer of the present invention has a linear structure with controlled branching. The polymer of the present invention has a hydroxyl group, a methoxy group, a methoxyphenyl group, a hydroxyphenyl group or the like introduced for each monomer unit, and is useful as an engineering plastic having a functional group. For example, a polymer having a hydroxyphenyl group can be easily used as a heat-resistant photosensitive polymer by combining diazonaphthoquinone or an acid generator and a crosslinking agent.
本発明の重合体の数平均分子量(Mn)は、重合反応条件(反応温度、反応時間等)によって制御することができるが、一般に5,000〜100,000、好ましくは10,000〜50,000の範囲内である。分子量が5,000未満であると、強靭なフィルムを作製することがでなくなるおそれがあり、100,000を超えると、粘性が高すぎて取り扱いにくくなるおそれがある。 The number average molecular weight (Mn) of the polymer of the present invention can be controlled by polymerization reaction conditions (reaction temperature, reaction time, etc.), but is generally 5,000 to 100,000, preferably 10,000 to 50, Within the range of 000. If the molecular weight is less than 5,000, it may not be possible to produce a tough film, and if it exceeds 100,000, the viscosity may be too high and handling may be difficult.
II.重合体の製造方法
本発明の重合体は、
(A)下記式(2)
(B)求核性の溶媒を添加して重合反応を停止させる工程
を含む製造方法によって製造することができる。
II. Production method of polymer The polymer of the present invention comprises:
(A) The following formula (2)
上記工程(A)で用いる超強酸としては、トリフルオロメタンスルホン酸(CF3SO3H)、フルオロスルホン酸(HSO3F)等があげられる。 Examples of the super strong acid used in the step (A) include trifluoromethanesulfonic acid (CF 3 SO 3 H), fluorosulfonic acid (HSO 3 F), and the like.
上記工程(B)で用いる求核性の溶媒は、目的とする重合体の有する置換基(−R1)によって適宜選択できるが、水、メタノール、エタノール、フェノール、チオフェノール、アニリン、アニソール等を用いることができる。 The nucleophilic solvent used in the step (B) can be appropriately selected depending on the substituent (—R 1 ) of the target polymer, but water, methanol, ethanol, phenol, thiophenol, aniline, anisole, etc. Can be used.
(1)モノマーの製造
本発明の重合体の製造原料である上記式(2)で示されるモノマーは、4−トリフルオロアセチル−4’−フェノキシジフェニルエーテル(以下、TPPEということがある)である。
TPPEは、公知化合物であり、例えば、下記のように製造することができる。
1,4−ジフェノキシベンゼンとジメチルアミノピリジン(DMAP)を、窒素雰囲気下で脱水ジクロロメタンに溶解し、反応液を冷却しながら、トリフルオロ酢酸無水物を滴下し、塩化アルミニウムを加え、反応液の温度を徐々に室温に戻しながら16時間反応させる。その後、反応液を氷水に加え、ジクロロメタンと飽和食塩水を用いて生成物を抽出する。ジクロロメタンを留去後、ヘキサンで洗浄することによって固体(2置換体)を取り除き、薄層クロマトグラフィー(TLC)によって精製(ヘキサン:酢酸エチル=99:1)することにより、TPPEを得る。
また、TPPEを大量に合成する場合は、2置換体を取り除いた後、ヘキサンを用いた再結晶により精製を行う。しかしながら、ヘキサン再結晶による収率は10%程度と非常に低い。この原因は1,4−ジフェノキシベンゼンとTPPEの分離が非常に困難なためである。従って、再結晶溶媒や精製方法の改善によって収率の向上が可能であると考えられる。
(1) Production of Monomer The monomer represented by the above formula (2), which is a raw material for producing the polymer of the present invention, is 4-trifluoroacetyl-4′-phenoxydiphenyl ether (hereinafter sometimes referred to as TPPE).
TPPE is a known compound and can be produced, for example, as follows.
1,4-diphenoxybenzene and dimethylaminopyridine (DMAP) are dissolved in dehydrated dichloromethane under a nitrogen atmosphere, and while cooling the reaction solution, trifluoroacetic anhydride is added dropwise, aluminum chloride is added, and the reaction solution is mixed. The reaction is carried out for 16 hours while gradually returning the temperature to room temperature. Thereafter, the reaction solution is added to ice water, and the product is extracted using dichloromethane and saturated brine. After distilling off dichloromethane, the solid (disubstituted product) is removed by washing with hexane, and purified by thin layer chromatography (TLC) (hexane: ethyl acetate = 99: 1) to obtain TPPE.
Moreover, when synthesizing TPPE in large quantities, after removing 2 substitution products, it refine | purifies by recrystallization using hexane. However, the yield by hexane recrystallization is as low as about 10%. This is because 1,4-diphenoxybenzene and TPPE are very difficult to separate. Therefore, it is considered that the yield can be improved by improving the recrystallization solvent and the purification method.
(2)重合体の製造
本発明の重合体の製造方法においては、上記工程(A)の段階で、下記式(2−a)で示されるカルボカチオンが生成される。本発明者らは、このカルボカチオン(2−a)が、超強酸中では安定に存在することを見出した。このカルボカチオン(2−a)が安定に存在することによって、分岐度の制御された直鎖状の重合体が得られる。
工程(A)において、超強酸であるトリフルオロメタンスルホン酸を用いて重合反応を行い、工程(B)において、求核性の溶媒として、水、メタノール、アニソール又はフェノールを用いた場合に生じる一般式(1)で示される構造単位を有する重合体を下記に示す。
本発明の製造方法によれば、重合停止に用いる溶媒を変えることによってポリマーの主鎖に様々な官能基を導入することが可能である。このように、重合停止溶媒を換えるだけで、モノマー単位に様々な官能基を自在に導入できる重合系は全く新しく例がない。 According to the production method of the present invention, it is possible to introduce various functional groups into the main chain of the polymer by changing the solvent used for terminating the polymerization. As described above, there is no new example of a polymerization system that can freely introduce various functional groups into the monomer unit simply by changing the polymerization termination solvent.
上述したように、本発明の重合体の製造方法は、高収率で官能基を導入できる特性を有しており、官能基を有するエンジニアリングプラスチックとして有用である。例えば、ヒドロキシフェニル基を有するポリマーはジアゾナフトキノンや酸発生剤と架橋剤の組み合わせで容易に耐熱性の感光性ポリマーとして使用できる。 As described above, the method for producing a polymer of the present invention has a characteristic that a functional group can be introduced at a high yield, and is useful as an engineering plastic having a functional group. For example, a polymer having a hydroxyphenyl group can be easily used as a heat-resistant photosensitive polymer by combining diazonaphthoquinone or an acid generator and a crosslinking agent.
以下、本発明を実施例によってさらに具体的に説明するが、本発明は、これらの実施例によって何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by these Examples.
下記の製造例及び実施例で用いた測定機器は次の通りである。
(1)赤外吸収スペクトル測定(IR)
HORIBA FT−720 フーリエ変換赤外分光光度計を用いて測定した。
(2)核磁気共鳴吸収スペクトル測定 (1H−NMR、13C−NMR)
Bruker DPX 300 スペクトロメーター 1H−NMR(300MHz)
(3)ゲル浸透クロマトグラフィー(GPC)CHCl3
カラム:JASCO CO−1565
ポンプ:JASCO PU−1580
UV検出器:JASCO UV−1575
溶離液:CHCl3(流量1mL/分、カラム温度40℃)
The measuring instruments used in the following production examples and examples are as follows.
(1) Infrared absorption spectrum measurement (IR)
Measured using a HORIBA FT-720 Fourier Transform Infrared Spectrophotometer.
(2) Nuclear magnetic resonance absorption spectrum measurement ( 1 H-NMR, 13 C-NMR)
Bruker DPX 300 spectrometer 1 H-NMR (300 MHz)
(3) Gel permeation chromatography (GPC) CHCl 3
Column: JASCO CO-1565
Pump: JASCO PU-1580
UV detector: JASCO UV-1575
Eluent: CHCl 3 (flow
製造例1
4−トリフルオロアセチル−4’−フェノキシジフェニルエーテル(TPPE)の合成
Synthesis of 4-trifluoroacetyl-4'-phenoxydiphenyl ether (TPPE)
収量:0.1132g
収率:41%
融点:41℃
元素分析 計算値 C:67.04、H:3.66
実測値 C:67.29、H:3.86
また、得られたTPPEの1H−NMR、13C−NMR及びIRチャートを図1〜3に示す。
Yield: 0.1132g
Yield: 41%
Melting point: 41 ° C
Elemental analysis calculated C: 67.04, H: 3.66
Actual value C: 67.29, H: 3.86
Moreover, 1 H-NMR, 13 C-NMR and IR chart of the obtained TPPE are shown in FIGS.
実施例1
重合体(1−1)の合成
Synthesis of polymer (1-1)
収量:0.049g
収率:98%
分子量:18,100
多分散性指数(PDI):1.7
また、得られた重合体(1−1)のIR、1H−NMR及び13C−NMRチャートを図4〜6に示す。
Yield: 0.049g
Yield: 98%
Molecular weight: 18,100
Polydispersity index (PDI): 1.7
In addition, IR, 1 H-NMR and 13 C-NMR charts of the resulting polymer (1-1) are shown in FIGS.
実施例2
重合体(1−2)の合成
Synthesis of polymer (1-2)
収量:0.0517g
収率:99%
分子量:17,200
多分散性指数(PDI):1.8
また、得られた重合体(1−2)のIR、1H−NMR及び13C−NMRチャートを図7〜9に示す。
Yield: 0.0517g
Yield: 99%
Molecular weight: 17,200
Polydispersity index (PDI): 1.8
In addition, IR, 1 H-NMR and 13 C-NMR charts of the resulting polymer (1-2) are shown in FIGS.
実施例3
重合体(1−3)の合成
Synthesis of polymer (1-3)
収量:0.0613g
収率:98%
分子量:14,000
多分散性指数(PDI):1.7
また、得られた重合体(1−3)のIR、1H−NMR及び13C−NMRチャートを図10〜12に示す。
Yield: 0.0613g
Yield: 98%
Molecular weight: 14,000
Polydispersity index (PDI): 1.7
In addition, IR, 1 H-NMR and 13 C-NMR charts of the obtained polymer (1-3) are shown in FIGS.
実施例4
重合体(1−4)の合成
Synthesis of polymer (1-4)
収量:0.0607g
収率:99%
分子量:30,407
多分散性指数(PDI):1.6
また、得られた重合体(1−4)のIR、1H−NMRをそれぞれ図13及び14に示す。
Yield: 0.0607g
Yield: 99%
Molecular weight: 30,407
Polydispersity index (PDI): 1.6
Further, IR and 1 H-NMR of the polymer (1-4) obtained are shown in FIGS. 13 and 14, respectively.
本発明の重合体は、分岐が制御された直鎖状の構造を有している。そして、本発明の重合体は、1モノマー単位毎にヒドロキシル基、メトキシ基、メトキシフェニル基、及びヒドロキシフェニル基等が導入されており、官能基を有するエンジニアリングプラスチックとして有用である。例えば、ヒドロキシフェニル基を有するポリマーはジアゾナフトキノンや酸発生剤と架橋剤の組み合わせで容易に耐熱性の感光性ポリマーとして使用できる。 The polymer of the present invention has a linear structure with controlled branching. The polymer of the present invention has a hydroxyl group, a methoxy group, a methoxyphenyl group, a hydroxyphenyl group or the like introduced for each monomer unit, and is useful as an engineering plastic having a functional group. For example, a polymer having a hydroxyphenyl group can be easily used as a heat-resistant photosensitive polymer by combining diazonaphthoquinone or an acid generator and a crosslinking agent.
Claims (8)
で示される化合物に、超強酸を加えて重合反応を行う工程、及び
(B)求核性の溶媒を添加して重合反応を停止させる工程
を含む、下記一般式(1)で示される構造単位を有する重合体の製造方法。
A structural unit represented by the following general formula (1), which comprises a step of adding a super strong acid to the compound represented by the formula (1) and carrying out a polymerization reaction to stop the polymerization reaction by adding a nucleophilic solvent. The manufacturing method of the polymer which has this.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008118073A JP5283107B2 (en) | 2008-04-30 | 2008-04-30 | Functionalized linear polymer and process for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2008118073A JP5283107B2 (en) | 2008-04-30 | 2008-04-30 | Functionalized linear polymer and process for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2009263595A JP2009263595A (en) | 2009-11-12 |
JP5283107B2 true JP5283107B2 (en) | 2013-09-04 |
Family
ID=41389851
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2008118073A Active JP5283107B2 (en) | 2008-04-30 | 2008-04-30 | Functionalized linear polymer and process for producing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5283107B2 (en) |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3744902B2 (en) * | 2003-01-14 | 2006-02-15 | 独立行政法人科学技術振興機構 | Process for producing poly (oxyphenylene) s having substituted phenyl ether in the side chain |
-
2008
- 2008-04-30 JP JP2008118073A patent/JP5283107B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
JP2009263595A (en) | 2009-11-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Ates et al. | Synthesis, characterization and thermally activated curing of polysulfones with benzoxazine end groups | |
EP1712537A1 (en) | Calixarene compound, process for producing the same, intermediate therefor, and composition thereof | |
Ozlem et al. | Synthesis and pyrolysis of ABC type miktoarm star copolymers with polystyrene, poly (lactic acid) and poly (ethylene glycol) arms | |
JP2019099802A (en) | Method for manufacturing stable thermal polymerizable vinyl, amino or oligomer phenoxy benzoxy cyclobutene monomer having improved hardening rate | |
Tasdelen et al. | Orthogonal synthesis of block copolymer via photoinduced cuaac and ketene chemistries | |
JPH0759619B2 (en) | Method for producing high molecular weight epoxy resin | |
US20210122883A1 (en) | High-grafting density cyclic comb shaped polymer and preparation method therefor | |
JP5283107B2 (en) | Functionalized linear polymer and process for producing the same | |
Ishida et al. | Ring-opening polymerization of aromatic 6-membered cyclic disulfide and characterization of the polymer | |
Sato et al. | Precise synthesis of α, ω-chain-end functionalized poly (dimethylsiloxane) with azide groups based on metal-free ring-opening polymerization and a quantitative azidation reaction | |
Patil et al. | A convenient synthesis of α, α′‐homo‐and α, α′‐hetero‐bifunctionalized poly (ε‐caprolactone) s by ring opening polymerization: The potentially valuable precursors for miktoarm star copolymers | |
Suresh et al. | Photocrosslinkable polymer based on 4-(3-(2, 4-dichlorophenyl)-3-oxoprop-1-enyl) phenylacrylate: synthesis, reactivity ratio, and crosslinking studies | |
Li et al. | Characterization of poly (butyl acrylate) diols prepared via atom transfer radical polymerization and subsequent modification | |
JP4431790B2 (en) | Resorcinol novolac derivatives | |
Ihara et al. | Thermally induced polymerization and copolymerization with styrene of diazoketones in the presence of benzoquinone | |
KR20120109052A (en) | Method of manufacturing polymer coating film of cardanol derivative and coating film manufactured by using the same | |
JP5730150B2 (en) | Polymerization initiator and production method thereof, and star polymer and production method thereof | |
Fukuoka et al. | Synthesis of a new class of high‐molecular‐weight soluble poly (amino acid) s by oxidative polymerization of polyfunctional macromolecules | |
Guliev et al. | Synthesis and polymerization of (p-Vinylphenyl) cyclopropylmethyl cinnamate | |
JP7113665B2 (en) | Composition and method for producing the same | |
RU2505557C2 (en) | Method of producing polyester ketones | |
Boakye et al. | Functionalized poly (ether ether ketone) analogs via reactivity ratio controlled polycondensation | |
JP4895683B2 (en) | Vinyl ether derivative polymer and production method and use thereof | |
Degirmenci et al. | Well‐Defined Cyclohexene Oxide Mid‐Chain Functional Polystyrene Macromonomer: Synthesis, Characterization and Photoinitiated Cationic Homo‐and Copolymerization | |
Otsuka et al. | Novel Reactive Polymers Containing Hemiacetal Ester and Vinyl Moieties: Synthesis and Selective Polymerization of 1‐Methoxyallyl Methacrylate Derived from Methacrylic Acid and Methoxyallene |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110201 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120830 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130423 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130522 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5283107 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |