JP2016210955A - Polymer, optical material and lens - Google Patents
Polymer, optical material and lens Download PDFInfo
- Publication number
- JP2016210955A JP2016210955A JP2015181360A JP2015181360A JP2016210955A JP 2016210955 A JP2016210955 A JP 2016210955A JP 2015181360 A JP2015181360 A JP 2015181360A JP 2015181360 A JP2015181360 A JP 2015181360A JP 2016210955 A JP2016210955 A JP 2016210955A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- temperature
- formula
- general formula
- showed
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 139
- 239000000463 material Substances 0.000 title claims description 9
- 230000003287 optical effect Effects 0.000 title claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 35
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 28
- 238000006116 polymerization reaction Methods 0.000 abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 18
- 239000002904 solvent Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 7
- 150000001408 amides Chemical class 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229920002100 high-refractive-index polymer Polymers 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000155 melt Substances 0.000 abstract description 2
- 238000010558 suspension polymerization method Methods 0.000 abstract description 2
- 230000000638 stimulation Effects 0.000 abstract 2
- 230000004043 responsiveness Effects 0.000 description 64
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- 238000005259 measurement Methods 0.000 description 40
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 39
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 30
- 239000003999 initiator Substances 0.000 description 30
- 239000007864 aqueous solution Substances 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 18
- 239000010408 film Substances 0.000 description 17
- 230000004044 response Effects 0.000 description 17
- 238000002835 absorbance Methods 0.000 description 16
- 230000008859 change Effects 0.000 description 13
- 238000005979 thermal decomposition reaction Methods 0.000 description 13
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000004611 spectroscopical analysis Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 4
- 238000001226 reprecipitation Methods 0.000 description 4
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical compound CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002954 polymerization reaction product Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000000391 spectroscopic ellipsometry Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- ILLHORFDXDLILE-UHFFFAOYSA-N 2-bromopropanoyl bromide Chemical compound CC(Br)C(Br)=O ILLHORFDXDLILE-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- YVGKLVZOQWYWTI-UHFFFAOYSA-N calixresorc[4]arene Chemical compound C1C(C(=CC=2O)O)=CC=2CC(C(=CC=2O)O)=CC=2CC(=C2)C(O)=CC(O)=C2CC2=CC1=C(O)C=C2O YVGKLVZOQWYWTI-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 2
- -1 cyclic aromatic compound Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- INWFLBXPENDFJW-UHFFFAOYSA-N 3,4-dimethyl-2-pyridin-2-ylpyridine Chemical compound CC1=CC=NC(C=2N=CC=CC=2)=C1C INWFLBXPENDFJW-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- VMGSQCIDWAUGLQ-UHFFFAOYSA-N n',n'-bis[2-(dimethylamino)ethyl]-n,n-dimethylethane-1,2-diamine Chemical compound CN(C)CCN(CCN(C)C)CCN(C)C VMGSQCIDWAUGLQ-UHFFFAOYSA-N 0.000 description 1
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 150000003553 thiiranes Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、高い屈折率を有するポリマー、光学材料及びレンズに関する。 The present invention relates to polymers, optical materials and lenses having a high refractive index.
近年、屈折率の高い有機材料の開発が進んでおり、例えば、特許文献1に記載のような材料が知られている。特許文献1にはノボラック型フェノール樹脂を出発原料に用いて、チイラン類を連続的に挿入し反応させることにより、高屈折率のノボラック型フェノール樹脂誘導体を得ている。非特許文献1には、ポリマーの構造を星型とすることで屈折率が高くなることが知られている。 In recent years, organic materials having a high refractive index have been developed. For example, materials as described in Patent Document 1 are known. In Patent Document 1, a novolak type phenol resin derivative having a high refractive index is obtained by continuously inserting and reacting thiiranes using a novolak type phenol resin as a starting material. It is known from Non-Patent Document 1 that the refractive index is increased by making the polymer structure into a star shape.
このような光学材料の開発においては、より一層高機能な材料の開発が求められており、その中でも特に、温度やpH変化などの外部刺激に応答する高屈折率材料の開発は、有機レンズ等の光学材料への応用の可能性の観点から非常に大きな課題である。
本発明は、外部刺激応答性部位を分子構造中に有する高屈折率ポリマーを提供することを目的とする。
In the development of such optical materials, the development of even more sophisticated materials is required. Among them, the development of high refractive index materials that respond to external stimuli such as temperature and pH changes is particularly important for organic lenses, etc. This is a very big problem from the viewpoint of the possibility of application to optical materials.
An object of the present invention is to provide a high refractive index polymer having an external stimulus responsive site in a molecular structure.
本発明者らは以下の手段によってこの課題を解決した。
下記一般式(1)で表されるポリマーであって、一般式(1)中のAが下記一般式(2)、一般式(3)又は一般式(4)で表されるいずれかの構造を有することを特徴とするポリマー。
A polymer represented by the following general formula (1), wherein A in the general formula (1) is any structure represented by the following general formula (2), general formula (3) or general formula (4) A polymer characterized by having
本発明によると、外部刺激応答性部位を分子構造中に有する高屈折率ポリマーを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the high refractive index polymer which has an external stimulus responsive part in a molecular structure can be provided.
以下、本発明のポリマーについて詳細に説明する。
本発明のポリマーは下記一般式(1)で示される。
一般式(1)中のAは下記一般式(2)、一般式(3)または一般式(4)で表されるいずれかの構造を示す。
The polymer of the present invention is represented by the following general formula (1).
A in the general formula (1) represents any structure represented by the following general formula (2), general formula (3), or general formula (4).
但し、上記一般式(2)、一般式(3)及び一般式(4)中のDは、塩素、臭素、ヨウ素等のハロゲン元素または水素から選ばれるいずれかの基であり、Eは水素または炭素数1〜2のアルキル基から選ばれるいずれかの基であり、FおよびGは水素または炭素数1又は2のアルキル基から選ばれるいずれかの基である。nは1〜500の整数を表す。また、一般式(2)、一般式(3)及び一般式(4)中の☆は隣接するAの★と同一の炭素を表す。 However, D in the said General formula (2), General formula (3), and General formula (4) is any group chosen from halogen elements, such as chlorine, bromine, and iodine, or hydrogen, and E is hydrogen or Any group selected from alkyl groups having 1 to 2 carbon atoms, and F and G are any groups selected from hydrogen or alkyl groups having 1 or 2 carbon atoms. n represents an integer of 1 to 500. Moreover, * in General formula (2), General formula (3), and General formula (4) represents the same carbon as * of adjacent A.
Dがハロゲン元素である場合は、それぞれのハロゲン元素を末端にもつ開始剤を用いて製造することで自由に選択できる。また重合後に精製処理を行うことにより、前記ハロゲン元素をそれぞれ水素に置き換えることが可能である。 When D is a halogen element, it can be freely selected by producing using an initiator having each halogen element at its terminal. Further, by performing a purification treatment after polymerization, it is possible to replace the halogen elements with hydrogen.
また一般式(2)、一般式(3)及び一般式(4)において、Eは水素または炭素数1又は2のアルキル基から選ばれるいずれかの基である。Eを前記いずれかの基とすることで、重合反応性が良好となり、所望の分子量のポリマーを得ることができる。
炭素数3以上のアルキル基の場合は、立体障害により重合反応性が著しく落ち、所望の分子量のポリマーが得られない。
Moreover, in General formula (2), General formula (3), and General formula (4), E is either group chosen from hydrogen or a C1-C2 alkyl group. By using E as any of the above groups, the polymerization reactivity is improved, and a polymer having a desired molecular weight can be obtained.
In the case of an alkyl group having 3 or more carbon atoms, the polymerization reactivity is remarkably lowered due to steric hindrance, and a polymer having a desired molecular weight cannot be obtained.
また一般式(2)、一般式(3)及び一般式(4)において、FおよびGは水素または炭素数1又は2のアルキル基から選ばれるいずれかの基である。F及びGを前記いずれかの基とすることで、重合度の制御が良好となり、所望の分子量のポリマーを得ることができる。炭素数3以上のアルキル基の場合は、立体障害により重合度が著しく落ち、所望の分子量のポリマーが得られない。 Moreover, in General formula (2), General formula (3), and General formula (4), F and G are either groups chosen from hydrogen or a C1-C2 alkyl group. By using F and G as any of the above groups, the degree of polymerization can be controlled well, and a polymer having a desired molecular weight can be obtained. In the case of an alkyl group having 3 or more carbon atoms, the degree of polymerization is significantly reduced due to steric hindrance, and a polymer having a desired molecular weight cannot be obtained.
なお、本発明のポリマーにおける下記一般式(11)で表される構造は、外部刺激応答性部位に相当する。
星型ポリマーの合成は懸濁重合法や溶液重合法で行われるのが一般的である。
しかしながら、前記懸濁重合法で、式(6)のモノマーおよび式(7)−1の開始剤を用いて下記式(5)−1及び式(5)−2で表される本発明の実施形態に係るポリマーを合成することを試みたが、懸濁重合法では星型ポリマーの製造は困難であった。
Star polymers are generally synthesized by suspension polymerization or solution polymerization.
However, in the suspension polymerization method, the present invention represented by the following formula (5) -1 and formula (5) -2 is carried out using the monomer of formula (6) and the initiator of formula (7) -1. Although an attempt was made to synthesize a polymer according to the form, it was difficult to produce a star polymer by suspension polymerization.
そこで、溶融重合法を用いてみたところ、合成に成功するに至った。
さらに、合成により得たポリマーの特性を評価したところ、従来のポリマーよりも優れた特性であることが分かった。
さらにNMP(N−メチルピロリドン)またはDMF(N、N’−ジメチルホルムアミド)またはDMSO(ジメチルスルホキシド)などのアミド系用溶媒を用いた溶液重合法では星型ポリマーの製造が困難であったが、アミド系溶媒と水とからなる混合溶媒中における溶液重合法を用いてみたところ、合成に成功することを見出した。
Then, when it tried using the melt polymerization method, it came to succeed in a synthesis | combination.
Furthermore, when the characteristics of the polymer obtained by synthesis were evaluated, it was found that the characteristics were superior to those of conventional polymers.
Furthermore, it was difficult to produce a star polymer by a solution polymerization method using an amide solvent such as NMP (N-methylpyrrolidone) or DMF (N, N′-dimethylformamide) or DMSO (dimethylsulfoxide). When the solution polymerization method in a mixed solvent composed of an amide solvent and water was used, it was found that the synthesis was successful.
またアミド系溶媒と水とからなる混合溶媒を用いた溶液重合法においては、重合温度は0℃以上100℃未満の温度範囲が好ましく、より好ましくは0℃から60℃、更に好ましくは0℃から15℃である。重合温度が低いほど、高い収率でポリマーが得ることが容易となる。しかし0℃未満では反応速度が遅くなるため好ましくない。
またアミド系溶媒と水とからなる混合溶媒を用いた溶液重合法においては、重合反応時間は、1時間以上96時間未満が好ましく、より好ましくは24時間以下である。96時間以上としても、収率や得られるポリマーの分子量は変わらず効果がない。1時間未満では反応が十分に進まず好ましくない。
In the solution polymerization method using a mixed solvent composed of an amide solvent and water, the polymerization temperature is preferably in the temperature range of 0 ° C. or higher and lower than 100 ° C., more preferably 0 ° C. to 60 ° C., further preferably 0 ° C. 15 ° C. The lower the polymerization temperature, the easier it is to obtain a polymer in high yield. However, if it is less than 0 ° C., the reaction rate is slow, which is not preferable.
In the solution polymerization method using a mixed solvent composed of an amide solvent and water, the polymerization reaction time is preferably 1 hour or more and less than 96 hours, and more preferably 24 hours or less. Even if it is 96 hours or more, the yield and the molecular weight of the obtained polymer are not changed and no effect is obtained. Less than 1 hour is not preferable because the reaction does not proceed sufficiently.
式(5)−1および式(5)−2で表されるポリマーの製造方法の詳細を以下に述べる。
本発明の前記式(5)−1で表されるポリマーは、前記式(6)で表されるモノマーと前記式(7)−1で表される開始剤により製造することができる。
前記式(6)で表されるモノマーは市販されているので、この市販品を用いることができる。
前記式(7)−1で表される開始剤は、例えば下記反応式(A)で示す反応によって製造できる。
The polymer represented by the formula (5) -1 of the present invention can be produced by using a monomer represented by the formula (6) and an initiator represented by the formula (7) -1.
Since the monomer represented by the formula (6) is commercially available, this commercially available product can be used.
The initiator represented by the formula (7) -1 can be produced, for example, by a reaction represented by the following reaction formula (A).
式(7)−1で表される開始剤の赤外分光分析結果を図1に、核磁気共鳴分光分析結果を図2にそれぞれ示す。 The infrared spectroscopic analysis result of the initiator represented by the formula (7) -1 is shown in FIG. 1, and the nuclear magnetic resonance spectroscopic analysis result is shown in FIG.
上記反応は、カリックス[4]レゾルシンアレーンを出発物質とし、テトラヒドロフラン等の反応溶媒中、トリエチルアミン等の塩基化合物存在下、系内を10℃未満に冷却し温度を維持したまま、2−ブロモイソブチリルブロマイドを滴下して30分程度攪拌した後、25℃以上で24時間以上攪拌することで達成できる。 In the above reaction, calix [4] resorcinarene was used as a starting material, and in the presence of a base compound such as triethylamine in a reaction solvent such as tetrahydrofuran, the system was cooled to less than 10 ° C., and the temperature was maintained while maintaining the temperature. This can be achieved by dripping ril bromide and stirring for about 30 minutes, followed by stirring at 25 ° C. or more for 24 hours or more.
攪拌後、析出物をろ過して取り除いたのち、ろ液をクロロホルム等の水に不溶な抽出溶媒にて希釈して有機層とし、これを炭酸水素ナトリウム水溶液で2回程度、塩化水素水溶液にて1回、純水にて3回洗浄したのち、有機層を無水硫酸マグネシウムで乾燥させる。固形物をろ別後、減圧濃縮し、メタノールに滴下して白色固体が得られ、これをろ別して、式(7)−1で表される開始剤を得ることができる。 After stirring, the precipitate is removed by filtration, and the filtrate is diluted with an extraction solvent insoluble in water such as chloroform to form an organic layer, which is about twice with an aqueous sodium bicarbonate solution and with an aqueous hydrogen chloride solution. After washing once with pure water three times, the organic layer is dried over anhydrous magnesium sulfate. The solid is filtered off, concentrated under reduced pressure, and added dropwise to methanol to obtain a white solid, which can be filtered to obtain the initiator represented by the formula (7) -1.
また2−ブロモイソブチリルブロマイドの代わりに2−ブロモプロピオニルブロミドを用いると、式(7)−2で表される開始剤を得ることができる。
式(5)−1で表されるポリマーは、式(6)で表されるモノマーと式(7)−1で表される開始剤と、遷移金属触媒と、触媒配位子を混合し、原子移動ラジカル重合反応にて製造することができる。反応溶媒や分散溶媒は必要としない。
式(5)−2で表されるポリマーは、式(6)で表されるモノマーと式(7)−2で表される開始剤と、遷移金属触媒と、触媒配位子を混合し、原子移動ラジカル重合反応にて製造することができる。
The polymer represented by Formula (5) -1 is a mixture of a monomer represented by Formula (6), an initiator represented by Formula (7) -1, a transition metal catalyst, and a catalyst ligand. It can be produced by an atom transfer radical polymerization reaction. No reaction solvent or dispersion solvent is required.
The polymer represented by Formula (5) -2 is a mixture of a monomer represented by Formula (6), an initiator represented by Formula (7) -2, a transition metal catalyst, and a catalyst ligand. It can be produced by an atom transfer radical polymerization reaction.
遷移金属触媒は特に限定するものではなく、原子移動ラジカル重合反応にて一般に市販されているもの、例えば、チタン、鉄、コバルト、ニッケル、モリブデン、ルテニウム、ロジウム、パラジウム、レニウム、オスミウム、銅系触媒などが挙げられるが、本発明においては、反応性の観点から銅系触媒が好ましく、より好ましくは臭化銅を用いることができる。 The transition metal catalyst is not particularly limited and is generally commercially available in an atom transfer radical polymerization reaction, for example, titanium, iron, cobalt, nickel, molybdenum, ruthenium, rhodium, palladium, rhenium, osmium, copper-based catalyst. In the present invention, a copper-based catalyst is preferable from the viewpoint of reactivity, and copper bromide can be used more preferably.
触媒配位子は特に限定するものではなく、原子移動ラジカル重合反応にて一般に市販されているもの、例えば、ビピリジン、ジメチルビピリジン、トリス[2−(ジメチルアミノ)エチル]アミン、N,N,N’,N”,N”−ペンタメチルジエチレントリアミン、N,N,N’,N’−テトラエチレンジアミンなどがあげられるが、本発明においては、反応性の観点からN,N,N’,N”,N”−ペンタメチルジエチレントリアミンが好ましい。 The catalyst ligand is not particularly limited, and is generally commercially available in an atom transfer radical polymerization reaction, such as bipyridine, dimethylbipyridine, tris [2- (dimethylamino) ethyl] amine, N, N, N ', N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N′-tetraethylenediamine, and the like. In the present invention, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine is preferred.
式(5)−1で表されるポリマーのより具体的な製造方法は以下の通りである。まず、式(6)で表されるモノマー1.1gと式(7)−1で表される開始剤0.0216gと臭化銅I0.017gを重合管に量り取った後、脱気処理を行って酸素を除去し、窒素雰囲気下でN,N,N’,N”,N”−ペンタメチルジエチレントリアミン0.025gを加えたのちに封管し、60℃以上に加熱して重合する。重合反応物にクロロホルムを1mL加えて希釈したものをジエチルエーテルに再沈殿処理し、固形物をろ別乾燥することにより、本発明のポリマーが得られる。 A more specific method for producing the polymer represented by the formula (5) -1 is as follows. First, 1.1 g of the monomer represented by the formula (6), 0.0216 g of the initiator represented by the formula (7) -1 and 0.017 g of copper bromide I were weighed in a polymerization tube, and then degassed. Then, oxygen is removed, 0.025 g of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine is added in a nitrogen atmosphere, and the tube is sealed and polymerized by heating to 60 ° C. or higher. The polymer of the present invention can be obtained by reprecipitation treatment of 1 mL of chloroform added to the polymerization reaction product and re-precipitation in diethyl ether, followed by filtration and drying of the solid matter.
式(5)−2で表されるポリマーのより具体的な製造方法は以下の通りである。
まず、式(6)で表されるモノマー1.1gと式(7)−2で表される開始剤0.0196gと臭化銅I0.017gを重合管に量り取った後、脱気処理を行って酸素を除去し、窒素雰囲気下でN,N,N’,N”,N”−ペンタメチルジエチレントリアミン0.025gを加えたのちに封管し、60℃以上に加熱して重合する。重合反応物にクロロホルムを1mL加えて希釈したものをジエチルエーテルに再沈殿処理し、固形物をろ別乾燥することにより、本発明のポリマーが得られる。
A more specific method for producing the polymer represented by the formula (5) -2 is as follows.
First, 1.1 g of the monomer represented by the formula (6), 0.0196 g of the initiator represented by the formula (7) -2 and 0.017 g of copper bromide I were weighed in a polymerization tube, and then degassing treatment was performed. Then, oxygen is removed, 0.025 g of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine is added in a nitrogen atmosphere, and the tube is sealed and polymerized by heating to 60 ° C. or higher. The polymer of the present invention can be obtained by reprecipitation treatment of 1 mL of chloroform added to the polymerization reaction product and re-precipitation in diethyl ether, followed by filtration and drying of the solid matter.
また、一般式(1)におけるAが一般式(3)で示される構造を有するものを合成するには開始剤として下記式(8)の(a)又は下記式(8)の(b)で表されるものを用いる。
なお、下記式(8)の(a)は立体異性体rcccを示し、下記式(8)の(b)は立体異性体rcttを示す。
In the following formula (8), (a) represents the stereoisomer rccc, and (b) in the following formula (8) represents the stereoisomer rctt.
式(7)−1および式(7)−2で表される開始剤と、本発明のポリマーの構造確認は、赤外分光分析と核磁気共鳴分光分析で行うことができる。ポリマーの数平均分子量、重量平均分子量、多分散度及び重合度(n)はサイズ排除クロマトグラフィーと核磁気共鳴分光分析により算出することができる。また、ポリマーの屈折率は分光エリプソメトリーにより測定することができる。
式(5)−1および式(5)−2で表されるポリマーの赤外分光分析結果をそれぞれ図5−1および図5−2に示した。
図5−2において、A)は式(7)−2で表される開始剤の赤外分光分析結果を示す図であり、B)は式(5)−2で表されるポリマーの赤外分光分析結果を示す図である。
また、式(5)−1および式(5)−2で表されるポリマーの核磁気共鳴分光分析結果をそれぞれ図6−1および図6−2に示した。
Structure confirmation of the initiators represented by the formulas (7) -1 and (7) -2 and the polymer of the present invention can be performed by infrared spectroscopic analysis and nuclear magnetic resonance spectroscopic analysis. The number average molecular weight, weight average molecular weight, polydispersity, and degree of polymerization (n) of the polymer can be calculated by size exclusion chromatography and nuclear magnetic resonance spectroscopy. The refractive index of the polymer can be measured by spectroscopic ellipsometry.
The infrared spectroscopic analysis results of the polymers represented by formula (5) -1 and formula (5) -2 are shown in FIGS. 5-1 and 5-2, respectively.
In FIG. 5-2, A) is a figure which shows the infrared spectroscopy analysis result of the initiator represented by Formula (7) -2, B) is the infrared of the polymer represented by Formula (5) -2. It is a figure which shows a spectroscopic analysis result.
Moreover, the nuclear magnetic resonance spectroscopic analysis result of the polymer represented by Formula (5) -1 and Formula (5) -2 is shown in FIGS. 6-1 and 6-2, respectively.
また、得られた式(5)−2で表されるポリマーの温度応答性評価結果を図7−1及び図7−2に示す。
図7−1は水溶液中のポリマーの温度応答性を示す図であり、図7−2はポリマーのフィルムの温度応答性を示す図である。
図中、(1)は後述する実施例6のポリマーについてのグラフを、(2)は実施例7のポリマーについてのグラフを、(3)は実施例8のポリマーについてのグラフをそれぞれ示す。
また、(4)は比較例1の市販の直鎖型PNIPAM(ポリN−イソプロピルアクリルアミド)についてのグラフを示す。
本発明のポリマーの水溶液中での温度応答性は市販の直鎖型PNIPAMよりも低い温度で吸光度が上昇しはじめ、また10℃から60℃の温度範囲における最大の吸光度は、直鎖型PNIPAMの2倍以上であり、良好な温度応答性を示した。
また本発明のポリマーのフィルムの温度応答性は、10℃から80℃の温度範囲において上に凸の放物線を描き、最大の屈折率を示す温度は、直鎖型PNIPAMよりも20℃以上低く、良好な温度応答性を示した。
Moreover, the temperature-responsive evaluation result of the polymer represented by Formula (5) -2 obtained is shown in FIGS. 7-1 and 7-2.
FIG. 7-1 is a diagram showing the temperature responsiveness of the polymer in the aqueous solution, and FIG. 7-2 is a diagram showing the temperature responsiveness of the polymer film.
In the figure, (1) is a graph for the polymer of Example 6 described later, (2) is a graph for the polymer of Example 7, and (3) is a graph for the polymer of Example 8.
Moreover, (4) shows a graph for the commercially available linear PNIPAM (poly N-isopropylacrylamide) of Comparative Example 1.
The temperature responsiveness of the polymer of the present invention in an aqueous solution starts to increase in absorbance at a temperature lower than that of commercially available linear PNIPAM, and the maximum absorbance in the temperature range of 10 ° C. to 60 ° C. is that of linear PNIPAM. It was 2 times or more and showed a good temperature response.
Further, the temperature responsiveness of the polymer film of the present invention draws a convex parabola in the temperature range of 10 ° C. to 80 ° C., and the temperature showing the maximum refractive index is 20 ° C. or more lower than that of linear PNIPAM, Good temperature responsiveness was exhibited.
また、得られた式(5)−2で表されるポリマーの熱重量測定を実施した結果を図8に示す。本発明の熱重量変化は市販の直鎖型PNIPAMと顕著な差異はなく、同等の熱分解特性を示した。
図中、(1)は実施例6のポリマーについてのグラフを、(2)は実施例7のポリマーについてのグラフを、(3)は実施例8のポリマーについてのグラフを、それぞれ示す。また、(4)は比較例1の市販の直鎖型PNIPAM(ポリN−イソプロピルアクリルアミド)についてのグラフを示す。
Moreover, the result of having conducted the thermogravimetric measurement of the polymer represented by Formula (5) -2 obtained is shown in FIG. The thermogravimetric change of the present invention was not significantly different from that of commercially available linear PNIPAM, and showed the same thermal decomposition characteristics.
In the figure, (1) is a graph for the polymer of Example 6, (2) is a graph for the polymer of Example 7, and (3) is a graph for the polymer of Example 8. Moreover, (4) shows a graph for the commercially available linear PNIPAM (poly N-isopropylacrylamide) of Comparative Example 1.
以下、実施例に基づいて本発明をより具体的に説明するが、本発明は、実施例に制限されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not restrict | limited to an Example.
まず、実施例及び比較例で得られたポリマーの分析方法の詳細について述べる。
<数平均分子量、重量平均分子量および分子量分布の算出>
数平均分子量、重量平均分子量及び分子量分布(Mw/Mn)は、ゲルパーミエイションクロマトグラフィー(GPC)法により、以下の条件で測定することができる。
・装置:HLC−8220(東ソー株式会社製)
・カラム:Shodex asahipak GF−510 HQ + GF−310×2(昭和電工株式会社製)
TSK G2000HXL及びG4000HXL(東ソー株式会社製)
・温度:40℃
・溶離液:20mM リチウムブロミド、20mMリン酸含有ジメチルホルムアミド溶液
・流速:0.5mL/分
・検出器:HLC−8200 内蔵RI−UV−8220
濃度0.5質量%の試料1mLを装置にセットし、上記の条件で測定したポリマー生成物の分子量分布から単分散ポリスチレン標準試料により作成した分子量校正曲線を使用してポリマー生成物の数平均分子量(Mn)、重量平均分子量(Mw)を算出した。分子量分布はMwをMnで除した値である。
First, details of the analytical methods of the polymers obtained in the examples and comparative examples will be described.
<Calculation of number average molecular weight, weight average molecular weight and molecular weight distribution>
The number average molecular weight, weight average molecular weight, and molecular weight distribution (Mw / Mn) can be measured under the following conditions by gel permeation chromatography (GPC).
・ Device: HLC-8220 (manufactured by Tosoh Corporation)
Column: Shodex asahipak GF-510 HQ + GF-310 × 2 (manufactured by Showa Denko KK)
TSK G2000HXL and G4000HXL (manufactured by Tosoh Corporation)
・ Temperature: 40 ℃
Eluent: 20 mM lithium bromide, 20 mM phosphoric acid-containing dimethylformamide solution Flow rate: 0.5 mL / min Detector: HLC-8200 Built-in RI-UV-8220
1 mL of a sample having a concentration of 0.5% by mass is set in the apparatus, and the number average molecular weight (Mn) of the polymer product is calculated using a molecular weight calibration curve prepared by a monodisperse polystyrene standard sample from the molecular weight distribution of the polymer product measured under the above conditions ), And the weight average molecular weight (Mw) was calculated. The molecular weight distribution is a value obtained by dividing Mw by Mn.
<核磁気共鳴分光分析>
環状芳香族化合物、星型ポリマーは、核磁気共鳴分光分析により、以下の条件で同定することができる。
・装置:JOEL−ECS−400K(日本電子株式会社製)
<Nuclear magnetic resonance spectroscopy>
A cyclic aromatic compound and a star polymer can be identified under the following conditions by nuclear magnetic resonance spectroscopy.
・ Device: JOEL-ECS-400K (manufactured by JEOL Ltd.)
(重合度:n)
磁気共鳴分光分析(=1H−NMR)により各部位の水素数を測定して算出する。
詳細には、開始剤由来の1Hの積分値総和(水素の数)と、繰り返し単位由来の1Hの積分値総和の比率から算出する。
例えば、式(1)中のAが式(2)で表される構造のポリマーにおいて、理論計算から、開始剤由来の水素数が72、繰り返し単位由来の水素数が88の場合、n=1となり、開始剤由来の水素数が72、繰り返し単位由来の水素数が176の場合、n=2となる。
すなわち、(72/88)×(繰り返し単位由来の水素数/開始剤由来の水素数)=nである。
(Degree of polymerization: n)
The number of hydrogen at each site is measured and calculated by magnetic resonance spectroscopy (= 1 H-NMR).
In particular, the integral value sum of the 1 H from initiator (the number of hydrogen), is calculated from the ratio of the integral value sum of the 1 H-derived repeat units.
For example, in a polymer having a structure in which A in formula (1) is represented by formula (2), n = 1 when the number of hydrogen derived from the initiator is 72 and the number of hydrogen derived from the repeating unit is 88 from theoretical calculation. Thus, when the number of hydrogen derived from the initiator is 72 and the number of hydrogen derived from the repeating unit is 176, n = 2.
That is, (72/88) × (number of hydrogen derived from repeating unit / number of hydrogen derived from initiator) = n.
<赤外分光分析>
環状芳香族化合物、星型ポリマーは、赤外分光分析により同定することができる。
・装置:FT/IR 4200(日本分光株式会社製)
<Infrared spectroscopic analysis>
Cyclic aromatic compounds and star polymers can be identified by infrared spectroscopy.
Apparatus: FT / IR 4200 (manufactured by JASCO Corporation)
<可視分光エリプソメトリー>
ポリマーの屈折率は分光エリプソメータを用いる分光エリプソメトリーにより測定することができる。
・装置:1H3LNWWP(堀場製作所株式会社製)
ポリマーをPGMEに溶解させ、シリコンウエハ上にスピンコートして薄膜を形成させ、波長632.8nmの光源を用いて測定した。
<Visible spectroscopic ellipsometry>
The refractive index of the polymer can be measured by spectroscopic ellipsometry using a spectroscopic ellipsometer.
・ Device: 1H3LNWWP (manufactured by Horiba Ltd.)
The polymer was dissolved in PGME, spin-coated on a silicon wafer to form a thin film, and measurement was performed using a light source having a wavelength of 632.8 nm.
<水溶液の温度応答性評価>
水溶液中でのポリマーの温度応答性は、分光光度計を用いて評価することができる。本発明のポリマー2.0mgを蒸留水20mlに溶解させた、10℃から60℃までの温度範囲において、5℃間隔で、それぞれの温度における400nmの吸光度を測定した。
<Evaluation of temperature response of aqueous solution>
The temperature responsiveness of the polymer in an aqueous solution can be evaluated using a spectrophotometer. Absorbance at 400 nm at each temperature was measured at 5 ° C. intervals in a temperature range from 10 ° C. to 60 ° C. in which 2.0 mg of the polymer of the present invention was dissolved in 20 ml of distilled water.
<フィルムの温度応答性評価>
フィルムの温度応答性は、アッベ屈折率計を用いて評価することができる。本発明のポリマー1.0mgをメタノール1.0mlに溶解させた溶液を、アッベ屈折率計のプリズム上にキャストして製膜した。10℃から80℃までの温度範囲にプリズムの温度を調節し、5℃間隔にて、それぞれの温度における538nmの屈折率を測定した。
<Evaluation of film temperature response>
The temperature responsiveness of the film can be evaluated using an Abbe refractometer. A solution prepared by dissolving 1.0 mg of the polymer of the present invention in 1.0 ml of methanol was cast on an Abbe refractometer prism to form a film. The temperature of the prism was adjusted to a temperature range from 10 ° C. to 80 ° C., and the refractive index of 538 nm at each temperature was measured at intervals of 5 ° C.
(実施例1)
カリックス[4]レゾルシンアレーンをテトラヒドロフランに溶解し、トリエチルアミンを加えた。次いで、系内を10℃未満に冷却し温度を維持したまま、2−ブロモイソブチリルブロマイドを滴下して30分程度攪拌した後、40℃で24時間攪拌した。反応液から析出物をろ過して取り除いた。ろ液をクロロホルムで希釈して有機層とし、これを炭酸水素ナトリウム水溶液で2回程度、塩化水素水溶液にて1回、純水にて3回洗浄したのち、有機層を無水硫酸マグネシウムで乾燥させた。固形物をろ別後、減圧濃縮し、メタノールに滴下して白色固体を得、これをろ別して、式(7)−1で表される開始剤を得た。
Example 1
Calix [4] resorcinarene was dissolved in tetrahydrofuran and triethylamine was added. Subsequently, while the system was cooled to less than 10 ° C. and the temperature was maintained, 2-bromoisobutyryl bromide was added dropwise and stirred for about 30 minutes, and then stirred at 40 ° C. for 24 hours. The precipitate was removed from the reaction solution by filtration. The filtrate is diluted with chloroform to form an organic layer, which is washed about twice with an aqueous sodium hydrogen carbonate solution, once with an aqueous hydrogen chloride solution and three times with pure water, and then dried over anhydrous magnesium sulfate. It was. The solid was filtered off, concentrated under reduced pressure, and dropped into methanol to obtain a white solid, which was filtered to obtain an initiator represented by the formula (7) -1.
開始点濃度を10×10−3mol/Lとなるように、市販のN−イソプロピルアクリルアミドと式(7)−1で表される開始剤と、臭化銅(I)を重合管に量り取った後、脱気処理を行って酸素を除去し、窒素雰囲気下でN,N,N’,N”,N”−ペンタメチルジエチレントリアミンを加えたのちに封管し、70℃に加熱して0.5時間重合した。重合反応物にクロロホルムを1mL加えて希釈したものをジエチルエーテルに再沈殿処理し、固形物をろ別乾燥して、ポリマーを得た。得られたポリマーは水、メタノール、THF,クロロホルム、ジクロロメタン、DMF,NMP、DMSOに対して良好な溶解性を示した。得られたポリマーの評価結果を表1に示した。 Commercially available N-isopropylacrylamide, an initiator represented by formula (7) -1 and copper (I) bromide are weighed into a polymerization tube so that the starting point concentration is 10 × 10 −3 mol / L. After that, deaeration treatment is performed to remove oxygen, and N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine is added in a nitrogen atmosphere, and then sealed, heated to 70 ° C. and heated to 0 ° C. Polymerized for 5 hours. The polymerization reaction product diluted with 1 mL of chloroform was reprecipitated in diethyl ether, and the solid was filtered and dried to obtain a polymer. The obtained polymer showed good solubility in water, methanol, THF, chloroform, dichloromethane, DMF, NMP and DMSO. The evaluation results of the obtained polymer are shown in Table 1.
また得られたポリマーの温度応答性を評価したところ、水溶液の温度応答性は市販の直鎖型PNIPAMよりも低い温度で吸光度が上昇しはじめ、また測定温度範囲における最大の吸光度は、直鎖型PNIPAMの2倍以上であり、良好な温度応答性を示した。
またフィルムの温度応答性は、測定温度範囲において上に凸の放物線を描き、最大の屈折率を示す温度は、直鎖型PNIPAMよりも20℃以上低く、良好な温度応答性を示した。
Further, when the temperature responsiveness of the obtained polymer was evaluated, the temperature responsiveness of the aqueous solution started to increase at a temperature lower than that of the commercially available linear PNIPAM, and the maximum absorbance in the measurement temperature range was linear. It was more than twice that of PNIPAM and showed a good temperature response.
Moreover, the temperature responsiveness of the film showed an upwardly convex parabola in the measurement temperature range, and the temperature showing the maximum refractive index was 20 ° C. or more lower than that of the linear PNIPAM, indicating a good temperature responsiveness.
(実施例2)
重合時間を1時間とした以外は実施例1と同様にし、ポリマーを得た。得られたポリマーは水、メタノール、THF,クロロホルム、ジクロロメタン、DMF,NMP、DMSOに対して良好な溶解性を示した。得られたポリマーの評価結果を表1に示した。
また得られたポリマーの温度応答性を評価したところ、水溶液の温度応答性は市販の直鎖型PNIPAMよりも低い温度で吸光度が上昇しはじめ、また測定温度範囲における最大の吸光度は、直鎖型PNIPAMの2倍以上であり、良好な温度応答性を示した。
またフィルムの温度応答性は、測定温度範囲において上に凸の放物線を描き、最大の屈折率を示す温度は、直鎖型PNIPAMよりも20℃以上低く、良好な温度応答性を示した。
また得られたポリマーの熱重量測定を実施した結果、熱重量変化は市販の直鎖型PNIPAMと顕著な差異はなく、同等の熱分解特性を示した。
(Example 2)
A polymer was obtained in the same manner as in Example 1 except that the polymerization time was 1 hour. The obtained polymer showed good solubility in water, methanol, THF, chloroform, dichloromethane, DMF, NMP and DMSO. The evaluation results of the obtained polymer are shown in Table 1.
Further, when the temperature responsiveness of the obtained polymer was evaluated, the temperature responsiveness of the aqueous solution started to increase at a temperature lower than that of the commercially available linear PNIPAM, and the maximum absorbance in the measurement temperature range was linear. It was more than twice that of PNIPAM and showed a good temperature response.
Moreover, the temperature responsiveness of the film showed an upwardly convex parabola in the measurement temperature range, and the temperature showing the maximum refractive index was 20 ° C. or more lower than that of the linear PNIPAM, indicating a good temperature responsiveness.
As a result of thermogravimetric measurement of the obtained polymer, the thermogravimetric change was not significantly different from that of commercially available linear PNIPAM, and showed the same thermal decomposition characteristics.
(実施例3)
重合時間を12時間とした以外は実施例1と同様にし、ポリマーを得た。得られたポリマーは水、メタノール、THF,クロロホルム、ジクロロメタン、DMF,NMP、DMSOに対して良好な溶解性を示した。得られたポリマーの評価結果を表1に示した。
また得られたポリマーの温度応答性を評価したところ、水溶液の温度応答性は市販の直鎖型PNIPAMよりも低い温度で吸光度が上昇しはじめ、また測定温度範囲における最大の吸光度は、直鎖型PNIPAMの2倍以上であり、良好な温度応答性を示した。
またフィルムの温度応答性は、測定温度範囲において上に凸の放物線を描き、最大の屈折率を示す温度は、直鎖型PNIPAMよりも20℃以上低く、良好な温度応答性を示した。
また得られたポリマーの熱重量測定を実施した結果、熱重量変化は市販の直鎖型PNIPAMと顕著な差異はなく、同等の熱分解特性を示した。
Example 3
A polymer was obtained in the same manner as in Example 1 except that the polymerization time was 12 hours. The obtained polymer showed good solubility in water, methanol, THF, chloroform, dichloromethane, DMF, NMP and DMSO. The evaluation results of the obtained polymer are shown in Table 1.
Further, when the temperature responsiveness of the obtained polymer was evaluated, the temperature responsiveness of the aqueous solution started to increase at a temperature lower than that of the commercially available linear PNIPAM, and the maximum absorbance in the measurement temperature range was linear. It was more than twice that of PNIPAM and showed a good temperature response.
Moreover, the temperature responsiveness of the film showed an upwardly convex parabola in the measurement temperature range, and the temperature showing the maximum refractive index was 20 ° C. or more lower than that of the linear PNIPAM, indicating a good temperature responsiveness.
As a result of thermogravimetric measurement of the obtained polymer, the thermogravimetric change was not significantly different from that of commercially available linear PNIPAM, and showed the same thermal decomposition characteristics.
(実施例4)
開始点濃度を25×10−3mol/Lとした以外は実施例3と同様にし、ポリマーを得た。得られたポリマーは水、メタノール、THF,クロロホルム、ジクロロメタン、DMF,NMP、DMSOに対して良好な溶解性を示した。得られたポリマーの評価結果を表1に示した。
また得られたポリマーの温度応答性を評価したところ、水溶液の温度応答性は市販の直鎖型PNIPAMよりも低い温度で吸光度が上昇しはじめ、また測定温度範囲における最大の吸光度は、直鎖型PNIPAMの2倍以上であり、良好な温度応答性を示した。
またフィルムの温度応答性は、測定温度範囲において上に凸の放物線を描き、最大の屈折率を示す温度は、直鎖型PNIPAMよりも20℃以上低く、良好な温度応答性を示した。
また得られたポリマーの熱重量測定を実施した結果、熱重量変化は市販の直鎖型PNIPAMと顕著な差異はなく、同等の熱分解特性を示した。
Example 4
A polymer was obtained in the same manner as in Example 3 except that the starting point concentration was 25 × 10 −3 mol / L. The obtained polymer showed good solubility in water, methanol, THF, chloroform, dichloromethane, DMF, NMP and DMSO. The evaluation results of the obtained polymer are shown in Table 1.
Further, when the temperature responsiveness of the obtained polymer was evaluated, the temperature responsiveness of the aqueous solution started to increase at a temperature lower than that of the commercially available linear PNIPAM, and the maximum absorbance in the measurement temperature range was linear. It was more than twice that of PNIPAM and showed a good temperature response.
Moreover, the temperature responsiveness of the film showed an upwardly convex parabola in the measurement temperature range, and the temperature showing the maximum refractive index was 20 ° C. or more lower than that of the linear PNIPAM, indicating a good temperature responsiveness.
As a result of thermogravimetric measurement of the obtained polymer, the thermogravimetric change was not significantly different from that of commercially available linear PNIPAM, and showed the same thermal decomposition characteristics.
(実施例5)
開始点濃度を50×10−3mol/Lとした以外は実施例3と同様にし、ポリマーを得た。得られたポリマーは水、メタノール、THF,クロロホルム、ジクロロメタン、DMF,NMP、DMSOに対して良好な溶解性を示した。得られたポリマーの評価結果を表1に示した。
また得られたポリマーの温度応答性を評価したところ、水溶液の温度応答性は市販の直鎖型PNIPAMよりも低い温度で吸光度が上昇しはじめ、また測定温度範囲における最大の吸光度は、直鎖型PNIPAMの2倍以上であり、良好な温度応答性を示した。
またフィルムの温度応答性は、測定温度範囲において上に凸の放物線を描き、最大の屈折率を示す温度は、直鎖型PNIPAMよりも20℃以上低く、良好な温度応答性を示した。
また得られたポリマーの熱重量測定を実施した結果、熱重量変化は市販の直鎖型PNIPAMと顕著な差異はなく、同等の熱分解特性を示した。
(Example 5)
A polymer was obtained in the same manner as in Example 3 except that the starting point concentration was 50 × 10 −3 mol / L. The obtained polymer showed good solubility in water, methanol, THF, chloroform, dichloromethane, DMF, NMP and DMSO. The evaluation results of the obtained polymer are shown in Table 1.
Further, when the temperature responsiveness of the obtained polymer was evaluated, the temperature responsiveness of the aqueous solution started to increase at a temperature lower than that of the commercially available linear PNIPAM, and the maximum absorbance in the measurement temperature range was linear. It was more than twice that of PNIPAM and showed a good temperature response.
Moreover, the temperature responsiveness of the film showed an upwardly convex parabola in the measurement temperature range, and the temperature showing the maximum refractive index was 20 ° C. or more lower than that of the linear PNIPAM, indicating a good temperature responsiveness.
As a result of thermogravimetric measurement of the obtained polymer, the thermogravimetric change was not significantly different from that of commercially available linear PNIPAM, and showed the same thermal decomposition characteristics.
(実施例6)
開始剤を、2−ブロモイソブチリルブロマイドの代わりに2−ブロモプロピオニルブロミドを用いて合成した式(7)−2とし、開始点濃度を5.0×10−4mol/Lとし、Nイソプロピルアクリルアミドの量を0.0127mmolとし、臭化銅(I)の量を0.014gとし、N,N,N’,N’’,N’’−ペンタメチルジエチレントリアミン (PMDETA) の量を0.021gとし、重合溶媒としてNMPとH2Oをそれぞれ1.5mLずつ用い、重合温度を0℃とし、重合時間を24時間とした以外は実施例1と同様にし、ポリマーを得た。収率は53%であった。得られたポリマーは水、メタノール、THF,クロロホルム、ジクロロメタン、DMF,NMP、DMSOに対して良好な溶解性を示した。得られたポリマーの評価結果を表1に示した。
また得られたポリマーの温度応答性を評価したところ、水溶液の温度応答性は市販の直鎖型PNIPAMよりも低い温度で吸光度が上昇しはじめ、また測定温度範囲における最大の吸光度は、直鎖型PNIPAMの2倍以上であり、良好な温度応答性を示した。
またフィルムの温度応答性は、測定温度範囲において上に凸の放物線を描き、最大の屈折率を示す温度は、直鎖型PNIPAMよりも20℃以上低く、良好な温度応答性を示した。
また得られたポリマーの熱重量測定を実施した結果、熱重量変化は市販の直鎖型PNIPAMと顕著な差異はなく、同等の熱分解特性を示した。
(Example 6)
The initiator is formula (7) -2 synthesized using 2-bromopropionyl bromide instead of 2-bromoisobutyryl bromide, the starting point concentration is 5.0 × 10 −4 mol / L, and N isopropyl The amount of acrylamide is 0.0127 mmol, the amount of copper (I) bromide is 0.014 g, and the amount of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (PMDETA) is 0.021 g. A polymer was obtained in the same manner as in Example 1, except that 1.5 mL each of NMP and H 2 O were used as polymerization solvents, the polymerization temperature was 0 ° C., and the polymerization time was 24 hours. The yield was 53%. The obtained polymer showed good solubility in water, methanol, THF, chloroform, dichloromethane, DMF, NMP and DMSO. The evaluation results of the obtained polymer are shown in Table 1.
Further, when the temperature responsiveness of the obtained polymer was evaluated, the temperature responsiveness of the aqueous solution started to increase at a temperature lower than that of the commercially available linear PNIPAM, and the maximum absorbance in the measurement temperature range was linear. It was more than twice that of PNIPAM and showed a good temperature response.
Moreover, the temperature responsiveness of the film showed an upwardly convex parabola in the measurement temperature range, and the temperature showing the maximum refractive index was 20 ° C. or more lower than that of the linear PNIPAM, indicating a good temperature responsiveness.
As a result of thermogravimetric measurement of the obtained polymer, the thermogravimetric change was not significantly different from that of commercially available linear PNIPAM, and showed the same thermal decomposition characteristics.
(実施例7)
開始点濃度を10×10−4mol/Lとした以外は実施例6と同様にし、ポリマーを得た。得られたポリマーは水、メタノール、THF,クロロホルム、ジクロロメタン、DMF,NMP、DMSOに対して良好な溶解性を示した。得られたポリマーの評価結果を表1に示した。
また得られたポリマーの温度応答性を評価したところ、水溶液の温度応答性は市販の直鎖型PNIPAMよりも低い温度で吸光度が上昇しはじめ、また測定温度範囲における最大の吸光度は、直鎖型PNIPAMの2倍以上であり、良好な温度応答性を示した。
またフィルムの温度応答性は、測定温度範囲において上に凸の放物線を描き、最大の屈折率を示す温度は、直鎖型PNIPAMよりも20℃以上低く、良好な温度応答性を示した。
また得られたポリマーの熱重量測定を実施した結果、熱重量変化は市販の直鎖型PNIPAMと顕著な差異はなく、同等の熱分解特性を示した。
(Example 7)
A polymer was obtained in the same manner as in Example 6 except that the starting point concentration was 10 × 10 −4 mol / L. The obtained polymer showed good solubility in water, methanol, THF, chloroform, dichloromethane, DMF, NMP and DMSO. The evaluation results of the obtained polymer are shown in Table 1.
Further, when the temperature responsiveness of the obtained polymer was evaluated, the temperature responsiveness of the aqueous solution started to increase at a temperature lower than that of the commercially available linear PNIPAM, and the maximum absorbance in the measurement temperature range was linear. It was more than twice that of PNIPAM and showed a good temperature response.
Moreover, the temperature responsiveness of the film showed an upwardly convex parabola in the measurement temperature range, and the temperature showing the maximum refractive index was 20 ° C. or more lower than that of the linear PNIPAM, indicating a good temperature responsiveness.
As a result of thermogravimetric measurement of the obtained polymer, the thermogravimetric change was not significantly different from that of commercially available linear PNIPAM, and showed the same thermal decomposition characteristics.
(実施例8)
開始点濃度を20×10−4mol/Lとした以外は実施例6と同様にし、ポリマーを得た。得られたポリマーは水、メタノール、THF,クロロホルム、ジクロロメタン、DMF,NMP、DMSOに対して良好な溶解性を示した。得られたポリマーの評価結果を表1に示した。
また得られたポリマーの温度応答性を評価したところ、水溶液の温度応答性は市販の直鎖型PNIPAMよりも低い温度で吸光度が上昇しはじめ、また測定温度範囲における最大の吸光度は、直鎖型PNIPAMの2倍以上であり、良好な温度応答性を示した。
またフィルムの温度応答性は、測定温度範囲において上に凸の放物線を描き、最大の屈折率を示す温度は、直鎖型PNIPAMよりも20℃以上低く、良好な温度応答性を示した。
また得られたポリマーの熱重量測定を実施した結果、熱重量変化は市販の直鎖型PNIPAMと顕著な差異はなく、同等の熱分解特性を示した。
(Example 8)
A polymer was obtained in the same manner as in Example 6 except that the starting point concentration was 20 × 10 −4 mol / L. The obtained polymer showed good solubility in water, methanol, THF, chloroform, dichloromethane, DMF, NMP and DMSO. The evaluation results of the obtained polymer are shown in Table 1.
Further, when the temperature responsiveness of the obtained polymer was evaluated, the temperature responsiveness of the aqueous solution started to increase at a temperature lower than that of the commercially available linear PNIPAM, and the maximum absorbance in the measurement temperature range was linear. It was more than twice that of PNIPAM and showed a good temperature response.
Moreover, the temperature responsiveness of the film showed an upwardly convex parabola in the measurement temperature range, and the temperature showing the maximum refractive index was 20 ° C. or more lower than that of the linear PNIPAM, indicating a good temperature responsiveness.
As a result of thermogravimetric measurement of the obtained polymer, the thermogravimetric change was not significantly different from that of commercially available linear PNIPAM, and showed the same thermal decomposition characteristics.
(実施例9)
重合温度を60℃とした以外は実施例8と同様にし、ポリマーを得た。収率は25%であった。得られたポリマーは水、メタノール、THF,クロロホルム、ジクロロメタン、DMF,NMP、DMSOに対して良好な溶解性を示した。得られたポリマーの評価結果を表1に示した。
また得られたポリマーの温度応答性を評価したところ、水溶液の温度応答性は市販の直鎖型PNIPAMよりも低い温度で吸光度が上昇しはじめ、また測定温度範囲における最大の吸光度は、直鎖型PNIPAMの2倍以上であり、良好な温度応答性を示した。
またフィルムの温度応答性は、測定温度範囲において上に凸の放物線を描き、最大の屈折率を示す温度は、直鎖型PNIPAMよりも20℃以上低く、良好な温度応答性を示した。
また得られたポリマーの熱重量測定を実施した結果、熱重量変化は市販の直鎖型PNIPAMと顕著な差異はなく、同等の熱分解特性を示した。
Example 9
A polymer was obtained in the same manner as in Example 8 except that the polymerization temperature was 60 ° C. The yield was 25%. The obtained polymer showed good solubility in water, methanol, THF, chloroform, dichloromethane, DMF, NMP and DMSO. The evaluation results of the obtained polymer are shown in Table 1.
Further, when the temperature responsiveness of the obtained polymer was evaluated, the temperature responsiveness of the aqueous solution started to increase at a temperature lower than that of the commercially available linear PNIPAM, and the maximum absorbance in the measurement temperature range was linear. It was more than twice that of PNIPAM and showed a good temperature response.
Moreover, the temperature responsiveness of the film showed an upwardly convex parabola in the measurement temperature range, and the temperature showing the maximum refractive index was 20 ° C. or more lower than that of the linear PNIPAM, indicating a good temperature responsiveness.
As a result of thermogravimetric measurement of the obtained polymer, the thermogravimetric change was not significantly different from that of commercially available linear PNIPAM, and showed the same thermal decomposition characteristics.
(実施例10)
重合温度を25℃とした以外は実施例8と同様にし、ポリマーを得た。収率は44%であった。得られたポリマーは水、メタノール、THF,クロロホルム、ジクロロメタン、DMF,NMP、DMSOに対して良好な溶解性を示した。得られたポリマーの評価結果を表1に示した。
また得られたポリマーの温度応答性を評価したところ、水溶液の温度応答性は市販の直鎖型PNIPAMよりも低い温度で吸光度が上昇しはじめ、また測定温度範囲における最大の吸光度は、直鎖型PNIPAMの2倍以上であり、良好な温度応答性を示した。
またフィルムの温度応答性は、測定温度範囲において上に凸の放物線を描き、最大の屈折率を示す温度は、直鎖型PNIPAMよりも20℃以上低く、良好な温度応答性を示した。
また得られたポリマーの熱重量測定を実施した結果、熱重量変化は市販の直鎖型PNIPAMと顕著な差異はなく、同等の熱分解特性を示した。
(Example 10)
A polymer was obtained in the same manner as in Example 8 except that the polymerization temperature was 25 ° C. The yield was 44%. The obtained polymer showed good solubility in water, methanol, THF, chloroform, dichloromethane, DMF, NMP and DMSO. The evaluation results of the obtained polymer are shown in Table 1.
Further, when the temperature responsiveness of the obtained polymer was evaluated, the temperature responsiveness of the aqueous solution started to increase at a temperature lower than that of the commercially available linear PNIPAM, and the maximum absorbance in the measurement temperature range was linear. It was more than twice that of PNIPAM and showed a good temperature response.
Moreover, the temperature responsiveness of the film showed an upwardly convex parabola in the measurement temperature range, and the temperature showing the maximum refractive index was 20 ° C. or more lower than that of the linear PNIPAM, indicating a good temperature responsiveness.
As a result of thermogravimetric measurement of the obtained polymer, the thermogravimetric change was not significantly different from that of commercially available linear PNIPAM, and showed the same thermal decomposition characteristics.
(実施例11)
重合時間を48時間とした以外は実施例8と同様にし、ポリマーを得た。収率は49%であった。得られたポリマーは水、メタノール、THF,クロロホルム、ジクロロメタン、DMF,NMP、DMSOに対して良好な溶解性を示した。得られたポリマーの評価結果を表1に示した。
また得られたポリマーの温度応答性を評価したところ、水溶液の温度応答性は市販の直鎖型PNIPAMよりも低い温度で吸光度が上昇しはじめ、また測定温度範囲における最大の吸光度は、直鎖型PNIPAMの2倍以上であり、良好な温度応答性を示した。
またフィルムの温度応答性は、測定温度範囲において上に凸の放物線を描き、最大の屈折率を示す温度は、直鎖型PNIPAMよりも20℃以上低く、良好な温度応答性を示した。
また得られたポリマーの熱重量測定を実施した結果、熱重量変化は市販の直鎖型PNIPAMと顕著な差異はなく、同等の熱分解特性を示した。
(Example 11)
A polymer was obtained in the same manner as in Example 8 except that the polymerization time was 48 hours. The yield was 49%. The obtained polymer showed good solubility in water, methanol, THF, chloroform, dichloromethane, DMF, NMP and DMSO. The evaluation results of the obtained polymer are shown in Table 1.
Further, when the temperature responsiveness of the obtained polymer was evaluated, the temperature responsiveness of the aqueous solution started to increase at a temperature lower than that of the commercially available linear PNIPAM, and the maximum absorbance in the measurement temperature range was linear. It was more than twice that of PNIPAM and showed a good temperature response.
Moreover, the temperature responsiveness of the film showed an upwardly convex parabola in the measurement temperature range, and the temperature showing the maximum refractive index was 20 ° C. or more lower than that of the linear PNIPAM, indicating a good temperature responsiveness.
As a result of thermogravimetric measurement of the obtained polymer, the thermogravimetric change was not significantly different from that of commercially available linear PNIPAM, and showed the same thermal decomposition characteristics.
(実施例12)
重合時間を72時間とした以外は実施例8と同様にし、ポリマーを得た。収率は55%であった。得られたポリマーは水、メタノール、THF,クロロホルム、ジクロロメタン、DMF,NMP、DMSOに対して良好な溶解性を示した。得られたポリマーの評価結果を表1に示した。
また得られたポリマーの温度応答性を評価したところ、水溶液の温度応答性は市販の直鎖型PNIPAMよりも低い温度で吸光度が上昇しはじめ、また測定温度範囲における最大の吸光度は、直鎖型PNIPAMの2倍以上であり、良好な温度応答性を示した。
またフィルムの温度応答性は、測定温度範囲において上に凸の放物線を描き、最大の屈折率を示す温度は、直鎖型PNIPAMよりも20℃以上低く、良好な温度応答性を示した。
また得られたポリマーの熱重量測定を実施した結果、熱重量変化は市販の直鎖型PNIPAMと顕著な差異はなく、同等の熱分解特性を示した。
(Example 12)
A polymer was obtained in the same manner as in Example 8 except that the polymerization time was 72 hours. The yield was 55%. The obtained polymer showed good solubility in water, methanol, THF, chloroform, dichloromethane, DMF, NMP and DMSO. The evaluation results of the obtained polymer are shown in Table 1.
Further, when the temperature responsiveness of the obtained polymer was evaluated, the temperature responsiveness of the aqueous solution started to increase at a temperature lower than that of the commercially available linear PNIPAM, and the maximum absorbance in the measurement temperature range was linear. It was more than twice that of PNIPAM and showed a good temperature response.
Moreover, the temperature responsiveness of the film showed an upwardly convex parabola in the measurement temperature range, and the temperature showing the maximum refractive index was 20 ° C. or more lower than that of the linear PNIPAM, indicating a good temperature responsiveness.
As a result of thermogravimetric measurement of the obtained polymer, the thermogravimetric change was not significantly different from that of commercially available linear PNIPAM, and showed the same thermal decomposition characteristics.
(実施例13)
重合時間を96時間とした以外は実施例8と同様にし、ポリマーを得た。収率は53%であった。得られたポリマーは水、メタノール、THF,クロロホルム、ジクロロメタン、DMF,NMP、DMSOに対して良好な溶解性を示した。得られたポリマーの評価結果を表1に示した。
また得られたポリマーの温度応答性を評価したところ、水溶液の温度応答性は市販の直鎖型PNIPAMよりも低い温度で吸光度が上昇しはじめ、また測定温度範囲における最大の吸光度は、直鎖型PNIPAMの2倍以上であり、良好な温度応答性を示した。
またフィルムの温度応答性は、測定温度範囲において上に凸の放物線を描き、最大の屈折率を示す温度は、直鎖型PNIPAMよりも20℃以上低く、良好な温度応答性を示した。
また得られたポリマーの熱重量測定を実施した結果、熱重量変化は市販の直鎖型PNIPAMと顕著な差異はなく、同等の熱分解特性を示した。
(Example 13)
A polymer was obtained in the same manner as in Example 8 except that the polymerization time was 96 hours. The yield was 53%. The obtained polymer showed good solubility in water, methanol, THF, chloroform, dichloromethane, DMF, NMP and DMSO. The evaluation results of the obtained polymer are shown in Table 1.
Further, when the temperature responsiveness of the obtained polymer was evaluated, the temperature responsiveness of the aqueous solution started to increase at a temperature lower than that of the commercially available linear PNIPAM, and the maximum absorbance in the measurement temperature range was linear. It was more than twice that of PNIPAM and showed a good temperature response.
Moreover, the temperature responsiveness of the film showed an upwardly convex parabola in the measurement temperature range, and the temperature showing the maximum refractive index was 20 ° C. or more lower than that of the linear PNIPAM, indicating a good temperature responsiveness.
As a result of thermogravimetric measurement of the obtained polymer, the thermogravimetric change was not significantly different from that of commercially available linear PNIPAM, and showed the same thermal decomposition characteristics.
(比較例1)
アルドリッチ社製のポリN−イソプロピルアクリルアミドを購入し、評価した評価結果を表1に示した。またポリマーの外部刺激応答性をアッベ屈折率計で評価したところ、5℃から50℃範囲においては温度応答性を示さなかった。
(Comparative Example 1)
Table 1 shows the evaluation results of purchasing and evaluating poly-N-isopropylacrylamide manufactured by Aldrich. When the external stimulus responsiveness of the polymer was evaluated with an Abbe refractometer, the temperature responsiveness was not exhibited in the range of 5 ° C to 50 ° C.
(比較例2)
開始剤として下記式(9)で表されるアルドリッチ社製の開始剤「Hexafunctional initiator 製品番号723207」を用いた以外は実施例3と同様にし、下記式(10)で示されるポリマーを得た。
得られたポリマーの評価結果を表1に示した。またポリマーの外部刺激応答性をアッベ屈折率計で評価したところ、5℃から50℃範囲においては温度応答性を示さなかった。
(Comparative Example 2)
A polymer represented by the following formula (10) was obtained in the same manner as in Example 3, except that an initiator “Hexafunctional initiator product number 723207” represented by the following formula (9) represented by the following formula (9) was used as the initiator.
The evaluation results of the obtained polymer are shown in Table 1. When the external stimulus responsiveness of the polymer was evaluated with an Abbe refractometer, the temperature responsiveness was not exhibited in the range of 5 ° C to 50 ° C.
(参考例1)
反応溶媒としてDMAcを用いた以外は実施例3と同様にしたところ、有意な量のポリマー生成物は得られなかった。
(Reference Example 1)
Except that DMAc was used as the reaction solvent, the same procedure as in Example 3 was carried out, but no significant amount of polymer product was obtained.
以上述べた様に、本発明のポリマーは硫黄元素を含まずに高い屈折率を実現する材料であり、光学レンズ、光学フィルム、光学フィルムを用いた液晶表示装置などの用途に適用することができる。 As described above, the polymer of the present invention is a material that does not contain sulfur element and realizes a high refractive index, and can be applied to applications such as an optical lens, an optical film, and a liquid crystal display device using the optical film. .
Claims (3)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015094314 | 2015-05-01 | ||
JP2015094314 | 2015-05-01 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2016210955A true JP2016210955A (en) | 2016-12-15 |
JP6740527B2 JP6740527B2 (en) | 2020-08-19 |
Family
ID=57550658
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2015181360A Expired - Fee Related JP6740527B2 (en) | 2015-05-01 | 2015-09-15 | Polymers, optical materials and lenses |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP6740527B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10562993B2 (en) | 2017-03-21 | 2020-02-18 | Ricoh Company, Ltd. | Polymer composition and optical material |
US10649242B2 (en) | 2016-07-27 | 2020-05-12 | Ricoh Company, Ltd. | Multilayer film, multilayer film composite, optical component, and window |
WO2021117537A1 (en) * | 2019-12-09 | 2021-06-17 | 国立大学法人京都大学 | Member for fogging prevention, suppression of water droplet adhesion, suppression of icing, or suppression of ice nucleus formation |
US11274174B2 (en) | 2015-09-15 | 2022-03-15 | Ricoh Company, Ltd. | Polymer, resin composition, light control material, optical waveguide material, athermal optical element, color display element, and optical material |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000319328A (en) * | 1999-04-06 | 2000-11-21 | L'oreal Sa | Composition containing polymer of star-structure, the polymer and use thereof |
US20030236354A1 (en) * | 2002-04-04 | 2003-12-25 | Kennedy Joseph P. | Star block copolymers comprising polyisobutylene-B-polyacrylonitrile arms radiating from an aromatic core |
JP2008208322A (en) * | 2007-01-30 | 2008-09-11 | Hitachi Chem Co Ltd | Phenol derivative which has anthracene residue in side chain, and its manufacturing method |
JP2008274171A (en) * | 2007-05-02 | 2008-11-13 | Univ Kanagawa | Molecular nanocapsule and its preparation method |
JP2009263605A (en) * | 2008-04-30 | 2009-11-12 | Jsr Corp | Molecular capsule and its producing method |
JP2010155880A (en) * | 2008-12-26 | 2010-07-15 | Lintec Corp | Stimuli-responsive crosslinked polymer and production method therefor |
-
2015
- 2015-09-15 JP JP2015181360A patent/JP6740527B2/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000319328A (en) * | 1999-04-06 | 2000-11-21 | L'oreal Sa | Composition containing polymer of star-structure, the polymer and use thereof |
US20030236354A1 (en) * | 2002-04-04 | 2003-12-25 | Kennedy Joseph P. | Star block copolymers comprising polyisobutylene-B-polyacrylonitrile arms radiating from an aromatic core |
JP2008208322A (en) * | 2007-01-30 | 2008-09-11 | Hitachi Chem Co Ltd | Phenol derivative which has anthracene residue in side chain, and its manufacturing method |
JP2008274171A (en) * | 2007-05-02 | 2008-11-13 | Univ Kanagawa | Molecular nanocapsule and its preparation method |
JP2009263605A (en) * | 2008-04-30 | 2009-11-12 | Jsr Corp | Molecular capsule and its producing method |
JP2010155880A (en) * | 2008-12-26 | 2010-07-15 | Lintec Corp | Stimuli-responsive crosslinked polymer and production method therefor |
Non-Patent Citations (1)
Title |
---|
ZHENG,A. ET AL.: "Amphiphilic star block copolymers as gene carrier Part I: Synthesis via ATRP using calix[4]resorcina", MATERIALS SCIENCE & ENGINEERING, C: MATERIALS FOR BIOLOGICAL APPLICATIONS, vol. 33, no. 1, JPN6019024166, 2013, pages 519 - 526, ISSN: 0004190254 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11274174B2 (en) | 2015-09-15 | 2022-03-15 | Ricoh Company, Ltd. | Polymer, resin composition, light control material, optical waveguide material, athermal optical element, color display element, and optical material |
US10649242B2 (en) | 2016-07-27 | 2020-05-12 | Ricoh Company, Ltd. | Multilayer film, multilayer film composite, optical component, and window |
US10562993B2 (en) | 2017-03-21 | 2020-02-18 | Ricoh Company, Ltd. | Polymer composition and optical material |
WO2021117537A1 (en) * | 2019-12-09 | 2021-06-17 | 国立大学法人京都大学 | Member for fogging prevention, suppression of water droplet adhesion, suppression of icing, or suppression of ice nucleus formation |
Also Published As
Publication number | Publication date |
---|---|
JP6740527B2 (en) | 2020-08-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6740527B2 (en) | Polymers, optical materials and lenses | |
JP6218059B2 (en) | Process for producing aromatic polyketone and aromatic polyketone | |
TW201544503A (en) | Dianhydride and polyimide | |
Wang et al. | New fluorinated poly (ether sulfone imide) s with high thermal stability and low dielectric constant | |
Mahindrakar et al. | Optically transparent, organosoluble poly (ether-amide) s bearing triptycene unit; synthesis and characterization | |
Wu et al. | Novel soluble and optically active polyimides containing axially asymmetric 9, 9′-spirobifluorene units: synthesis, thermal, optical and chiral properties | |
Wu et al. | Multifunctional polyimides by direct silyl ether reaction of pendant hydroxy groups: Toward low dielectric constant, high optical transparency and fluorescence | |
TW202204473A (en) | Polyamide, polyamide imide, and derivatives thereof, optical film and display device, as well as manufacturing methods thereof | |
Chen et al. | Synthesis and characterization of polyketones containing pendant carbazoles | |
Liu et al. | Synthesis of new fluorinated aromatic poly (ether ketone amide) s containing cardo structures by a heterogeneous palladium‐catalyzed carbonylative polycondensation | |
Nakazono et al. | Synthesis and properties of pendant fluorene moiety-tethered aliphatic polycarbonates | |
Shabbir et al. | Pyrimidine based carboxylic acid terminated aromatic and semiaromatic hyperbranched polyamide-esters: synthesis and characterization | |
Nechifor | Aromatic polyesters with photosensitive side chains: Synthesis, characterization and properties | |
JP6324787B2 (en) | Novel diol compounds and polyesters | |
Behniafar et al. | Synthesis and characterization of novel aromatic polyamides derived from 2, 2′‐bis (p‐phenoxyphenyl)‐4, 4′‐diaminodiphenyl ether | |
JP6999892B2 (en) | Polymer compounds, their manufacturing methods, and optical materials | |
CN109320443B (en) | Method for preparing compound and method for preparing polymer containing compound | |
CN108034049B (en) | Polyimide resin and preparation method thereof | |
CN105542155B (en) | A kind of soluble azopolyamide liquid crystal material of normal-butyl substitution and preparation method thereof | |
JP2020033340A (en) | Quaternary ammonium group-containing polyamide | |
CN106543438A (en) | A kind of preparation method of chlorinated and fluorinated polyamide-imide resin | |
Rhee et al. | Soluble and Processable Poly (p‐phenylene) with Pendant Imide Groups | |
JP5804460B2 (en) | Poly (arylene thioether) having a binaphthyl skeleton | |
JP6196731B2 (en) | Novel acid dianhydride, production method thereof, and polyimide produced therefrom | |
Rusu et al. | New polysulfones with pendant groups of cinnamate type |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150924 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180910 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20190612 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190626 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190816 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200110 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200306 |
|
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: 20200522 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20200617 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6740527 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
LAPS | Cancellation because of no payment of annual fees |