JPH03167226A - Block copolymer - Google Patents
Block copolymerInfo
- Publication number
- JPH03167226A JPH03167226A JP1308040A JP30804089A JPH03167226A JP H03167226 A JPH03167226 A JP H03167226A JP 1308040 A JP1308040 A JP 1308040A JP 30804089 A JP30804089 A JP 30804089A JP H03167226 A JPH03167226 A JP H03167226A
- Authority
- JP
- Japan
- Prior art keywords
- segment
- polymerization
- block copolymer
- polymer
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 21
- -1 acrylic ester Chemical class 0.000 claims abstract description 12
- 239000004642 Polyimide Substances 0.000 claims abstract description 7
- 229920001721 polyimide Polymers 0.000 claims abstract description 7
- 229920002312 polyamide-imide Polymers 0.000 claims abstract description 6
- 229920000728 polyester Polymers 0.000 claims abstract description 6
- 229920002635 polyurethane Polymers 0.000 claims abstract description 4
- 239000004814 polyurethane Substances 0.000 claims abstract description 4
- 239000004962 Polyamide-imide Substances 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 11
- 125000003277 amino group Chemical group 0.000 abstract description 6
- 238000012644 addition polymerization Methods 0.000 abstract description 4
- 238000006068 polycondensation reaction Methods 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 2
- 238000006116 polymerization reaction Methods 0.000 description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 125000002843 carboxylic acid group Chemical group 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- REIDAMBAPLIATC-UHFFFAOYSA-N 4-methoxycarbonylbenzoic acid Chemical compound COC(=O)C1=CC=C(C(O)=O)C=C1 REIDAMBAPLIATC-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000010550 living polymerization reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- ZNJXRXXJPIFFAO-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluoropentyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)F ZNJXRXXJPIFFAO-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- LTVRSJBNXLZFGT-UHFFFAOYSA-N 2-silylethenone Chemical compound [SiH3]C=C=O LTVRSJBNXLZFGT-UHFFFAOYSA-N 0.000 description 1
- YCGKJPVUGMBDDS-UHFFFAOYSA-N 3-(6-azabicyclo[3.1.1]hepta-1(7),2,4-triene-6-carbonyl)benzamide Chemical compound NC(=O)C1=CC=CC(C(=O)N2C=3C=C2C=CC=3)=C1 YCGKJPVUGMBDDS-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/401—Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/48—Polyesters
- B01D71/481—Polyarylates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
- B01D71/641—Polyamide-imides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/54—Polyureas; Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
Description
【発明の詳細な説明】 (産業上の利用分野) 本発明は新規なブロック共重合体に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a novel block copolymer.
(従来の技術)
性質の異なる高分子材料を組み合わせて新しい機能を発
現させる手法としてブロック共重合を利用する試みがあ
り、天然ゴム等のゴムを冷暗所で窒素中で単量体の存在
下で素練りして分子を剪断力で切断してラジカルを発生
させてブロック共重合体を得る方法、ポリブロビレンオ
キシドの存在下でエチレンオキシドを重合するポリエー
テルブロック共重合体の製法、テレフタル酸とエチレン
グリコールのほかにポリオキシエチレンを存在させて共
縮合させるブロック共重合体の製法などが知られている
。(Prior technology) There have been attempts to utilize block copolymerization as a method for combining polymeric materials with different properties to express new functions. A method to obtain a block copolymer by kneading and cutting molecules by shearing force to generate radicals, a method for producing a polyether block copolymer by polymerizing ethylene oxide in the presence of polypropylene oxide, terephthalic acid and ethylene glycol In addition to this, a method for producing a block copolymer in which polyoxyethylene is present and co-condensed is known.
(発明が解決しようとする課題)
しかし、従来の方法では組み合わせる高分子素材が限定
され、付加重合体同士あるいは重縮合体同士のブロック
重合体しか得られず、ユニークな性能のブロック共重合
体を得るために、より異なる機能の重合体を組み合わせ
たいという要望が強かった。(Problem to be solved by the invention) However, with conventional methods, the combination of polymeric materials is limited, and only block copolymers of addition polymers or polycondensates can be obtained, and block copolymers with unique performance cannot be obtained. There has been a strong desire to combine polymers with different functions in order to obtain
(課題を解決するための手段)
本発明者らはこのような状況に鑑み付加重合系ポリマー
と重縮合系ポリマーとを両セグメントとするブロック共
重合体が得られれば従来にない機能を通するポリマー素
材となることを考慮して鋭意検討した結果、そのような
ブロック共重合体を得ることに成功し、本発明に到達し
た。(Means for Solving the Problems) In view of this situation, the present inventors believe that if a block copolymer having both segments of an addition polymerization polymer and a polycondensation polymer can be obtained, it will have an unprecedented function. As a result of intensive studies considering the use of the block copolymer as a polymer material, we succeeded in obtaining such a block copolymer and arrived at the present invention.
すなわち、本発明の要旨は一般式A−B又はB−・A−
Bで表され、セグメントAがポリエステル、ポリアミド
、ポリイミド、ポリアミドイミド及びポリウレタンから
選ばれるものであり、セグメントBがポリ(メタ)アク
リル酸エステルの1種以上からなるものであるブロック
共重合体にある。That is, the gist of the present invention is that the general formula AB or B-・A-
B, segment A is selected from polyester, polyamide, polyimide, polyamideimide, and polyurethane, and segment B is composed of one or more poly(meth)acrylic esters. .
本発明のブロック共重合体におけるセグメントAとして
はポリエチレンテレフタレート、ポリブチレンテレフタ
レート、全芳香族ポリエステル等のポリエステル、ナイ
ロン6、ナイロン6−6、ナイロン11,ナイロンl2
、ナイロン6−10,ポリp−フエニレンテレフタルア
ミド、ポリm−フエニレンイソフタルアミド等のポリア
ミド、ビロメリット酸無水物、ジフエニルエーテル3,
4, 3゜,4−テトラカルボン酸無水物、、ジフエ
ニルメタン3,4.3゜.4゜−テトラカルボン酸無水
物、ジフエニルブロバン3, 4, 3゜,4゜−テト
ラカルボン酸無水物等のテトラカルボン酸無水物と芳香
族ジアミンとからのポリイミド等の芳香族ポリイミド、
トリメリット酸と芳香族ジアミンとからのポリアミドイ
ミド、ピロメリット酸無水物とイソフタル酸等のジカル
ボン酸の組み合わせと芳香族ジアミンとからのポリアミ
ドイミド等のポリアミドイミド、ジフエニルメタンジイ
ソシアネート、トリレンジイソシアネート、ヘキサメチ
レンジイソシアネート等のジイソシアネートとポリエチ
レングリコール、ポリブロピレングリコール等の両末端
ジオールポリオールやアジビン酸とエチレングリコール
、ブロビレングリコール、1.4−ブタンジオール等の
グリコールからの両末端ジオールポリエステルとからの
ポリウレタンを用いることができる。Segment A in the block copolymer of the present invention includes polyesters such as polyethylene terephthalate, polybutylene terephthalate, and wholly aromatic polyesters, nylon 6, nylon 6-6, nylon 11, and nylon 12.
, nylon 6-10, polyamides such as poly p-phenylene terephthalamide, poly m-phenylene isophthalamide, biromellitic anhydride, diphenyl ether 3,
4, 3°, 4-tetracarboxylic anhydride, diphenylmethane 3,4.3°. Aromatic polyimides such as polyimides made from tetracarboxylic anhydrides such as 4°-tetracarboxylic anhydride, diphenylbroban 3, 4, 3°, 4°-tetracarboxylic anhydrides, and aromatic diamines;
Polyamideimide made from trimellitic acid and aromatic diamine, polyamideimide made from combination of pyromellitic anhydride and dicarboxylic acid such as isophthalic acid and aromatic diamine, diphenylmethane diisocyanate, tolylene diisocyanate, Polyurethane made from a diisocyanate such as hexamethylene diisocyanate and a diol polyol at both ends such as polyethylene glycol or polypropylene glycol, or a diic acid polyester at both ends from a glycol such as ethylene glycol, brobylene glycol or 1,4-butanediol. can be used.
セグメントBとしてのポリ(メタ)アクリル酸エステル
としては一般式(1)
R2
(式中、R1は炭素数1〜18のアルキル基、弗化アル
キル基又はシクロヘキシル基を示し、R2は水素又はメ
チル基を示す。)で表されるものが好ましく、このよう
なポリ(メタ)アクリル酸エステルとしてメチルメタク
リレート、n−プチルメタクリレート、2−エチルへキ
シルメタクリレート、ラウリルメタクリレート、エチル
アクリレート、n−プチルアクリレート、2, 2.
2−トリフルオロエチルメタクリレート、オクタフルオ
ロペンチルメタクリレート、ヘブタデ力フルオロデシル
メタクリレート、2, 2. 2−トリフルオロエチル
アクリレート等を挙げることができる。The poly(meth)acrylic acid ester as segment B has the general formula (1) R2 (wherein R1 represents an alkyl group having 1 to 18 carbon atoms, a fluorinated alkyl group, or a cyclohexyl group, and R2 represents hydrogen or a methyl group. ) is preferred, and examples of such poly(meth)acrylic esters include methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl methacrylate, , 2.
2-trifluoroethyl methacrylate, octafluoropentyl methacrylate, fluorodecyl methacrylate, 2, 2. Examples include 2-trifluoroethyl acrylate.
本発明のブロック共重合体はセグメントAの重合時又は
重合後にその片又は両末端に水酸基又はアミノ基を導入
し、一方、セグメントBの重合時又は重合後にその片末
端にカルボン酸基を導入し、セグメントAの片又は両末
端に導入された水酸基又はアミノ基とセグメントBの片
末端に導入されたカルボン酸基との反応によるエステル
結合、アミド結合あるいはイミド結合を介して結合して
なるブロック共重合体である。In the block copolymer of the present invention, a hydroxyl group or an amino group is introduced into one or both ends of segment A during or after polymerization, and a carboxylic acid group is introduced into one end of segment B during or after polymerization. , a block compound formed by bonding via an ester bond, an amide bond, or an imide bond by a reaction between a hydroxyl group or an amino group introduced at one or both ends of segment A and a carboxylic acid group introduced at one end of segment B. It is a polymer.
本発明のブロック共重合体は用途に応じて各セグメント
の重合度を設定すれば良く、分子量により限定されるも
のではない。The degree of polymerization of each segment of the block copolymer of the present invention may be determined depending on the intended use, and is not limited by molecular weight.
本発明のブロック共重合体はセグメントAとセグメント
Bとを別個に重合し、セグメントAの重合においてはジ
オール又はジアミンを過剰に用いて両末端に水酸基又は
アミノ基を導入させ、片末端の場合は重合の際にモノオ
ール、モノアミン、モノカルボン酸、ジカルボン酸モノ
エステル等を一部併用することにより片末端水酸基又は
アミノ基のものとすることができる。重合体がポリイミ
ド、ポリアミドイミドの場合は無水フタル酸を一部併用
することで片末端のものが得られる。In the block copolymer of the present invention, segment A and segment B are separately polymerized, and in the polymerization of segment A, diol or diamine is used in excess to introduce a hydroxyl group or an amino group at both ends. By partially using a monool, monoamine, monocarboxylic acid, dicarboxylic acid monoester, etc. during polymerization, it is possible to obtain a polymer having a hydroxyl group or an amino group at one end. When the polymer is polyimide or polyamideimide, one end can be obtained by partially using phthalic anhydride.
セグメントBの重合は重合終了時あるいは終了後にその
片末端にカルボン酸や酸無水物基を導入することからイ
オン重合あるいは基転移重合法で重合するのが好ましく
、ポリ(メタ)アクリル酸エステルの重合度、分子量分
布、組成のコントロールが比較的容易であることから基
転移重合法で重合するのがより好ましい。この基転移重
合法とは特開昭58− 1 3603号公報に開示され
ている重合法であり、シリルケテンアセタール等の開始
剤を用いて室温でリビング重合を行うもので、ポリ(メ
タ)アクリル酸エステルの重合に適している。アニオン
リビング重合の場合はトリメチルシリルオキシ,モノク
ロロアルカン(アルカンとしては例えばエタン、ブロバ
ン等を挙げることができる)を用いればセグメントBに
水酸基を導入でき、これとジカルボン酸モノハライドや
無水トリメリット酸ハライド等との反応により末端にカ
ルボン酸基を導入できる。又、2−メルカブトエタノー
ルのような連鎖移動剤を用いてラジカル重合を行うこと
により末端に水酸基を導入し、これとジカルボン酸モノ
ハライド等との反応によりカルボン酸基を導入できる。Polymerization of segment B is preferably carried out by ionic polymerization or group transfer polymerization because a carboxylic acid or acid anhydride group is introduced into one end of the segment B at or after the completion of polymerization. It is more preferable to carry out the polymerization by a group transfer polymerization method because it is relatively easy to control the polymerization degree, molecular weight distribution, and composition. This group transfer polymerization method is a polymerization method disclosed in JP-A-58-13603, in which living polymerization is carried out at room temperature using an initiator such as silyl ketene acetal. Suitable for polymerizing acid esters. In the case of anionic living polymerization, a hydroxyl group can be introduced into segment B by using trimethylsilyloxy, monochloroalkane (alkanes include ethane, broban, etc.), and this and dicarboxylic acid monohalide, trimellitic anhydride halide, etc. A carboxylic acid group can be introduced at the terminal by reaction with Furthermore, a hydroxyl group can be introduced at the end by radical polymerization using a chain transfer agent such as 2-mercabutoethanol, and a carboxylic acid group can be introduced by reacting this with dicarboxylic acid monohalide or the like.
本発明のセグメントBの製造において基転移重合法を用
いる場合はその重合条件、重合共触媒、重合溶媒等につ
いては該公報に記載されたものを同様の条件で用いるこ
とができる.
開始剤として](2−メチル−1−[2−( トリメチ
ルシロキシ)エトキシ]−1−ブロペニル)オキシ]ト
リメチルシランを用いて重合後、重合停止のため重合開
始末端のトリメチルシリル基を脱離させると末端に水酸
基が残るので好ましい。セグメントBの片末端にカルボ
ン酸あるいは酸無水物を導入する方法としてはこの末端
の水酸基とトリメリット酸無水物モノ酸クロリドの反応
による酸無水物基の導入、無水コハク酸、無水グルタル
酸、無水フタル酸、テレフタル酸モノメチルエステルと
の反応によるカルボン酸基の導入を挙げることができる
。When the group transfer polymerization method is used in the production of segment B of the present invention, the polymerization conditions, polymerization cocatalyst, polymerization solvent, etc. described in the publication can be used under similar conditions. After polymerization using [2-methyl-1-[2-(trimethylsiloxy)ethoxy]-1-bropenyl)oxy]trimethylsilane as an initiator, the trimethylsilyl group at the polymerization initiation terminal is removed to terminate the polymerization. This is preferable because a hydroxyl group remains at the end. Methods for introducing a carboxylic acid or acid anhydride to one end of segment B include introducing an acid anhydride group by reacting the hydroxyl group at this end with trimellitic anhydride monoacid chloride, succinic anhydride, glutaric anhydride, and anhydride. Introduction of a carboxylic acid group by reaction with phthalic acid or terephthalic acid monomethyl ester can be mentioned.
このようにして得られたセグメントAとセグメントBと
を適切な溶媒、例えばジメチルアセトアミド等の溶媒中
で混合、必要であれば加熱することによりブロック共重
合体を得ることができる。A block copolymer can be obtained by mixing segment A and segment B thus obtained in a suitable solvent, for example, dimethylacetamide, and heating if necessary.
本発明のブロック共重合体には目的とする用途によって
は安定剤、着色剤等の各種添加剤を添加しても良い。Depending on the intended use, various additives such as stabilizers and colorants may be added to the block copolymer of the present invention.
(実施例) 以下に実施例を用いて本発明を更に説明する。(Example) The present invention will be further explained below using Examples.
参考例1
アルゴン導入管、撹拌器、熱電対、乾燥管を具備した5
00mβフラスコ内を充分乾燥するとともにアルゴン置
換した後、これにビス(4−アミノフエニル)エーテル
11.0g,乾燥ジメチルアセトアミド178gを入れ
、この溶液を撹拌しながら室温で無水ビロメリット酸1
1.0gを2〜3分かけて滴下した。酸無水物の添加に
より反応系の温度が38℃まで上昇したが、約30分で
室温に戻った。室温で更に2時間撹拌を続けて固有粘度
0.7dg/g (30℃)のポリアミド酸溶液を得た
。Reference Example 1 5 equipped with an argon introduction tube, a stirrer, a thermocouple, and a drying tube
After sufficiently drying the inside of the 00mβ flask and purging it with argon, 11.0 g of bis(4-aminophenyl) ether and 178 g of dry dimethylacetamide were added to it, and while stirring this solution, 1 ml of biromellitic anhydride was added at room temperature.
1.0 g was added dropwise over 2 to 3 minutes. The temperature of the reaction system rose to 38°C due to the addition of the acid anhydride, but returned to room temperature in about 30 minutes. Stirring was continued for another 2 hours at room temperature to obtain a polyamic acid solution with an intrinsic viscosity of 0.7 dg/g (30°C).
参考例2
アルゴン導入管、撹拌器、熱電対、排気管を具備した5
00mj2フラスコ内を充分乾燥するとともにアルゴン
置換した後、これにテトラヒドロフラン2 5 0mj
?. トリスジメチルアミノスルホニウムビフルオラ
イドの0.04モルアセトニトリル溶液5.0mj2、
[(2−メチル−1−[2−( }リメチルシロキシ)
エトキシJ−1−ブロペニル)オキシ]トリメチルシラ
ン2.Ogを入れ、これを撹拌しながら、反応系の温度
が50℃を越えないように注意をしつつ、2, 2.
2− トリフルオロエチルメタクリレート67gを10
分かけて滴下した。Reference example 2 5 equipped with an argon introduction pipe, a stirrer, a thermocouple, and an exhaust pipe
After thoroughly drying the inside of the flask and purging it with argon, add 250mj of tetrahydrofuran to it.
? .. 0.04 molar acetonitrile solution of trisdimethylaminosulfonium bifluoride 5.0 mj2,
[(2-methyl-1-[2-( }limethylsiloxy)
EthoxyJ-1-bropenyl)oxy]trimethylsilane2. 2. Add Og and stir while being careful not to let the temperature of the reaction system exceed 50°C.
2- 67g of trifluoroethyl methacrylate in 10
It was dripped over several minutes.
滴下終了後も反応系の温度が30℃以下になるまで撹拌
を続けた後、l Omj2のメタノールを添加して重合
を停止させた。これにより重合開始末端のトリメチルシ
リル基が脱離し、ポリマー末端に水酸基が形成された。After the dropwise addition was completed, stirring was continued until the temperature of the reaction system became 30° C. or lower, and then 1 Omj2 of methanol was added to stop the polymerization. As a result, the trimethylsilyl group at the polymerization initiation terminal was removed, and a hydroxyl group was formed at the polymer terminal.
得られた溶液をヘキサン中に滴下してポリマーを沈殿さ
せ、沈殿物を乾燥して白色パウダー上のポリマーを得た
。このポリマーの分子量は約12000であった。The obtained solution was dropped into hexane to precipitate the polymer, and the precipitate was dried to obtain a polymer as a white powder. The molecular weight of this polymer was approximately 12,000.
このポリマー18.6gと乾燥テトラヒドロフラン20
0mβとを十分にアルゴン置換した500mgの反応容
器に入れ、これを水冷下で撹拌しながらこれに無水トリ
メリット酸クロリド4.3g1 トリエチルアミン2.
0gを添加したところ、直ちに白色固体(トリエチルア
ミン塩酸塩〉が析出したのでこれを濾別し、濾別後の溶
液なヘキサン中に滴下してポリマーを沈殿させ、乾燥し
、これを200mI2のメタノール中に入れて撹拌、精
製した後、濾別乾燥して末端に酸無水物を持つ白色パウ
ダー状ポリマーを得た。18.6 g of this polymer and 20 g of dry tetrahydrofuran
0 mβ was placed in a 500 mg reaction vessel which had been sufficiently purged with argon, and while stirring under water cooling, 4.3 g of trimellitic anhydride 2. triethylamine was added.
When 0 g was added, a white solid (triethylamine hydrochloride) was immediately precipitated, so this was filtered off, and the solution after filtration was added dropwise to hexane to precipitate the polymer. It was dried, and this was poured into 200 ml of methanol. After stirring and purifying the mixture, it was filtered and dried to obtain a white powdery polymer having an acid anhydride at its terminal.
実施例l
参考例lで得たポリアミド酸のジメチルアセトアミド溶
液90gと、参考例2で得たポリマー1gを乾燥ジメチ
ルアセトアミド9gに溶解した溶液とを混合した後、約
100℃で4時間撹拌して褐色の共重合体溶液を得た。Example 1 90 g of the dimethylacetamide solution of the polyamic acid obtained in Reference Example 1 and a solution of 1 g of the polymer obtained in Reference Example 2 dissolved in 9 g of dry dimethylacetamide were mixed, and then stirred at about 100 ° C. for 4 hours. A brown copolymer solution was obtained.
これがブロック共重合体であることはこのポリマーをメ
タノールで再沈殿させた後NMRで確認した。The fact that this was a block copolymer was confirmed by NMR after reprecipitating the polymer with methanol.
このポリマーを透明導電性ガラス基板上にスビンコート
し,250℃で2時間熱処理を行ったところ、ポリアミ
ド酸が脱水閉環し、ポリ2, 2. 2− }リフルオ
ロエチルメタクリレートとポリイミドとを両セグメント
とするブロック共重合体の薄膜が得られた。この基盤を
綿布で両面ラビングして配向処理し、これを用いてセル
ギャップ2.3μmとしてギャップ内に強誘電性液晶(
チッソ■製、CS− 1 0 1 4)を注入して強誘
電性液晶セルを作成した.このセルに電圧をパルス幅1
m S %パルス高±40Vで印加し、そのメモリー
性の評価を行ったところ良好な双安定性を示した。When this polymer was coated on a transparent conductive glass substrate and heat treated at 250°C for 2 hours, the polyamic acid was dehydrated and ring-closed, forming poly2, 2. 2-} A thin film of a block copolymer having both segments of trifluoroethyl methacrylate and polyimide was obtained. This substrate was aligned by rubbing both sides with cotton cloth, and using this, the cell gap was set to 2.3 μm, and the ferroelectric liquid crystal (
A ferroelectric liquid crystal cell was created by injecting CS-1014) manufactured by Chisso ■. Apply voltage to this cell with a pulse width of 1
When m S % pulse height was applied at ±40 V and its memory property was evaluated, it showed good bistability.
(発明の効果)
本発明のブロック共重合体は付加重合系セグメントと重
縮合系セグメントとからなるので付加重合系ポリマーの
特徴と重縮合系ポリマーの特徴を合わせ持ち、相溶剤、
塗料、各種機能性膜等の分野で有用な素材である。(Effects of the Invention) Since the block copolymer of the present invention is composed of an addition polymerization segment and a polycondensation segment, it has both the characteristics of an addition polymerization polymer and the characteristics of a polycondensation polymer.
It is a useful material in the fields of paints and various functional films.
Claims (1)
Aがポリエステル、ポリアミド、ポリイミド、ポリアミ
ドイミド及びポリウレタンから選ばれるものであり、セ
グメントBがポリ(メタ)アクリル酸エステルの1種以
上からなるものであるブロック共重合体。1) Represented by the general formula A-B or B-A-B, segment A is selected from polyester, polyamide, polyimide, polyamideimide, and polyurethane, and segment B is one type of poly(meth)acrylic ester. A block copolymer consisting of the above.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1308040A JPH03167226A (en) | 1989-11-28 | 1989-11-28 | Block copolymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1308040A JPH03167226A (en) | 1989-11-28 | 1989-11-28 | Block copolymer |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03167226A true JPH03167226A (en) | 1991-07-19 |
Family
ID=17976162
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1308040A Pending JPH03167226A (en) | 1989-11-28 | 1989-11-28 | Block copolymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03167226A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018191954A1 (en) * | 2017-04-21 | 2018-10-25 | Henkel Ag & Co. Kgaa | (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer, preparation method and use thereof |
-
1989
- 1989-11-28 JP JP1308040A patent/JPH03167226A/en active Pending
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018191954A1 (en) * | 2017-04-21 | 2018-10-25 | Henkel Ag & Co. Kgaa | (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymer, preparation method and use thereof |
CN110546175A (en) * | 2017-04-21 | 2019-12-06 | 汉高股份有限及两合公司 | (meth) acrylate functionalized poly (meth) acrylate-block-polyimide-block-poly (meth) acrylate copolymers, method for the production thereof and use thereof |
JP2020517769A (en) * | 2017-04-21 | 2020-06-18 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンHenkel AG & Co. KGaA | Poly(meth)acrylate-block-polyimide-block-poly(meth)acrylate copolymers with (meth)acrylate functional groups, their preparation and use |
US11066549B2 (en) | 2017-04-21 | 2021-07-20 | Henkel IP & Holding GmbH | (Meth)acrylate functionalized poly(meth)acrylate-block-polyimide- block-poly(meth)acrylate copolymer, preparation method and use thereof |
CN110546175B (en) * | 2017-04-21 | 2022-01-04 | 汉高股份有限及两合公司 | Functionalized poly (meth) acrylate-polyimide-poly (meth) acrylate block copolymers, methods and uses thereof |
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