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WO1997034877A1 - Derives de cyanopyrazine, polymeres, procede de production et articles moules - Google Patents

Derives de cyanopyrazine, polymeres, procede de production et articles moules Download PDF

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Publication number
WO1997034877A1
WO1997034877A1 PCT/JP1996/000663 JP9600663W WO9734877A1 WO 1997034877 A1 WO1997034877 A1 WO 1997034877A1 JP 9600663 W JP9600663 W JP 9600663W WO 9734877 A1 WO9734877 A1 WO 9734877A1
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WO
WIPO (PCT)
Prior art keywords
group
compound
general formula
polymer
formula
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.)
Ceased
Application number
PCT/JP1996/000663
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English (en)
Japanese (ja)
Inventor
Masashi Kamiyama
Atsushi Yanagisawa
Hiroshi Takahashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Soda Co Ltd
Original Assignee
Nippon Soda Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to JP7263470A priority Critical patent/JPH08143553A/ja
Priority claimed from JP7263470A external-priority patent/JPH08143553A/ja
Application filed by Nippon Soda Co Ltd filed Critical Nippon Soda Co Ltd
Priority to PCT/JP1996/000663 priority patent/WO1997034877A1/fr
Publication of WO1997034877A1 publication Critical patent/WO1997034877A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D241/26—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with nitrogen atoms directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate

Definitions

  • the present invention relates to novel cyano virazine derivatives and polymers useful as functional dyes, a method for producing them, and molded articles.
  • An object of the present invention is to provide a 3.6-diamino-2,5-virazine dicarbonitrile derivative excellent in light stability that can withstand long-term outdoor use, and a molded article containing the same. Structure of the invention
  • R 1 , R 2 , R 3 , and R each independently represent a divalent hydrocarbon group which may have an ether bond, an ester bond, or an amide bond; May have a substituent, X 1 , X 2 , X 3.
  • X 4 is a hydrogen atom, an acryloyloxy group or a methacryloyloxy group, and X ′, X 2 , X 3 And at least one of X 4 is an acryloyloxy group or a methacryloyloxy group.
  • the compound represented by the general formula [I] undergoes radical polymerization to polymerize at an acryloyl or methacryloyl moiety.
  • the polymer is intended to mean a homopolymer and a copolymer of the monomer unit represented by the general formula [I], and a copolymer including a monomer unit other than the monomer unit represented by the general formula [I]. I do.
  • the divalent hydrocarbon group which may have an ether bond, an ester bond, or an amide bond of R 1 , R 2 , R 3 , and R 4 is a saturated or unsaturated linear or branched chain.
  • substituent of the hydrocarbon group examples include a hydroxyl group, an amino group, a mono- or di-alkylamino group, a carboxyl group, an acyl group, a formyl group, an alkoxyl group, an alkylyl group, an aryl group such as phenyl, and the like. Alkylsilyl group, halogen atom, heterocyclic group, etc. These substituents include, for example, an alkyl group, a hydroxyl group, an amino group, a mono- or dialkylamino group, a carboxyl group, an acyl group, a formyl group, an alkoxyl group, an alkenyloxy group, and an alkynyloxy group.
  • the chain hydrocarbon group usually has 2 to 22 carbon atoms, 1 to 6 for alkyl, and 2 to 6 for alkenyl and alkynyl.
  • Examples of the compound capable of radical polymerization include methyl methacrylate, methyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, methyl methacrylate Tertiary butyl acrylate, 2-methacrylic acid 2-ethylhexyl, octyl methacrylate, indecyl methacrylate, lauryl methacrylate, lauryl methacrylate Tridecyl, tridecyl methacrylate, cetyl-stearyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid, methacrylic acid 2—Hydrox-kishetil, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, getylaminoethyl methacrylate, metal Tertiary butyl aminoethyl
  • the radical polymerization initiator used for the polymerization of the compound of the general formula [I] or the mixture of the compound of the general formula [I] and the radically polymerizable compound may be azobisisobutyronitrile, azobis — 2,4-Dimethylpa X relonitrile, azobiscyclohexanecarbonitrile, azobi
  • R 1 , R 2 , R 3 , X ′, X 2 , X 3 , and X 4 have the same meanings as described above.
  • a known reaction or a similar reaction is appropriately selected. Can be manufactured.
  • HOCOCR CH 2 where L 1 , L 2 , L 3 , L 4 , L 3.
  • L G , L 7 , L 8 , L 0 , LL ", L 12 are OH, halogen atom, methane Represents a leaving group such as a sulfonyloxy group, a p-toluenesulfonyl group, etc.
  • R represents a hydrogen atom or a methyl group.
  • the reactions 1) to 4) may be performed simultaneously. If necessary, use a base and a dehydrating condensing agent.
  • the base and the dehydrating condensing agent include, for example, sodium hydroxide, sodium hydroxide, sodium carbonate, sodium carbonate, cesium carbonate, lithium hydroxide, and sodium hydroxide.
  • Examples of dehydrating condensing agents such as pyridine and triethylamine include mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as aromatic sulfonic acid, 1,3-dicyclohexylcarpoimide (DCC), and 1-ethyl- Examples include organic condensing agents such as 3- (3'-dimethylaminopropyl) carbodiimide (WSCI).
  • the solvent used in the reaction is not particularly limited as long as it is inert to the reaction reagent.
  • Examples thereof include dimethylformamide (DMF), dimethylacetamide (DMAC), dimethylsulfoxide (DMSO), Dimethyethane (DME), tetrahydrofuran (THF), etc.
  • BTX-based solvents such as ethers and benzene, chlorine-based solvents such as black form, acetate nitrile
  • reaction may be carried out without a solvent by using an excess of the reaction reagent.
  • R 1 , R, R 3 , and R 1 have an ether bond, an ester bond, or an amide bond, these bonds can be formed by an ordinary method.
  • L '3, L 14, L ' 5, L 16, L 17 represents a leaving group as described above.
  • n an integer of 1 to 8.
  • the compound of the present invention is also produced by the following method.
  • Hal and hal represent a halogen atom
  • Y 1 , Y 2 , Y 3 , and Y 1 each independently represent C, C alkyl, (CH 2 ) n 0 C 0 R 8 , and (iC , ⁇ C 22 alkyl, C, ⁇ C 22 haloalkyl, C 2 -C 22 alkenyl, optionally substituted phenyl, aralkyl, haloaralalkyl, Z represents sodium or potassium
  • n represents 1
  • X 5 represents an acryloyloxy group or a methyl acryloyloxy group
  • R 5 , R 6 , R 7 , and R 8 each independently represent C, -C 6 alkyl, (CH 2) n 0 C oR 9, a (CH 2) n X 5, R 5, R 6, R 7, one or more of R 8 is (CH 2) "X 5. )
  • the polymer of the present invention can be prepared by subjecting a compound represented by the general formula [I] or a mixture of the compound represented by the general formula [I] and a compound capable of radical polymerization to a known radical polymerization method, for example, bulk polymerization, solution polymerization, and the like. In this case, it can be produced by polymerization using a method such as emulsion polymerization or suspension polymerization. Degree of polymerization: 10 to 10
  • the amount of the radical polymerization initiator is 0.05 to 5 parts by weight based on 100 parts by weight of the monomer.
  • a known method may be applied to obtain a polymer having a crosslinked structure. That is, a copolymer with a monomer having two or more polymerizable double bonds or a monomer having a functional group such as a carboxyl group ⁇ hydroxyl group, for example, methacrylic acid ⁇ 2-hydroxyhexyl methacrylate After copolymerization with such a compound, a polymer having a cross-linked structure can be obtained by using in combination with an appropriate cross-linking agent, for example, an amino resin, an isocyanate compound, or an epoxy resin. Models with two or more polymerizable double bonds
  • the degree of cross-linking, expressed in mol% of nomer is between 0.11 and 99.999%, preferably between 0.1 and 50%.
  • the mixing ratio between the compound of the general formula [1] and the compound capable of undergoing radical polymerization is from 1: 0 to 1: 100,000, preferably from 1: 5 to 1: 200, by weight.
  • the polymer When the polymer is pulverized or emulsion polymerization or suspension polymerization for easy use, it can be used as it is as a fluorescent powder.
  • the molded article may be the polymer of the present invention as it is, or may be contained in a polymer compound.
  • Examples of the high molecular compound include (soft, semi-rigid, and rigid) PVC; polyethylene; polypropylene; polyvinyl alcohol; polymethyl acrylate; polymethyl methacrylate; poly (vinylidene chloride); Ril; Polybutadiene; Polystyrene; Ethylene-vinyl acetate copolymer; Vinyl chloride-vinyl acetate copolymer; Polyvinyl butyral; Polyvinyl formal; Polyesters such as PET and PBT; Polyarylates; Polyester carbonate; phenoxy resin; polyamides such as nylon 6, nylon 6Z6, nylon 11, nylon 12, and MXD6 nylon; polydimethylsiloxane; polytrimethylsilylpropyl; N; ionomers; serov Emission: polyether Chirenserofa emissions; cellulose ⁇ cetearyl Ichito; cellulose propionate Bok; Echiruseruro scan; two Bok b cellulose; ⁇ such hard resins.
  • the molded article is, for example, a plate, a film, a fiber, a nonwoven fabric, a fiber, a powder, a fine particle, or the like.
  • the manufacturing method of the molded body there are no particular restrictions on the manufacturing method of the molded body, and extrusion molding (single layer or laminated), inflation molding (single layer or fertile layer), calender molding, injection molding, It can be manufactured by transfer molding or the like, or by coating or impregnating a varnish containing the polymer of the present invention on glass, plastic, a reflector, a film, a woven fabric, a nonwoven fabric, a paper, or the like. .
  • the type and amount of the molded article satisfying the conditions for use and do not impair the object of the present invention such as UV absorbers, antioxidants, hindered amine light stabilizers, lubricants, anti-S agents, dropping agents, etc. Of additives can be distributed.
  • the pyrazine ring yield determined by absorbance measurement was 75.9%.
  • Example 4 (Production of crosslinked polymer) Compound A 0.05 g, methylmethacrylate 1.35 g, trimethylolpropane trimethacrylate 0.12 g, and azobisisoptirononitrile 49 mg were mixed. The resulting homogeneous solution was sealed after purging with nitrogen, and polymerized and cured in a 70 ° C. water bath for 3 hours. Force of immersing the obtained base body in black-hole form; polymer did not dissolve. It was immersed in a black-mouthed form for further 20 hours, crushed, filtered and washed with a black-mouthed form. The polymer slightly swollen with a black hole form was dried under reduced pressure. The obtained polymer exhibited a red fluorescent color as in Example 2. Yield 1.
  • Example 3 Each of the polymers obtained in Example 3 and Example 4 was ground using a mortar.
  • the resulting powder was ground using a mortar.
  • the powder having a particle size of 32 ⁇ m or less was prepared by passing through a 32 ⁇ m sieve.
  • the powder of Example 2 is powder (A)
  • the powder of Example 3 is powder (B).
  • the mixing ratio shown in Table 1 is 0.
  • a soft PVC film with a thickness of ⁇ 0.2 mm was formed by hot pressing.
  • Powder (A) was dissolved in PVC during kneading and film (A) became a transparent film, but powder (B) did not dissolve and film (B) became a fine particle-dispersed film.
  • a soft salt bifilm (C) was prepared in the same manner as in Example 4 by using 3,6-dimethylamino 2,5-virazin dicarponitrile (F) described in JP-A-5-32640. . Compound (F) dissolved in PVC during kneading, and film (C) became a transparent film.
  • the compound (molded product) of the present invention has excellent light fastness and water fastness because the dye component is chemically bonded to the polymer chain.
  • the compound of the present invention can be expected to be used as an intermediate for agricultural chemicals, fragrances, polymers, etc., and is expected to be used as a functional material such as electoruluminescence, wavelength conversion material, etc. Is done.
  • the molded article having a wavelength conversion function of the present invention is not limited to a light collector for a solar cell or a covering material of a greenhouse, but also a multi-film, a reflection (multi) film, and sunlight are averagely radiated in the house. It can be used in reflectors, plastic nets, woven fabrics, non-woven fabrics, bags for bagging fruits, etc., as well as in prepaid cards, traffic signs, decoration, and display fields. You.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un dérivé de la cyanopyrazine convenant particulièrement à une utilisation comme matière d'extrusion, ce dérivé étant représenté par la formule générale (I), où R?1, R2, R3 et R4¿ sont chacun indépendamment un groupe hydrocarbure bivalent éventuellement substitué qui peut porter une liaison éther, ester ou amide, et où X?1, X2, X3 et X4¿ sont chacun hydrogène, acryloxy ou méthacryloxy, l'un au moins des X?1, X2, X3 et X4¿ devant obligatoirement être acryloxy ou méthacryloxy. Les articles moulés ainsi fabriqués présentent une bonne stabilité à la lumière et supportent une utilisation prolongée en plein air.
PCT/JP1996/000663 1994-09-19 1996-03-15 Derives de cyanopyrazine, polymeres, procede de production et articles moules Ceased WO1997034877A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP7263470A JPH08143553A (ja) 1994-09-19 1995-09-18 シアノピラジン誘導体、重合体、製法及び成形体
PCT/JP1996/000663 WO1997034877A1 (fr) 1995-09-18 1996-03-15 Derives de cyanopyrazine, polymeres, procede de production et articles moules

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP7263470A JPH08143553A (ja) 1994-09-19 1995-09-18 シアノピラジン誘導体、重合体、製法及び成形体
PCT/JP1996/000663 WO1997034877A1 (fr) 1995-09-18 1996-03-15 Derives de cyanopyrazine, polymeres, procede de production et articles moules

Publications (1)

Publication Number Publication Date
WO1997034877A1 true WO1997034877A1 (fr) 1997-09-25

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PCT/JP1996/000663 Ceased WO1997034877A1 (fr) 1994-09-19 1996-03-15 Derives de cyanopyrazine, polymeres, procede de production et articles moules

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07149736A (ja) * 1993-10-07 1995-06-13 Nippon Soda Co Ltd シアノピラジン誘導体および成形体

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07149736A (ja) * 1993-10-07 1995-06-13 Nippon Soda Co Ltd シアノピラジン誘導体および成形体

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