WO2013020469A1 - Composé ester bis-phosphonyl phosphonate - Google Patents

Composé ester bis-phosphonyl phosphonate Download PDF

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Publication number
WO2013020469A1
WO2013020469A1 PCT/CN2012/079445 CN2012079445W WO2013020469A1 WO 2013020469 A1 WO2013020469 A1 WO 2013020469A1 CN 2012079445 W CN2012079445 W CN 2012079445W WO 2013020469 A1 WO2013020469 A1 WO 2013020469A1
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WIPO (PCT)
Prior art keywords
compound
meth
formula
reaction
ethylenically unsaturated
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Application number
PCT/CN2012/079445
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English (en)
Chinese (zh)
Inventor
陈婷
王瑜
Original Assignee
Chen Ting
Wang Yu
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
Application filed by Chen Ting, Wang Yu filed Critical Chen Ting
Publication of WO2013020469A1 publication Critical patent/WO2013020469A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/32—Esters thereof
    • C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/3247—Esters of acids containing the structure -C(=X)-P(=X)(R)(XH) or NC-P(=X)(R)(XH), (X = O, S, Se)
    • C07F9/3252—Esters of acids containing the structure -C(=X)-P(=X)(R)(XH) or NC-P(=X)(R)(XH), (X = O, S, Se) containing the structure -C(=X)-P(=X)(R)(XR), (X = O, S, Se)
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents

Definitions

  • the invention relates to the technical field of new materials for UV light radiation radical polymerization, in particular to a structural formula such as
  • phosphono-type structural compounds are important photoinitiators in the field of UV ultraviolet radiation curing due to their long-wavelength light absorption and photobleaching properties, and have been widely disclosed in the patent literature, such as US 5,218,009, EP 0 615 980 A2, and CN 1 659 175 A. New preparation processes for some phosphono-type structural compounds have also been the focus of recent research. Representative patent documents such as WO2006/056541 Al o However, the cost and price of phosphono-type photoinitiator compounds are often significantly higher than other photoinitiator compounds.
  • the disclosed preparation process inevitably uses highly air-sensitive alkali metals (sodium, potassium, or lithium metal) to undergo lengthy reaction times and operational steps to prepare corresponding
  • the metal phosphine compound the yield is low (for example, the final product obtained in the above-mentioned latest process WO2006/056541A1 often has a yield of less than 30%), and the production safety hazard is large, which severely limits the economic and environmentally friendly promotion of the compound. . Therefore, the identification of new and more economical phosphono-type structural compounds, as well as the development of its new preparation process and application, is a very valuable application challenge in the field of new UV radiation curing materials.
  • a bisphosphonophosphonate compound of the formula I is an effective ethylenically unsaturated compound system UV radical photopolymerization curing photoinitiator.
  • Compound I (as defined in the following claims) is not only a new structure not reported, but equally important they must be prepared in a new economical process that is completely different from the literature disclosure method.
  • R is a linear or branched fluorenyl group having 1 to 24 carbon atoms, and the fluorenyl group may be no more than 4 non-continuous oxygen atoms, nitrogen atoms, silicon atoms, or sulfur atoms.
  • the fluorenyl group may have 1 to 40 fluorine atoms; or R is a phenyl group having 6 to 24 carbon atoms or a substituted phenyl group having 1 to 4 substituents, and these substituents may also be no more than Four discontinuous oxygen atoms, nitrogen atoms, silicon atoms, or sulfur atoms are interrupted.
  • R methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, phenyl, tolyl.
  • the bisphosphono-type compound manufacturing method disclosed in the literature can prepare a series of structures containing a fluorenyl group (branched or linear) or an aryl group (multiple substituents) on a phosphorus atom, such as a patented technology.
  • WO2006/056541A1 and CN1659175A but their phosphorus-carbon bond formation chemical reaction characteristics determine that it is not possible to prepare phosphorus-containing structures of the formula I containing an OR group (decyloxy or aryloxy) on a phosphorus atom. Oxygen bond compound.
  • the present application has now found that compounds of formula I can be conveniently produced economically via the following reaction formula.
  • the industrially inexpensive and safe H 3 PO 2 iypophosphorous acid is the key starting material, and the intermediate hypophosphite is obtained via the R-based esterification reaction, followed by the homo-xylene formaldehyde.
  • the carbonyl nucleophilic addition reaction gives a higher intermediate.
  • the target compound I can be obtained by catalytic oxidation of B by a hydroxyl group.
  • the core feature of this process is the preparation of a hydroxyphosphonate higher intermediate of the general formula B by a bis-carbonyl nucleophilic addition reaction using a hypophosphite of the formula ⁇ and a mesitylene formaldehyde.
  • the reaction may be carried out as a pure compound, or may be carried out in an in situ mixture after completion of the hypophosphite reaction under suitable conditions.
  • Suitable esterification conditions may be the reaction of hypophosphorous acid [or its corresponding form as MOP C H2 amine salt, hydrazine preferably N3 ⁇ 4, PhNH 3 , HNEt 3 , the same below] and the decyl orthoformate, or hypophosphorous acid. (or the corresponding amine salt) and the alcohol ROH and the acid chloride to promote the reaction, or inferior race phosphorous acid (or the corresponding amine salt) with the form of SI oR;) 4 the reaction of silicone embankment.
  • R is methyl, Phosphorus, Sulfur and Silicon and the Related Elements, 177(6-7), 1793-1796; 2002; R is ethyl , Tetrahedron Letters, 42(30), 5033-5036; 2001; R is isopropyl, Chemistry Letters, 33(2), 116-117; 2004 and Medicinal Chemistry Letters, 2(1), 11-16; 2011; R is tert-butyl, Tetrahedron Letters, 37(4), 425-8; 1996; R is n-butyl, Journal of Organic Chemistry, 70(10), 4064-4072; 2005 and JOMrwa/of Organometallic Chemistry, 643-644, 154-163; 2002; R is phenyl, Journal of Organometallic Chemistry, 643-644, 154-163; 2002.
  • the condensation of the hypophosphite and the aldehyde may employ a suitable base promoter, and the preferred base is an organic tertiary amine compound such as Et 3 N, Bu 3 N, or ' Pr 2 NEt.
  • Suitable oxidation catalysts are selected from metal salts containing Mo, W or V, such as vanadium oxyacetate, molybdates, molybdates, phosphomolybdates, tungstic anhydrides, tungstates, or heteropoly containing these metals.
  • metal salts containing Mo, W or V such as vanadium oxyacetate, molybdates, molybdates, phosphomolybdates, tungstic anhydrides, tungstates, or heteropoly containing these metals.
  • Suitable terminal oxidizing agents can be organic peroxides such as t-butanol peroxide and the like.
  • Such a system comprises at least one polymerizable ethylenically unsaturated component and comprises at least one compound of formula I as one of a photoinitiator or a photoinitiator component.
  • a suitable amount of the compound of the formula I is contained in an amount of from 0.05 to 15 parts by weight, preferably from 0.5 to 8 parts by weight, per 100 parts by weight based on the total of the ethylenically unsaturated component in the system.
  • the suitable UV-curable system disclosed in the present application comprises a polymerizable ethylenically unsaturated component which is a compound or mixture which can be crosslinked by free radical polymerization of the double bond, the ethylenically unsaturated component It may be a monomer, an oligomer or a prepolymer, or a mixture or copolymer thereof.
  • Suitable free-radically polymerizable monomers are, for example, ethylenically-containing polymerizable monomers including, but not limited to, (meth) acrylates, acrolein, olefins, conjugated diolefins, styrene, maleic anhydride, fumaric anhydride, Vinyl acetate, vinylpyrrolidone, vinylimidazole, (meth)acrylic acid, (meth)acrylic acid derivatives such as (meth)acrylamide, vinyl halide, vinylidene halide, and the like.
  • ethylenically-containing polymerizable monomers including, but not limited to, (meth) acrylates, acrolein, olefins, conjugated diolefins, styrene, maleic anhydride, fumaric anhydride, Vinyl acetate, vinylpyrrolidone, vinylimidazole, (meth)acrylic acid, (meth)acryl
  • Suitable prepolymers and oligomers include, but are not limited to, (meth)acryloyl functional (meth)acrylic copolymers, urethane (meth) acrylates, polyester (meth) acrylates, Unsaturated polyester, polyether (meth) acrylate, siloxane (meth) acrylate, epoxy (meth) acrylate, etc.
  • Suitable number average molecular weights thereof may vary, for example, from 500 to 10,000, preferably from 500 to 5,000.
  • UV light curing application examples 30 parts: epoxy acrylate
  • Example photoinitiator compound 4 parts: Example photoinitiator compound.
  • the above components were sufficiently ground and sprayed on a white substrate to form a coating of about 5 ⁇ m.
  • a 200 W high-pressure mercury lamp was used as a light source to irradiate at a distance of 12 cm from the sample.
  • a finger-scratch method determines the complete cure of the coating.
  • the above-mentioned examples of the compounds 1 to 5 all caused the film layer to be completely cured, showing good photoinitiation properties.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)

Abstract

La présente invention concerne le domaine technique de nouvelles matières polymérisées par radicaux libres sous rayonnement UV, en particulier un composé ester bis-phosphonyl phosphonate tel que représenté par la formule I, un procédé de préparation de celui-ci, une utilisation de celui-ci comme photoinitiateur pour un système de composé insaturé à teneur en alcényle pour effectuer une polymérisation et un durcissement par radicaux libres sous rayonnement UV, et un système de matières de polymérisation et durcissement par radicaux libres sous rayonnement UV contenant le composé.
PCT/CN2012/079445 2011-08-09 2012-07-31 Composé ester bis-phosphonyl phosphonate WO2013020469A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN 201110227608 CN102924509A (zh) 2011-08-09 2011-08-09 双膦酰膦酸酯化合物
CN201110227608.4 2011-08-09

Publications (1)

Publication Number Publication Date
WO2013020469A1 true WO2013020469A1 (fr) 2013-02-14

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WO (1) WO2013020469A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014095724A1 (fr) * 2012-12-19 2014-06-26 Basf Se Dérivés d'acide bisacylphosphinique, leur préparation et leur utilisation en tant que photo-initiateurs
US9644068B2 (en) 2012-12-18 2017-05-09 Basf Se Semiconducting materials based on naphthalenediimide-vinylene-oligothiophene-vinylene polymers
US9796740B2 (en) 2013-07-08 2017-10-24 Basf Se Liquid bisacylphosphine oxide photoinitiator
WO2018186822A1 (fr) * 2017-04-03 2018-10-11 Hewlett-Packard Development Company, L.P. Agents photoactifs

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103333202B (zh) * 2013-06-08 2016-09-07 广东博兴新材料科技有限公司 一种基于环氧化合物的含磷酸酯基的长波吸收光引发剂及其制备方法
KR102575896B1 (ko) * 2016-01-11 2023-09-07 헨켈 아게 운트 코. 카게아아 실리콘-상용성 화합물
CN109867693B (zh) * 2019-01-08 2021-08-10 广东博兴新材料科技有限公司 一种氟碳链改性亚磷酸酯类丙烯酸酯化合物及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5534559A (en) * 1993-03-18 1996-07-09 Ciba-Geigy Corporation Daylight curing compositions containing bisacylphosphine oxide photoinitiators
CN101065388A (zh) * 2004-11-23 2007-10-31 西巴特殊化学品控股有限公司 制备酰基磷烷及其衍生物的方法
CN102471150A (zh) * 2010-06-30 2012-05-23 帝斯曼知识产权资产管理有限公司 D1492液体双酰基氧化膦光引发剂及其在可辐射固化组合物中的用途

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5534559A (en) * 1993-03-18 1996-07-09 Ciba-Geigy Corporation Daylight curing compositions containing bisacylphosphine oxide photoinitiators
CN101065388A (zh) * 2004-11-23 2007-10-31 西巴特殊化学品控股有限公司 制备酰基磷烷及其衍生物的方法
CN102471150A (zh) * 2010-06-30 2012-05-23 帝斯曼知识产权资产管理有限公司 D1492液体双酰基氧化膦光引发剂及其在可辐射固化组合物中的用途

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9644068B2 (en) 2012-12-18 2017-05-09 Basf Se Semiconducting materials based on naphthalenediimide-vinylene-oligothiophene-vinylene polymers
WO2014095724A1 (fr) * 2012-12-19 2014-06-26 Basf Se Dérivés d'acide bisacylphosphinique, leur préparation et leur utilisation en tant que photo-initiateurs
US9796740B2 (en) 2013-07-08 2017-10-24 Basf Se Liquid bisacylphosphine oxide photoinitiator
WO2018186822A1 (fr) * 2017-04-03 2018-10-11 Hewlett-Packard Development Company, L.P. Agents photoactifs
US10858380B2 (en) 2017-04-03 2020-12-08 Hewlett-Packard Development Company, L.P. Photo active agents

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