WO2016165979A1 - Dihydro-oligo-cyclopentadiényl(méth)acrylates - Google Patents

Dihydro-oligo-cyclopentadiényl(méth)acrylates Download PDF

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Publication number
WO2016165979A1
WO2016165979A1 PCT/EP2016/057420 EP2016057420W WO2016165979A1 WO 2016165979 A1 WO2016165979 A1 WO 2016165979A1 EP 2016057420 W EP2016057420 W EP 2016057420W WO 2016165979 A1 WO2016165979 A1 WO 2016165979A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
acrylates
dihydrooligocyclopentadienyl
general formula
Prior art date
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PCT/EP2016/057420
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German (de)
English (en)
Inventor
Andrea Misske
Friederike Fleischhaker
Christoph Fleckenstein
Martin KALLER
Ulrik Stengel
Mathieu BLANCHOT
Marek Pazicky
Ritesh Nair
Original Assignee
Basf Se
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.)
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Publication of WO2016165979A1 publication Critical patent/WO2016165979A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0037—Production of three-dimensional images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/90—Ring systems containing bridged rings containing more than four rings
    • C07C2603/91—Polycyclopentadienes; Hydrogenated polycyclopentadienes

Definitions

  • the present invention relates Dihydrooligocyclopentadienyl (meth) acrylates having 3 to 7 derived from cyclopentadiene units, their preparation and copolymers containing them and their use.
  • Dihydrodicyclopentadienyl (meth) acrylate, in the form of its copolymers, is used as UV crosslinker in radiation-curable coatings.
  • WO 97/25385 discloses radiation-curable lacquers to be processed from melt, solution or dispersion comprising as binders copolymers of a) (meth) acrylic acid or (meth) acrylates and / or (meth) acrylamides, b) dihydrodicyclopentadienyl (meth) acrylate and optionally c) further copolymerizable ethylenically unsaturated monomers.
  • Dihydrodicyclopentadienyl (meth) acrylate is suitable as a monomer for UV crosslinking of copolymers containing this monomer, in particular because it has two differently reactive double bonds. In addition, it has a very high glass transition temperature. However, it has a very intense and unpleasant odor.
  • the object of the invention is to provide an alternative monomer to Dihydrodicyclopentadienyl (meth) acrylate, which has its advantageous properties, but is not so odorous.
  • the monomer should be liquid at room temperature and have a low viscosity of preferably ⁇ 50 mPas at 70 ° C, to be useful also in ink formulations for 3D printing (e.g., by photopolymer jetting).
  • dihydrocyclopentadienyl (meth) acrylate has been used as described in US 2010/0201019, US 2008/0286450, US 2012/0282439 and US 201 1/0104500.
  • n 1, 2, 3, 4 or 5.
  • the present invention also provides mixtures of dihydrocyclopentadienyl (meth) acrylates of the general formula (I).
  • the dihydrooligocyclopentadienyl (meth) acrylates can be prepared from the corresponding oligocyclopentadienes and (meth) acrylic acid by adding the acid to a double bond of the oligocyclopentadienes in the presence of boron trifluoride or a strong acid as catalyst and a polymerization inhibitor.
  • the invention also provides a process for preparing dihydrooligocyclopentadienyl (meth) acrylates of the general formula (I) in which oligocyclopentadienes of the general formula (II)
  • the reaction of the oligocyclopentadiene can be carried out in a solvent or solvent-free.
  • Suitable solvents are aromatic solvents, e.g. Toluene, xylene, aliphatic solvents, e.g. n-heptane, cydohexane, tert-butylcyclohexane, chlorinated hydrocarbons such as chlorobenzene, dichlorobenzene, dichloromethane or ethers such as e.g. Diethyl ether, tert-butyl methyl ether, tetrahydrofuran or mixtures thereof.
  • (meth) acrylic acid is preferably used in stoichiometric excess.
  • the molar ratio of acid to oligocyclopentadiene is preferably from 10: 1 to 1: 1, more preferably from 3: 1 to 1.1: 1.
  • the catalyst boron trifluoride is generally present in amounts of 0.1 to 5 wt .-%, preferably from 0.1 to 1 wt .-% in the reaction mixture.
  • Boron trifluoride is used as adduct. It is possible to use complexes such as e.g. BF3-methanol, BF3-ethanol, BF3-propanol, BF3-n-butanol, BF3-dihydrate, BF3-diethyl etherate, BF3-dimethyl etherate, BF3-tetrahydrofuran, BF3-tert-butylmethyl etherate or mixtures thereof.
  • Boron trifluoride is preferably used as boron trifluoride dimethyl etherate and / or boron trifluoride diethyl etherate.
  • acids having a pKA ⁇ 1 can be used, for example sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid.
  • Suitable polymerization inhibitors are for example N-oxides (nitroxyl or N-oxyl radicals, ie compounds which have at least one NO group), such as. 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetoxy-2,2,6,6- tetramethylpiperidine-N-oxyl, 2,2,6,6-tetramethylpiperidine-N-oxyl, bis (1-oxyl-2,6,6-tetramethylpiperidines-4-yl) sebacate, 4,4 ', 4 Tris (2,2,6,6-tetramethylpiperidine-N-oxyl) phosphite or 3-oxo-2,2,5,5-tetramethylpyrrolidine-N-oxyl; mono- or polyhydric phenols which may be have one or more alkyl groups, such as, for example, alkylphenols, for example o-, m-
  • hydroquinone hydroquinone monomethyl ether, phenothiazine, 4-hydroxy-2, 2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, 2-tert-butylphenol , 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, 2,6-di tert-butyl-4-methylphenol and 2-methyl-4-tert-butylphenol.
  • oxygen can additionally be used as the polymerization inhibitor.
  • an oxygen-containing gas preferably air or a mixture of air and nitrogen (lean air) may be present.
  • the reaction is generally carried out at temperatures of 40 to 1 10 ° C.
  • the reaction time is generally 0.5 to 10, preferably 1 to 5 hours.
  • the reaction may optionally be diluted with an organic solvent.
  • Suitable solvents are aromatic solvents, e.g. Toluene, xylene, aliphatic solvents, e.g. n-heptane, cyclohexane, methylcyclohexane, chlorinated solvents such as chlorobenzene, dichlorobenzene, dichloromethane or ethers such as e.g. Diethyl ether, tert-butyl methyl ether, tetrahydrofuran or mixtures thereof.
  • the reaction mixture which still contains catalyst and excess (meth) acrylic acid, in a washing apparatus with a 5 to 25 wt .-%, preferably 5 to 20 wt .-%, more preferably 5 to 15 wt .-% aqueous Solution of a base, such as. B. sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, calcium hydroxide, ammonia water or potassium carbonate, optionally 5 to 15 wt .-% sodium chloride, potassium chloride, ammonium chloride or ammonium sulfate may be added, preferably with sodium bicarbonate solution, sodium hydroxide or sodium hydroxide. Saline solution neutralized.
  • a base such as. B.
  • the addition of the base takes place in such a way that the temperature in the apparatus does not rise above 35 ° C, preferably between 20 and 35 ° C and the pH is 8 to 14.
  • the heat of neutralization is optionally removed by cooling the container by means of internal cooling coils or by double-wall cooling.
  • the quantitative ratio of reaction mixture: neutralizing liquid is generally 1: 0.1 to 1, preferably 1: 0.2 to 0.8, particularly preferably 1: 0.3 to 0.7.
  • the laundry can be carried out, for example, in a stirred tank or in another conventional apparatus, for example in a column or mixer-settler apparatus.
  • reaction mixture is treated with water or a 5 to 30% strength by weight, preferably 5 to 20% strength by weight, particularly preferably 5 to 15% strength by weight saline solution.
  • the quantitative ratio of reaction mixture: washing liquid is generally 1: 0.1 to 1, preferably 1: 0.2 to 0.8, particularly preferably 1: 0.3 to 0.7.
  • the solvent can be separated by distillation.
  • the washed reaction mixture can first be admixed with an amount of storage stabilizer, preferably hydroquinone monomethyl ether, such that after removal of the solvent 100 to 500 ppm, preferably 200 to 500 ppm and particularly preferably 200 to 400 ppm thereof are contained in the target ester.
  • the distillative removal of the main amount of solvent is carried out, for example, in a stirred tank with double wall heating and / or heating coils under reduced pressure, for example at 20 to 700 mbar, preferably 30 to 500 mbar and more preferably 50 to 150 mbar and a temperature of 40 to 80 ° C.
  • the distillation can also take place in a falling film or thin film evaporator.
  • the reaction mixture preferably several times in the circulation, under reduced pressure, for example at 20 to 700 mbar, preferably 30 to 500 mbar, more preferably 50 to 150 mbar and a temperature of 40 to 80 ° C passed through the apparatus.
  • an oxygen-containing gas preferably air or a mixture of air and nitrogen (lean air) are introduced into the distillation apparatus, for example 0.1 to 1 m 3 / m 3 h, preferably 0.2 to 0.8 m 3 / m 3 h and particularly preferably 0.3 to 0.7 m 3 / m 3 h, based on the volume of the reaction mixture.
  • the residual solvent content in the residue after distillation is generally below 5% by weight, preferably 0 to 2% by weight.
  • the separated solvent is condensed and preferably used again.
  • Oligocyclopentadiene mixtures are obtained in a known manner by polycycloaddition of cyclopentadiene under pressure at temperatures of 170 to 300 ° C. These mixtures can be worked up by distillation. Processes for the preparation of oligocyclopentadienes are also described in US 3,701,812 and US 5,446,222.
  • Copolymers which comprise the dihydrooligocyclopentadienyl (meth) acrylates of the general formula (I) according to the invention in copolymerized form can be used as UV-crosslinking binders in curable compositions, for example radiation-curable coatings or in inks for 3D printing (for example photopolymer jetting).
  • curable compositions for example radiation-curable coatings or in inks for 3D printing (for example photopolymer jetting.
  • dihydrocyclopentadienyl (meth) acrylates which smell intensely and unpleasantly
  • dihydrooligocyclopentadiene enyl (meth) acrylates have the advantage that they are odorless or smell much less intense and unpleasant.
  • Subject of the invention are also
  • R 1 H or CH 3 or C 2 H 5 and
  • Suitable further monomers b1) of the general formula (III) are, for example, the esters of acrylic acid and methacrylic acid with aliphatic, cycloaliphatic, araliphatic and aromatic alcohols having 1 to 30, preferably 1 to 20, carbon atoms, for example methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl
  • Suitable compounds of the general formula (IV) are, for example, (meth) acrylamides, such as acrylic acid, methacrylic acid, 3-phenylacrylic acid, hydroxyalkyl (meth) acrylates, such as ethyl glycol mono (meth) acrylate, butylglycol mono (meth) acrylate, hexanediol mono (meth) acrylate , Ether (meth) acrylates such as methoxyethyl glycol monomethacrylate, ethyloxyethyl glycol mono (meth) acrylate, butyloxyethylglycol mono (meth) acrylate, phenyloxyethyl glycol mono (meth) acrylate, glycidyl acrylate, glycidyl methacrylate, and amino (meth) acrylates such as 2-aminoethyl (meth) acrylate.
  • (meth) acrylamides such
  • the copolymers contain as monomers b1) acrylic or methacrylic acid (cyclo) alkyl esters having 1 to 10 carbon atoms in the alkyl radical or mixtures thereof with glycidyl (meth) acrylate and / or methacrylic acid.
  • the copolymers according to the invention contain, as further monomers b1), a compound selected from the group consisting of isobornyl acrylate, isobornyl methacrylate, isobornyl methacrylate, isobornyl cinnamate, adamanthaneacrylate, adamanthan methacrylate, adamanthanethacrylate and adamanthanemoninnamate.
  • other copolymerizable monomers B may also be styrene, 4-tert-butylstyrene and / or 1-methylstyrene as further monomers b2).
  • other monomers B besides b1) and optionally b2) may also be copolymerized copolymerizable, ethylenically unsaturated compounds b3) which are capable of hydrogen abstraction in the triplet-excited state.
  • Such compounds b3) are preferably derived from an aromatic or partially aromatic ketone, preferably from benzophenone and its derivatives, or have thioxanthone structures.
  • Such monomers b3) are disclosed, for example, in WO 97/25385, structures (III) to (XLIII).
  • the dihydrooligocyclopentadienyl (meth) acrylates are generally contained in the copolymers according to the invention in amounts of from 2 to 90% by weight, preferably from 10 to 60% by weight, based on the total amount of the monomers.
  • the present invention also relates to the use of the copolymers of dihydrooligocyclopentadienyl (meth) acrylates of the general formula (I) and other ethylenically unsaturated monomers which can be copolymerized with these as binders in curable compositions, such as, for example, radiation-curable varnishes or in inks for 3D printing (for example, photopolymer jetting).
  • curable compositions such as, for example, radiation-curable varnishes or in inks for 3D printing (for example, photopolymer jetting).
  • oligocyclopentadiene oligomer mixture with a determined via H-NMR quotient of CH-unsaturated: CH saturated of 0.18: calculated according to a mixture of tetra and Pentacyclopentadiene
  • 284 mg of boron trifluoride diethyl etherate are added.
  • the reaction mixture is heated to 90 ° C. After 2 h is cooled and 100 mL of methylene chloride and 50 mL of 8% NaHCOs solution are added.
  • the product dihydrotriccyclopentadienyl acrylate is obtained quantitatively in a purity of> 90% (H-NMR). It contains 130 ppm MeHQ (HPLC).
  • the dynamic viscosity is 402 mPa * s at 25 ° C and 24 mPa * s at 70 ° C.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des dihydro-oligo-cyclopentadiényl(méth)acrylates de formule générale (I) dans laquelle R représente H ou CH3; n vaut 1, 2, 3, 4 ou 5.
PCT/EP2016/057420 2015-04-15 2016-04-05 Dihydro-oligo-cyclopentadiényl(méth)acrylates WO2016165979A1 (fr)

Applications Claiming Priority (2)

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US201562147625P 2015-04-15 2015-04-15
US62/147,625 2015-04-15

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11028040B2 (en) 2017-01-27 2021-06-08 Basf Se Methods for producing (meth)acrylic acid norbornyl esters
CN114746392A (zh) * 2019-12-02 2022-07-12 引能仕株式会社 脂环式丙烯酸酯化合物、脂环式环氧丙烯酸酯化合物、固化性组合物和固化物

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3701812A (en) 1970-10-05 1972-10-31 Monsanto Co Process for preparation of tricyclopentadiene
DE4136660A1 (de) 1991-11-07 1993-05-13 Basf Ag Verfahren zur herstellung von estern aus dicyclopentadien und 1 bis 5 c-atome aufweisenden organischen carbonsaeuren
US5446222A (en) 1994-06-17 1995-08-29 Mobil Oil Corporation Oligomers of cyclopentadiene and process for making them
WO1997025385A1 (fr) 1996-01-04 1997-07-17 Basf Aktiengesellschaft Peintures durcissant aux rayonnements
US20080286450A1 (en) 2005-02-02 2008-11-20 Dsm Ip Assets B.V. Method and composition for reducing waste in photo-imaging applications
JP2009075553A (ja) * 2007-08-03 2009-04-09 Fujifilm Corp スペーサ及びその製造方法、液晶表示装置用基板、液晶表示装置
JP2009175647A (ja) * 2008-01-28 2009-08-06 Fujifilm Corp 感光性樹脂組成物、フォトスペーサー及びその形成方法、保護膜、着色パターン、表示装置用基板、並びに表示装置
EP2230284A1 (fr) * 2009-03-17 2010-09-22 Fujifilm Corporation Tintenzusammensetzung und Tintenaufzeichnungsverfahren
US20110104500A1 (en) 2009-03-13 2011-05-05 John Southwell Radiation curable resin composition and rapid three-dimensional imaging process using the same
US20120282439A1 (en) 2006-05-01 2012-11-08 Dsm Ip Assets B.V. Radiation curable resin composition and rapid three dimensional imaging process using the same

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3701812A (en) 1970-10-05 1972-10-31 Monsanto Co Process for preparation of tricyclopentadiene
DE4136660A1 (de) 1991-11-07 1993-05-13 Basf Ag Verfahren zur herstellung von estern aus dicyclopentadien und 1 bis 5 c-atome aufweisenden organischen carbonsaeuren
US5446222A (en) 1994-06-17 1995-08-29 Mobil Oil Corporation Oligomers of cyclopentadiene and process for making them
WO1997025385A1 (fr) 1996-01-04 1997-07-17 Basf Aktiengesellschaft Peintures durcissant aux rayonnements
US20080286450A1 (en) 2005-02-02 2008-11-20 Dsm Ip Assets B.V. Method and composition for reducing waste in photo-imaging applications
US20100201019A1 (en) 2005-02-02 2010-08-12 Dsm Ip Assets B.V. Method and composition for reducing waste in photo-imaging applications
US20120282439A1 (en) 2006-05-01 2012-11-08 Dsm Ip Assets B.V. Radiation curable resin composition and rapid three dimensional imaging process using the same
JP2009075553A (ja) * 2007-08-03 2009-04-09 Fujifilm Corp スペーサ及びその製造方法、液晶表示装置用基板、液晶表示装置
JP2009175647A (ja) * 2008-01-28 2009-08-06 Fujifilm Corp 感光性樹脂組成物、フォトスペーサー及びその形成方法、保護膜、着色パターン、表示装置用基板、並びに表示装置
US20110104500A1 (en) 2009-03-13 2011-05-05 John Southwell Radiation curable resin composition and rapid three-dimensional imaging process using the same
EP2230284A1 (fr) * 2009-03-17 2010-09-22 Fujifilm Corporation Tintenzusammensetzung und Tintenaufzeichnungsverfahren

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Title
"Ull-mann's Encyclopedia of Industrial Chemistry", 2013
M. K. MAMEDOV ET AL: "Synthesis of bi- and tricyclic acrylates in the presence of boron trifluoride etherate", RUSSIAN JOURNAL OF ORGANIC CHEMISTRY., vol. 46, no. 5, 1 May 2010 (2010-05-01), US, pages 628 - 630, XP055277455, ISSN: 1070-4280, DOI: 10.1134/S1070428010050039 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11028040B2 (en) 2017-01-27 2021-06-08 Basf Se Methods for producing (meth)acrylic acid norbornyl esters
CN114746392A (zh) * 2019-12-02 2022-07-12 引能仕株式会社 脂环式丙烯酸酯化合物、脂环式环氧丙烯酸酯化合物、固化性组合物和固化物

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