WO2008047812A1 - Procédé de fabrication d'un monomère hydrophile - Google Patents

Procédé de fabrication d'un monomère hydrophile Download PDF

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Publication number
WO2008047812A1
WO2008047812A1 PCT/JP2007/070206 JP2007070206W WO2008047812A1 WO 2008047812 A1 WO2008047812 A1 WO 2008047812A1 JP 2007070206 W JP2007070206 W JP 2007070206W WO 2008047812 A1 WO2008047812 A1 WO 2008047812A1
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Prior art keywords
compound
formula
group
production method
hydrophilic monomer
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Application number
PCT/JP2007/070206
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English (en)
Japanese (ja)
Inventor
Hiroshige Ishino
Original Assignee
Kuraray Medical Inc.
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
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Priority to JP2008539835A priority Critical patent/JPWO2008047812A1/ja
Publication of WO2008047812A1 publication Critical patent/WO2008047812A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides

Definitions

  • the present invention relates to a method for producing a hydrophilic monomer having a polymerization-reactive acyloxy group such as a (meth) atalylooxy group at the end of an alkyl chain and a hydroxyl group in a side chain of the alkyl chain.
  • a polymerization-reactive acyloxy group such as a (meth) atalylooxy group at the end of an alkyl chain and a hydroxyl group in a side chain of the alkyl chain.
  • the alkyl chain has a polymerization-reactive acyloxy group such as a (meth) atalylooxy group at the end of the alkyl chain, and a hydroxyl group in the side chain of the alkyl chain.
  • Hydrophilic monomers hereinafter such compounds are referred to as crosslinkable hydroxyl group-containing (meth) acrylate-like compounds), in particular erythritol dimetatalylate (EDMA), xylitol dimethacrylate (XDMA) and sorbitol.
  • Dimetatalylate (SDMA) has become useful in applications such as ink materials, coating materials, gel materials, adhesive materials, especially dental adhesives.
  • R represents a hydrogen atom or an aliphatic saturated hydrocarbon group
  • p is an integer of 1 or more
  • Examples of a method for producing a crosslinkable hydroxyl group-containing (meth) acrylate-like compound include, for example, a patent document (Japanese Patent Laid-Open No. 49 110622 corresponding to US Pat. No. 3,950,399) and a non-patent document.
  • the method described in the literature International Journal of Polymeric Materials, 1997, 37, 1-14
  • 1, 2-3, 4-diepoxy Tan and methacrylic acid are reacted.
  • this method uses 1,2-3,4-diepoxybutane, which is extremely toxic, there are problems in its industrial implementation.
  • the present invention provides a method capable of producing a bridging hydroxyl group-containing (meth) acrylate-like compound easily and inexpensively using a highly safe raw material. Is Mejiro-an.
  • the present invention relates to the formula (1)
  • n an integer of 1 or more.
  • R 1 represents a hydrogen atom or an aliphatic hydrocarbon group having from 10 to 10 carbon atoms
  • X represents a halogen atom, or a formula (3)
  • R 1 has the same meaning as described above.
  • the arrangement order of the unit having a hydroxyl group and the unit having k ester groups is arbitrary.
  • hydrophilic monomer (4) (Hereinafter also referred to as hydrophilic monomer (4)). ⁇ Manufacturing method.
  • n is an integer of 2 to 4! /.
  • k is preferably 0.
  • R 1 is preferably a hydrogen atom or a methyl group.
  • X is preferably a chlorine atom or an aromatic atom.
  • reaction temperature is preferably -30 ° C to 120 ° C.
  • the production method of the present invention preferably further includes a step of treating the reaction mixture of the compound (1) and the compound (2) with a hydrocarbon compound.
  • the hydrocarbon compound preferably has 5 to 18 carbon atoms.
  • the hydrocarbon compound is at least one selected from the group consisting of pentane, hexane, heptane, octane, cyclopentane, cyclohexylene, toluene, xylene and mesitylene. More preferred.
  • a crosslinkable hydroxyl group-containing (meth) acrylate-like compound can be produced inexpensively and easily using a highly safe raw material.
  • compound (1) and compound (2) are used as starting materials.
  • n is an integer of 1 or more, the availability of raw materials, and the hydrophilic monomer (4) ink material and coating that are the final product of the production method of the present invention From the viewpoint of utility in applications such as materials, gel materials, adhesive materials, and particularly dental adhesives, an integer of 2 to 4 is preferable.
  • Compound (1) may be a mixture of two or more compounds in which n is different within the above definition.
  • Compound (1) can be produced according to a known method. Some are available as a commercial product, and in that case, a commercial product may be used.
  • R 1 is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 10 carbon atoms.
  • the aliphatic hydrocarbon group having from 10 to 10 carbon atoms include an alkyl group having 1 to 10 carbon atoms, an alkyl group having 2 to 10 carbon atoms, an alkenyl group having 10 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and the like.
  • Examples of the alkyl group of carbon number;! To 10 may be linear, branched or cyclic.
  • Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, and butyl group.
  • alkenyl group having 2 to 10 carbon atoms which may be linear, branched or cyclic, include, but are not limited to, butyl, allyl, butur, hexenyl, otatur, and decenyl. Groups and the like.
  • alkynyl group having 2 to 10 carbon atoms which may be linear, branched or cyclic, include an ethur group, a propynyl group, a butur group, a hexul group, an otatur group, a decynyl group, etc. Can be mentioned.
  • R 1 is preferably a hydrogen atom or a methyl group from the viewpoint of radical polymerization reactivity of the final product.
  • Compound (2) may be a mixture of two or more compounds wherein R 1 is different within the above definition! /.
  • X is a halogen atom or a group represented by the formula (3). Therefore Compound (2) is an acid halide compound or an acid anhydride. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. X is preferably a chlorine atom or a bromine atom from the viewpoint of reactivity and easy availability of raw materials.
  • Compound (2) can be produced according to a known method. Some are available as commercial products, and in that case, commercial products may be used.
  • the production method of the present invention includes a step of reacting compound (1) with compound (2) (reaction step).
  • the reaction step can be performed, for example, by mixing the compound (1) with the compound (2) in the presence of a solvent and a basic compound.
  • compound (2) may be added to compound (1), and compound (1) may be added to compound (2)! /.
  • the addition of compound (2) to compound (1) may be performed stepwise.
  • the amount of compound (2) to be used is preferably 1 ⁇ 5 to k + 3 mol, more preferably 1.8 to k + 2.5 mol, relative to 1 mol of compound (1) (k is And is synonymous with k in the hydrophilic monomer (4), the same shall apply hereinafter).
  • k is And is synonymous with k in the hydrophilic monomer (4), the same shall apply hereinafter.
  • the amount of the compound (2) used is less than 1.5 mol, the yield of the hydrophilic monomer (4) tends to decrease, and when it exceeds k + 3 mol, the side chain hydroxyl group of the compound (1) There is a possibility that a large amount of by-products that are all reacted with the compound (2) may be produced.
  • Solvents include N, N dimethylformamide (DMF), N, N dimethylacetamide, N methylpyrrolidone, acetonitrile, propionitryl, pyridine, 4-dimethylaminopyridine, quinoline, triethylamine, trimethylamine Nitrogen-containing compounds such as dimethylsulfoxide, sulfolane and other sulfur-containing compounds, jetyl ether, diisopropyl etherenole, di-butinoreethenole, tert-butinoremethinoleetenore, tetrahydrofuran, 1,4 di-dioxane, Ethers such as anisole, ethylene glycol dimethyl ether, diethylene glycol retino chinenoate ethere, triethyleneglycolino methino ree tenole, tetraethylene glycol dimethyl ether, dichloromethane, 1,2-dichloroethane, black Halogenated
  • solvents may be used alone or in admixture of two or more.
  • the amount of the solvent used is preferably ⁇ 10 to 100000 parts by weight, more preferably ⁇ 100 to 10,000 parts by weight, with respect to 100 parts by weight of the compound (1).
  • the basic compounds include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, diisopropylethylamine, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 4-dimethylamino.
  • DBU Undecene 1-7
  • lithium carbonate sodium carbonate, potassium carbonate, sodium hydrogen carbonate sodium hydroxide, potassium hydroxide, lithium hydroxide, tetramethylammonium hydroxide, tetraptylammonium hydroxide, etc.
  • triethylamine, pyridine, 4-dimethylamine Pyridine are preferred.
  • the amount of the basic compound used is preferably 1 ⁇ 5 to k + 10 mol, more preferably 2 to k + 5 mol, relative to 1 mol of the compound (1).
  • These basic compounds may be used alone or in admixture of two or more. Further, these basic compounds may be used as a solvent.
  • a small amount of a polymerization inhibitor may be added.
  • polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether (MEH Q), 2, 4 dimethyl-6 tert butyl hydroquinone, phenol, teconole, phenols such as tert-butylcatechol, phenothiazine, p-phenylenediamine, Amines such as diphenylamine, copper complexes such as copper dimethyldithiocarbamate, copper jetyldithiocarbamate, copper dibutyldithiocarbamate, inorganic copper compounds such as copper sulfate, copper oxide, copper chloride These may be used alone or in admixture of two or more.
  • the reaction temperature is -30 to 120 ° C force S, preferably -20 to 90 ° C. If the reaction temperature is within this range, the compound (2) has a particularly high rate of selective reaction with the terminal hydroxyl group out of the side chain and terminal hydroxyl groups of the compound (1). A polymerization reaction Is also suppressed.
  • the reaction time may be appropriately determined based on the concentrations of the compounds (1) and (2), the reaction temperature, etc., but 0.;! To 120 hours is preferred 0.5 to 48 hours Is preferred.
  • the hydrophilic monomer (4) can be isolated from the reaction mixture according to a conventional method (for example, concentration, column chromatography, etc.).
  • the reaction mixture obtained in the above reaction step is a compound represented by the following formula (5) in which the side chain of the alkyl chain is not esterified (hereinafter also referred to as hydrophilic monomer (5)).
  • hydrophilic monomer (5) a compound represented by the following formula (6) in which the side chain of the alkyl chain is esterified ⁇ hereinafter also referred to as compound (6).
  • the compound (1) and the compound (2 The step of treating the mixture with a hydrocarbon compound (purification step) may be performed.
  • the compound (6) Since the side chain hydroxyl group is also esterified, the compound (6) has higher lipophilicity than the hydrophilic monomer (5). Therefore, for hydrocarbon compounds, the compound () is overwhelmingly more soluble than the hydrophilic monomer (5), so that the treatment allows the hydrophilic monomer (5) and The force S removes the compound 1 ⁇ 2) from the mixture of the compound 1 ⁇ 2) by dissolving it in the hydrocarbon compound.
  • the hydrocarbon compound is liquid at the treatment temperature. Therefore, the number of carbon atoms of the hydrocarbon compound is 5 to 18;
  • the hydrocarbon compound either aliphatic or aromatic can be used, and it may be a saturated compound or an unsaturated compound.
  • hydrocarbon compound examples include aliphatic saturated hydrocarbon compounds such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptazane, Octadecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like.
  • aliphatic unsaturated hydrocarbon compound examples include hexene, otaten, decene, and cyclohexagen.
  • aromatic hydrocarbon compound examples include benzene, toluene, xylene, mesitylene and the like.
  • pentane, hexane, heptane, octane, cyclopentane, cyclohexane, low boiling point and easy removal from the hydrophilic monomer (5) are easy.
  • Toluene, xylene and mesitylene are preferred.
  • These hydrocarbon compounds can be used alone or in admixture of two or more.
  • Treating the mixture with a hydrocarbon compound refers to bringing the mixture into contact with the hydrocarbon compound so that the compound (6) is dissolved in the hydrocarbon compound.
  • a hydrocarbon compound may be added to a mixture of the hydrophilic monomer (5) and the compound (6) and mixed and stirred, but water and hydrocarbons may be added to the mixture.
  • a method of adding a compound and performing a liquid separation treatment may be simple.
  • the amount of the hydrocarbon compound used is preferably 10 to 100000 parts by weight with respect to 100 parts by weight of the mixture of the hydrophilic monomer (5) and the compound (6). It is more preferably 50 to 10,000 parts by weight.
  • the treatment is preferably performed at 30 to 120 ° C, more preferably at 10 to 90 ° C.
  • the hydrophilic monomer (5) can be recovered according to a conventional method. For example, when water and a hydrocarbon compound are added to the above mixture for liquid separation treatment, the aqueous layer is separated from a hydrophobic solvent in which the hydrophilic monomer (5) is soluble (eg, ethyl acetate, diethyl acetate).
  • the hydrophilic monomer (5) can be recovered by treating with isopropyl ether or the like and concentrating the hydrophobic solvent in which the hydrophilic monomer (5) is dissolved.
  • the recovered hydrophilic monomer (5) can be further purified by recrystallization or the like.
  • the production method of the present invention uses a highly safe raw material, and is an inexpensive and easy method and contains a crosslinkable hydroxyl group-containing (meth) acrylate with EDMA, XDMA, SDMA, etc.
  • EDMA ethylene glycol
  • XDMA XDMA
  • SDMA Secure Digital Multimedia Subsystem
  • the purity of the hydrophilic monomer (5) can be improved by treating the reaction mixture with a hydrocarbon compound, which enables purification by recrystallization. It is. This facilitates industrial production of high-purity hydrophilic monomer (5).
  • the method of removing the compound (6) by treating the hydrophilic monomer (5) containing the compound (6) with a hydrocarbon compound, which is performed in the above purification step, is hydrophilic. Since the compound (6) can be easily and efficiently separated from the monomer (5), it is useful as a method for purifying the hydrophilic monomer (5).
  • a hydrophilic step including a step of obtaining a mixture of the hydrophilic monomer (5) and the compound (6) and a step of treating the mixture with a hydrocarbon compound.
  • Monomer (5) This production method is also an inexpensive and easy method using a highly safe raw material and is useful.
  • the step of obtaining a mixture of the hydrophilic monomer (5) and the compound (6) is not limited to the reaction step described above, but in the above formula (2), X is an OR 2 group (R 2 is a carbon number of 1 to A step of reacting the ester compound (20 hydrocarbon group) with the compound (1) may be performed.
  • Example 2 The same reaction step as in Example 1 was performed, and in the purification step of Example 1, hexane was substituted. A similar operation was carried out except that cyclohexane was used. 64.0 g (0.248 mol, yield 60%) of erythritol dimethacrylate was obtained as white crystals.
  • Example 3 The same reaction step as in Example 3 was performed, and the same operation was performed in the purification step of Example 3 except that cyclohexane was used instead of hexane. 58.7 g (0.227 mol, yield 55%) of erythritol dimethacrylate was obtained as white crystals.
  • the present invention is useful as a method for producing a crosslinkable hydroxyl group-containing (meth) acrylate-like compound mainly used for ink materials, coating materials, gel materials, adhesive materials, particularly dental adhesives, and the like. Also suitable for industrial production.

Abstract

L'invention concerne un procédé de production simple d'un composé de type (méth)acrylate contenant un groupement hydroxyle réticulable à faible coût en utilisant une matière première très sûre. L'invention concerne spécifiquement un procédé de fabrication d'un monomère hydrophile représenté par la formule (4) ci-dessous, comprenant une étape consistant faire réagir un composé représenté par la formule (1) ci-dessous avec un composé représenté par la formule (2) ci-dessous. (Dans les formules, les symboles sont tels que définis dans la description.)
PCT/JP2007/070206 2006-10-20 2007-10-16 Procédé de fabrication d'un monomère hydrophile WO2008047812A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008539835A JPWO2008047812A1 (ja) 2006-10-20 2007-10-16 親水性単量体の製造方法

Applications Claiming Priority (4)

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JP2006-286906 2006-10-20
JP2006-286908 2006-10-20
JP2006286906 2006-10-20
JP2006286908 2006-10-20

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WO2008047812A1 true WO2008047812A1 (fr) 2008-04-24

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009263286A (ja) * 2008-04-25 2009-11-12 Kuraray Medical Inc 重合性単量体、重合性組成物及び歯科用材料
JP2013177517A (ja) * 2012-02-29 2013-09-09 Toyo Ink Sc Holdings Co Ltd 重合性組成物、およびそれを用いた活性エネルギー線硬化型インクジェットインキ
US8557893B2 (en) 2010-09-15 2013-10-15 3M Innovative Properties Company Substituted saccharide compounds and dental compositions

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49110622A (fr) * 1973-02-23 1974-10-22
JPH054942A (ja) * 1991-02-26 1993-01-14 Mitsui Petrochem Ind Ltd アクリレート化合物および歯科用接着剤
JPH1072404A (ja) * 1996-08-28 1998-03-17 Dainippon Ink & Chem Inc ソルビトールの（メタ）アクリル酸エステル及びその製法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49110622A (fr) * 1973-02-23 1974-10-22
JPH054942A (ja) * 1991-02-26 1993-01-14 Mitsui Petrochem Ind Ltd アクリレート化合物および歯科用接着剤
JPH1072404A (ja) * 1996-08-28 1998-03-17 Dainippon Ink & Chem Inc ソルビトールの（メタ）アクリル酸エステル及びその製法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009263286A (ja) * 2008-04-25 2009-11-12 Kuraray Medical Inc 重合性単量体、重合性組成物及び歯科用材料
US8557893B2 (en) 2010-09-15 2013-10-15 3M Innovative Properties Company Substituted saccharide compounds and dental compositions
JP2013177517A (ja) * 2012-02-29 2013-09-09 Toyo Ink Sc Holdings Co Ltd 重合性組成物、およびそれを用いた活性エネルギー線硬化型インクジェットインキ

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