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WO2002088151A1 - Ester phosphorique polymerisable et procede de production de celui-ci - Google Patents

Ester phosphorique polymerisable et procede de production de celui-ci Download PDF

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Publication number
WO2002088151A1
WO2002088151A1 PCT/JP2002/004192 JP0204192W WO02088151A1 WO 2002088151 A1 WO2002088151 A1 WO 2002088151A1 JP 0204192 W JP0204192 W JP 0204192W WO 02088151 A1 WO02088151 A1 WO 02088151A1
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Prior art keywords
polymerizable
general formula
phosphoric acid
acid ester
reaction
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English (en)
Japanese (ja)
Inventor
Masahiko Yamanaka
Kenji Aoyagi
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New Japan Chemical Co Ltd
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New Japan Chemical Co Ltd
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Publication of WO2002088151A1 publication Critical patent/WO2002088151A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl

Definitions

  • the present invention relates to t BACKGROUND generally relates polymerizable phosphoric acid ester and its manufacturing method, the polymerizable phosphoric acid ester has a strong affinity for metal, and other Modification of base resins such as paints, coatings, and adhesives to improve adhesion to metals and to provide functions such as fire prevention and flame retardancy due to their copolymerizability with vinyl monomers Used as a monomer for
  • Hydroxyalkyl (meth) acrylate is reacted with oxychloride phosphorus to obtain a phosphoryl chloride intermediate.
  • a volatile solvent is used for the purpose of reducing the viscosity of the reaction system and removing the reaction heat as latent heat of evaporation.
  • the volatile solvent is limited to aprotic solvents such as methylene chloride, benzene, and toluene.
  • hydrolysis is performed to obtain a crude polymerizable phosphoric acid ester.
  • a basic compound such as pyridine, triethylamine, sodium hydroxide or the like is usually used for the purpose of capturing by-produced hydrogen chloride. Thereafter, salts produced as by-products are removed by washing with water or solvent extraction, and then the volatile solvent and the like are distilled off under heating and reduced pressure to obtain the desired product.
  • the content of the remaining volatile solvent is 50 ppm or less, preferably 10 ppm or less, and the content of corrosive impurities such as (meth) acrylic acid and chlorine is 1% by weight or less.
  • a polymerizable phosphate ester preferably 0.1% by weight or less.
  • the volatile solvent content is 50 ppm or less, and the (meth) acrylic acid content is 1% by weight. The following have not been obtained in the past.
  • the present invention relates to a polymerizable organic acid which is substantially free of volatile solvents and chlorine and has a content of polymerizable organic acids such as acrylic acid and methacrylic acid by-produced below a certain level.
  • An object of the present invention is to provide a phosphoric acid ester and a method for producing the polymerizable phosphoric acid ester which is safe and simple and industrially excellent without causing abnormal polymerization.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, when producing a polymerizable phosphate ester, using the polymerizable phosphate ester instead of using a volatile solvent as a reaction solvent, By reacting polyphosphoric acid with hydroxyalkyl-substituted acrylate, by-products and abnormal polymerization of polymerizable organic acids can be suppressed. As a result, the content of volatile solvents is 50 ppm or less.
  • the present inventors have found that the polymerizable phosphoric acid ester having a polymerizable organic acid content of 1% by weight or less can be produced, and have completed the present invention.
  • the present invention provides the following polymerizable phosphate and a method for producing the same.
  • R 1 represents hydrogen or an alkynole group having 1 to 4 carbon atoms.
  • R 2 represents a linear or branched alkylene group having 2 to 6 carbon atoms.
  • n represents an integer of 1 or 2.
  • R 1 represents hydrogen or an alkyl group having 1 to 4 carbon atoms.
  • Item 2 The polymerizable phosphoric acid ester according to the above item 1, wherein in the general formula (1), R 1 is hydrogen.
  • Item 3 The polymerizable phosphoric acid ester according to the above item 1, wherein in the general formula (1), R 1 is hydrogen and R 2 is an ethylene group.
  • Item 4 The method for producing a polymerizable phosphoric acid ester according to the above item 1, wherein the polymerizable phosphoric acid ester is used as a reaction solvent,
  • R 3 represents hydrogen or an alkyl group having 1 to 4 carbon atoms.
  • R 4 represents a linear or branched alkylene group having 2 to 6 carbon atoms.
  • Item 6 A polyphosphoric acid solution obtained by dissolving polyphosphoric acid in a polymerizable phosphoric acid ester, The hydroxyalkyl mono- ⁇ -substituted acrylate represented by the general formula (3) is added little by little, or the hydroxyalkyl mono- ⁇ -substituted acrylate represented by the general formula (3) is added to the polymerizable phosphoric acid ester. 6.
  • the hydroxyalkyl a-substituted acrylate represented by the general formula (3) is used in an amount of 0.2 mol to 1.2 mol based on 1 equivalent of polyphosphoric acid.
  • the compound represented by the general formula (3) is represented by the general formula (4)
  • R 5 represents a linear or branched alkylene group having 2 to 6 carbon atoms.
  • Item 13 A polymerizable phosphate ester which can be produced by the method according to any one of Items 4 to 12 above.
  • Item 14 General formula (1)
  • R 1 represents hydrogen or an alkyl group having 1 to 4 carbon atoms.
  • R 2 represents a linear or branched alkylene group having 2 to 6 carbon atoms.
  • n represents an integer of 1 or 2.
  • the solvent content is 50 ppm or less and the general formula (2)
  • R 1 represents hydrogen or an alkyl group having 1 to 4 carbon atoms.
  • a polymerizable ester having a polymerizable organic acid content of 1% by weight or less which can be produced by the method described in any one of the above items 4 to 12.
  • R 1 is hydrogen or an alkyl group having 1 to 4 carbon atoms
  • R 2 is an ethylene group, a trimethylene group, a propylene group, A linear or branched alkylene group having 2 to 6 carbon atoms such as ethylethylene group, tetramethylene group, pentamethylene group, and hexamethylene group, wherein n is 1 or 2 and at least one compound is contained. Or a mixture.
  • R 1 is hydrogen
  • R 2 is an ethylene group (—CH 2 —CH 2 —) is more preferable.
  • the volatile solvent according to the present invention is a volatile organic compound having a boiling point at normal pressure of the volatile solvent in the range of 50 to 200 ° C.
  • hexane, heptane Aliphatic hydrocarbons such as tan, nonane, decane, benzene, toluene, xylene, ethylbenzene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3-trimethylbenzene, p- Aromatic hydrocarbons such as benzene with dichloro, hydrocarbons containing halogen such as chloroform, trichloroethylene, tetrachloroethylene, 1,1,1-trichloroethane, 1,2-dichloroethane, 1,2-dichloropropane Ethers such as dimethoxyethane and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, and methyl ethy
  • the polymerizable phosphoric acid ester of the present invention has a reduced content of the above-mentioned volatile solvent, and is usually 5 Oppm or less, particularly 2 Oppm or less, and preferably 10 ppm or less. Therefore, the polymerizable phosphoric acid ester of the present invention has the conventional problems associated with the volatilization of residual solvents, such as the problem of reduced safety and health in enclosed spaces, contamination of products in the fields of foods, pharmaceuticals, and electronic materials, and quality. There is no problem such as lowering.
  • R 1 represents hydrogen or an alkyl group having 1 to 4 carbon atoms.
  • polymerizable organic acid represented by is acrylic acid, methylacrylic acid, ⁇ -ethylacrylic acid, ⁇ - ⁇ -butylacrylic acid, and the like.
  • the content of the polymerizable organic acid is also reduced, and is usually 1% by weight or less, particularly 0.2% by weight or less, preferably 0.1% by weight or less.
  • the polymerizable phosphoric acid ester of the present invention has an advantage that, unlike the conventional polymerizable phosphoric acid ester, the metal member does not substantially corrode due to the polymerizable organic acid.
  • the polymerizable phosphoric acid ester of the present invention since no chlorine-containing raw material is used, the polymerizable phosphoric acid ester of the present invention has an extremely low chlorine content and substantially contains chlorine. Not. Therefore, there is also an advantage that corrosion of the metal member caused by chlorine does not substantially occur.
  • polyphosphoric acid used as a raw material is not particularly limited.
  • k is an integer of 2 or more, particularly 3 to 6.
  • the compound represented by is recommended.
  • Industrially available polyphosphoric acid is generally called strong phosphoric acid or condensed phosphoric acid, and is a mixture of polyphosphoric acids having different values of k (condensation degree) in the above chemical formula.
  • Such a polyphosphoric acid is appropriately selected according to the purpose.
  • a polyphosphoric acid having a phosphoric acid content of 114% by weight (the average value of k corresponds to 3) or more must be used.
  • polyphosphoric acid with a phosphoric acid content of 118 wt% or less (the average value of k is equivalent to 6). Is recommended. Therefore, in the present invention, it is preferable to use polyphosphoric acid having an average value of k of 3 to 6 (that is, a phosphoric acid content of 114 to 118% by weight).
  • Examples of the hydroxyalkyl_ ⁇ -substituted acrylate represented by the general formula (3) include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 3-hydroxypropyl acrylate.
  • Acrylates such as 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate, 5-hydroxy-3-methylpentyl acrylate, 2-hydroxyethyl methacrylate, Methacrylates such as 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl methacrylate, 5-hydroxy-3-methylpentyl methyl acrylate,And 2-hydroxyethyl-1 0; -ethyl acrylate, 2-hydroxyethyl- ⁇ - ⁇ -propyl acrylate, ⁇ -alkyl such as 2-hydroxyethyl- ⁇ _ ⁇ -butyl acrylate ( Examples thereof include
  • —Hydroxyethyl acrylate is recommended.
  • the polymerizable phosphoric acid ester of the present invention is used as a reaction solvent, but the first reaction solvent used is produced without using the polymerizable phosphoric acid ester of the present invention.
  • the phosphate ester is formed in this way, it functions as a reaction solvent, and thereafter, becomes a reaction system similar to the production method of the present invention.
  • a compound having the general formula (3) is charged into a flask having a capacity of 500 m1 with about 50 g of polyphosphoric acid, while sufficiently stirring, introducing (blowing) air (oxygen), and cooling. (Preferably containing a polymerization inhibitor described below) is slowly added dropwise. Since this reaction generates a large amount of heat, the dropwise addition is carried out at a rate effective to suppress the temperature of the reaction system to 120 ° C. or lower, preferably 100 ° C. or lower, while cooling if necessary. This produces a small amount of polymerizable phosphoric acid ester. Thereafter, according to the present invention, the reaction is continued by gradually increasing the reactant volume. In this case, the products (polymerizable phosphate) obtained in each step have almost the same composition, and can be used as a solvent for producing the polymerizable phosphate of the present invention.
  • a larger amount of the polymerizable phosphoric acid ester of the present invention can be produced by performing the production method of the present invention using this as a reaction solvent. This can be used as a reaction solvent in the production method of the present invention.
  • the compound represented by the general formula (3) used in producing the polymerizable phosphoric acid ester used as a reaction solvent is obtained by using the reaction solvent according to the esterification reaction of the present invention.
  • the compound represented by the formula (3) may be different from the compound represented by the formula (3), but is usually preferably the same.
  • the polymerizable phosphoric ester used as a reaction solvent and the product of the production method of the present invention become the same, so that there is an advantage that there is no need to separate them.
  • the polymerizable phosphoric acid ester desired as a reaction solvent is used.
  • a tell There is no particular limitation other than the use of a tell.
  • the amount of the polymerizable phosphoric acid ester used as the reaction solvent is preferably equal to or more than the weight of the polyphosphoric acid, and particularly preferably about 3 to 3 times the weight of the polyphosphoric acid. If the weight is less than the equivalent weight, it tends to be difficult to remove the heat of reaction.
  • the following method is specifically mentioned as a production example.
  • a polyphosphoric acid solution obtained by dissolving polyphosphoric acid in a desired polymerizable phosphoric acid ester is obtained. Then, a hydroxyalkyl- ⁇ -substituted acrylate represented by the general formula (3) is added to the obtained polyphosphoric acid solution. Continuous or intermittent addition, esterification reaction,
  • the hydroxyalkyl ⁇ -substituted acrylate represented by the general formula (3) is dissolved in the desired polymerizable phosphoric acid ester, and polyphosphoric acid is continuously or intermittently added to the obtained hydroxyalkyl mono- ⁇ -substituted acrylate solution. And then subjecting it to an esterification reaction.
  • the hydroxyalkyl mono-substituted acrylate residue in the compound represented by the general formula (3) (from the compound of the general formula (3), the hydrogen atom at the right end of the general formula (3) is removed).
  • the residue obtained by excluding the residue may be different from the hydroxyalkyl- ⁇ -substituted acrylate residue constituting the polymerizable phosphate used as the reaction solvent, but may be represented by the general formula (3).
  • the compound to be used is a compound containing a hydroxyalkyl mono (3 ⁇ 4-substituted acrylate residue) (hereinafter referred to as “general formula (3) corresponding to the reaction solvent) that constitutes the polymerizable phosphoric acid ester used as the reaction solvent. )).
  • the hydroxyphosphoric acid solution is added to the polyphosphate solution.
  • the method of adding a substituted acrylate and conducting an esterification reaction is particularly preferred.
  • polyphosphoric acid is divided into small portions and the polymerizable phosphoric acid is divided into small portions.
  • a hydroxyalkyl mono-substituted acrylate represented by the general formula (3) is added little by little to a polyphosphoric acid solution obtained by dissolving polyphosphoric acid in a polymerizable phosphoric acid ester, or
  • the esterification reaction can be carried out by adding the polyphosphoric acid little by little to a solution obtained by dissolving the hydroxyalkyl monosubstituted acrylate represented by the general formula (3) in the polymerizable phosphate ester.
  • the addition rate when the hydroxyalkyl mono-a-substituted acrylate represented by the general formula (3) is added little by little can be appropriately selected.
  • the addition rate is not particularly limited, but is usually adjusted so that the concentration of unreacted polyphosphoric acid in the polyphosphoric acid solution does not exceed 50% by weight. Is preferred. In other words, it is preferable to adjust the amount of polyphosphoric acid dissolved in 100 parts by weight of the polymerizable phosphoric acid ester as a solvent so as not to exceed 100 parts by weight.
  • the reaction apparatus is not particularly limited, for example, it can be manufactured using a stirred tank type reactor.
  • the total volume of polymerizable phosphate ester and polyphosphoric acid added in advance is appropriately determined according to the stirring capacity and cooling capacity of the reactor used, but 30% of the capacity of the reactor is used. It is preferable from the viewpoint of the stirring efficiency and the cooling efficiency to be about the same, and it is preferable to use the polyphosphoric acid in an amount of 50% by weight or less based on the polymerizable phosphoric acid ester. That is, it is preferable that the amount of the polyphosphoric acid dissolved in 100 parts by weight of the polymerizable phosphoric acid ester as the solvent is adjusted so as not to exceed 50 parts by weight.
  • the concentration of the solution of the compound represented by the general formula (3) is not particularly limited, but is preferably 50% by weight or less.
  • polyphosphoric acid and a hydroxyalkyl-Q! -Substituted compound represented by the general formula (3) Since the reaction with acrylate is an exothermic reaction, for example, it is preferable to add the hydroxyalkyl-Q! -Substituted acrylate represented by the general formula (3) little by little.
  • the amount of the hydroxyalkyl-a-substituted acrylate represented by the general formula (3) per 1 equivalent of polyboric acid is not particularly limited, but may be from 0.2 mol to 1.2 mol, particularly from 0 mol. 5 mol to 1.0 mol is recommended.
  • One equivalent of polyphosphoric acid indicates the amount of polyphosphoric acid containing several phosphorus atoms of Apogadro.
  • the desired polymerizable phosphoric acid ester and the hydroxyalkyl mono-a-substituted acrylate represented by the general formula (3) as a raw material have a polymerizable vinyl bond, so that in the above reaction, It is preferable to use an inhibitor and control the reaction temperature within the temperature range described below.
  • polymerization inhibitor examples include, but are not particularly limited to, quinone having a hydrid, 2,5-di-tert-butylhydroquinone, p-tert-butyl diethanol, p-methoxyphenol, — Phenolic compounds such as tert-butyl-4-methoxyphenol and 2,6-ditert-butyl-4-methylphenol; phenothiazine; methylene blue; It is recommended that these polymerization inhibitors be used in an amount of usually 0.0001 to 1% by weight, preferably 0.01 to 0.5% by weight, based on the resulting polymerizable phosphate ester. You. Further, the polymerization inhibitor is preferably present in both the polymerizable ester phosphate previously added as a solvent and the hydroxyalkyl-1-a-substituted acrylate added later.
  • the amount of the polymerization inhibitor used is represented by the general formula (3).
  • Hydroxyalkyl usually in the range of 0001% to 2% by weight, preferably 0.01% to 1% by weight, based on monosubstituted acrylate. It is recommended that they be used in boxes.
  • an oxygen-containing gas such as air, an air / nitrogen mixture, or an oxygen / nitrogen mixture into the reaction solution, if necessary, together with the addition of the polymerization inhibitor. It is preferable that the oxygen-containing gas be removed of water through calcium chloride, silica gel, or the like, or by an air compressor or the like.
  • the blowing rate of the oxygen-containing gas can be selected from a wide range. For example, when air is used, 0.1 to: L per kg of the final target product (including the polymerizable phosphate used as a reaction solvent)
  • the speed is preferably about 0 m1 Zmin, particularly about 0.5 to 5 ml Zmin.
  • the blowing of the oxygen-containing gas may be performed throughout the entire reaction time of the esterification reaction, or may be performed during a part of the reaction time.
  • the reaction temperature is preferably in the range of room temperature to 120 ° C., more preferably in the range of 401 to 100 :.
  • the reaction temperature is lower than room temperature, the viscosity of the reaction solution tends to be high and stirring tends to be difficult, and when the reaction temperature is higher than 120 ° C, it is difficult to suppress the polymerization. Tend to be.
  • the pressure during the reaction is not particularly limited, but is preferably normal pressure or pressurized (for example, about 0.10 to 0.15 MPa). When the reaction pressure is reduced, polymerization tends to easily occur due to lack of oxygen or the like.
  • the reaction time depends on the type of the reaction apparatus, the type of raw materials, the amount charged, the reaction temperature, and the like, and can be appropriately set so that the above-mentioned esterification reaction is completed.
  • the reaction type may be either a batch type or a continuous type.
  • the reaction mixture thus obtained is the polymerizable phosphate ester of the present invention.
  • the polymerizable phosphate ester has a volatile solvent content of 5 ppm or less and is represented by the general formula (2). Content of the polymerizable organic acid is 1% by weight or less.
  • the reaction mixture thus obtained, that is, the polymerizable phosphoric ester of the present invention can be used as it is for the following applications.
  • the polymerizable phosphoric acid ester of the present invention thus obtained can be used in the same applications as conventionally known polymerizable phosphoric acid esters.
  • such a polymerizable phosphate ester has a polymerizable vinyl bond, has a good copolymerizability with other vinyl monomers, and has a strong affinity with a metal, so that it can be used for paints, coating agents, It can be used as a monomer for modifying base resins such as adhesives.
  • 2-hydroxyethyl acrylate, 2-ethylhexyl acrylate, 4 It is mixed and used with commercially available vinyl monomers such as butanediol diacrylate, 1,6-hexanedioldiol diacrylate, diethylene glycol diacrylate, and neopentyl glycol diacrylate, and is used in combination with benzophenones, thioxanthones, Commercially available photopolymerization initiators such as polyhydroxyalkylphenones and acylphosphinoxides are added in an amount of 1% by weight to 5% by weight to be photocured.
  • It has excellent corrosion protection because corrosive impurities are reduced to 1% by weight or less, has flame retardancy, and has virtually no environmental pollution due to residual solvents. Or, it is a material that is particularly suitable for coating and bonding applications such as kitchen metal articles, automotive components, and electronic components.
  • the polymerizable phosphoric acid ester and its polymer can be used as a chelating agent, an antistatic agent, an anti-fogging agent, a flame retardant, and an anti-oxidant. Examples Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.
  • the specific gravity of the polymerizable phosphoric acid ester was measured according to JIS K 061-4, and the viscosity was measured according to JIS K 7171-1.
  • the polymerizable phosphoric acid ester used as the reaction solvent was prepared as follows. 2-hydroxyhexyl acrylate in which 50 g (0.59 equivalents) of the same polyphosphoric acid as above was charged into a 500 ml tank reactor of the same type as above, and 0.475 g of p-methoxyphenol was dissolved 68. 7 g (0.59 mol) was allowed to react dropwise with stirring while blowing air at 5 ml / min to prepare a reaction solvent to be used first. During the dropwise addition, a large amount of heat was generated. Thus, the mixture was added dropwise over 6 hours while maintaining the temperature of the reaction system at 60. After the addition, the mixture was further aged at 60 ° C. for 1 hour.
  • the reaction was continued according to the present invention, with the volume of the reactants being increased stepwise. That is, 119 g (1.4 equivalents) of the same polyphosphoric acid as described above was charged into a reactor containing 119.2 g of the product obtained above, and air was supplied to the resulting mixture at 5 m1 Zmin. After stirring at 60 ° C for 0.5 hour while blowing, 163.5 g (1.4mo1) of 2-hydroxyethyl acrylate in which 1.13 g of p-methoxyphenol was dissolved was added under stirring. The solution was dropped at 60 ° C. for 2 hours, and aged at 60 ° C. for 1 hour.
  • the pale yellow transparent liquid contained 0.1% by weight of hydroquinone as a polymerization inhibitor.
  • the liquid was a phosphoric acid ester of 2-hydroxypropyl methacrylate, that is, the polymerizable phosphoric acid ester according to the present invention. That is, in the above reaction product, the absorption at 3430 cm- 1 (0-H bond) observed in the raw material in the IR analysis disappeared, and 1024 to 103
  • the polymerizable phosphoric ester used as the reaction solvent was prepared in the same manner as in Example 1 except that 2-hydroxypropyl methacrylate was used instead of 2-hydroxyethyl acrylate.
  • the polymerizable phosphoric acid ester used as the reaction solvent was produced in the same manner as in Example 1.
  • Example 2 The same reaction as in Example 1 was carried out except that a volatile solvent was used instead of the polymerizable phosphate ester (reaction solvent) previously added.
  • the method for producing a polymerizable phosphate according to the present invention is substantially free of harmful volatile organic compounds and chlorine, and becomes cloudy or gel-like due to abnormal polymerization during the production process. It is possible to reduce corrosive impurities as much as possible without causing generation of rust.

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Abstract

L'invention concerne un ester phosphorique polymérisable comprenant au moins un composé représenté par la formule générale (1), dans laquelle R1 représente hydrogène ou C¿1-4? alkyle; R?2¿ représente C¿2-6? alkylène linéaire ou ramifié ; et n est égal à 1 ou 2. La teneur du solvant volatil est de 50 ppm ou moins et celle des acides organiques polymérisables représentés par la formule générale (2), dans laquelle R?1¿ représente hydrogène ou C¿1-4 ?alkyle, est de 1 % en poids ou moins. Par ailleurs, l'invention concerne un procédé de production dudit ester phosphorique polymérisable, qui consiste à utiliser l'ester phosphorique polymérisable comme solvant réactionnel pour faire réagir un acide polyphosphorique avec un acrylate d'hydroxyalkyle α-substitué.
PCT/JP2002/004192 2001-04-27 2002-04-26 Ester phosphorique polymerisable et procede de production de celui-ci Ceased WO2002088151A1 (fr)

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JP2001131105 2001-04-27

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004309625A (ja) * 2003-04-03 2004-11-04 Seed Co Ltd イオン性眼用レンズ
WO2007074926A1 (fr) * 2005-12-26 2007-07-05 Kao Corporation Procede pour produire un ester de phosphate polymerisable
JP2009507934A (ja) * 2005-05-27 2009-02-26 ビーエーエスエフ コーティングス アクチェンゲゼルシャフト 被覆材料、その製造方法および付着性の、着色および／または効果付与被覆剤を製造するためのその使用
JP2010235586A (ja) * 2009-03-30 2010-10-21 Rohm & Haas Co 改良された重合性組成物
JP2010235920A (ja) * 2009-03-30 2010-10-21 Rohm & Haas Co 改良された重合性組成物
CN113512284A (zh) * 2021-04-27 2021-10-19 骏能化工（龙南）有限公司 一种高阻燃聚氨酯复合材料的制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59139392A (ja) * 1983-01-31 1984-08-10 Kuraray Co Ltd リン酸モノエステルの製造法
EP0225030A1 (fr) * 1985-10-22 1987-06-10 Minnesota Mining And Manufacturing Company Composés d'ester d'acide phosphorique durcissables par irradiation et agent d'enregistrement magnétique encluant les esters phosphoriques durcis
JPH07138270A (ja) * 1993-11-17 1995-05-30 Kao Corp リン酸ジエステル多価金属塩、その製法及び該リン酸ジエステル多価金属塩を含有する油ゲル化剤

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59139392A (ja) * 1983-01-31 1984-08-10 Kuraray Co Ltd リン酸モノエステルの製造法
EP0225030A1 (fr) * 1985-10-22 1987-06-10 Minnesota Mining And Manufacturing Company Composés d'ester d'acide phosphorique durcissables par irradiation et agent d'enregistrement magnétique encluant les esters phosphoriques durcis
JPH07138270A (ja) * 1993-11-17 1995-05-30 Kao Corp リン酸ジエステル多価金属塩、その製法及び該リン酸ジエステル多価金属塩を含有する油ゲル化剤

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004309625A (ja) * 2003-04-03 2004-11-04 Seed Co Ltd イオン性眼用レンズ
JP2009507934A (ja) * 2005-05-27 2009-02-26 ビーエーエスエフ コーティングス アクチェンゲゼルシャフト 被覆材料、その製造方法および付着性の、着色および／または効果付与被覆剤を製造するためのその使用
WO2007074926A1 (fr) * 2005-12-26 2007-07-05 Kao Corporation Procede pour produire un ester de phosphate polymerisable
US8207367B2 (en) 2005-12-26 2012-06-26 Kao Corporation Method for producing polymerizable phosphate ester
JP2010235586A (ja) * 2009-03-30 2010-10-21 Rohm & Haas Co 改良された重合性組成物
JP2010235920A (ja) * 2009-03-30 2010-10-21 Rohm & Haas Co 改良された重合性組成物
KR101248236B1 (ko) 2009-03-30 2013-03-27 롬 앤드 하아스 컴패니 개선된 중합성 조성물
CN113512284A (zh) * 2021-04-27 2021-10-19 骏能化工（龙南）有限公司 一种高阻燃聚氨酯复合材料的制备方法
CN113512284B (zh) * 2021-04-27 2022-07-12 骏能化工（龙南）有限公司 一种高阻燃聚氨酯复合材料的制备方法

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