WO2012011519A1 - Agent ignifuge contenant un sel d'amine cyclique, et composition de résine ignifuge - Google Patents

Agent ignifuge contenant un sel d'amine cyclique, et composition de résine ignifuge Download PDF

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Publication number
WO2012011519A1
WO2012011519A1 PCT/JP2011/066534 JP2011066534W WO2012011519A1 WO 2012011519 A1 WO2012011519 A1 WO 2012011519A1 JP 2011066534 W JP2011066534 W JP 2011066534W WO 2012011519 A1 WO2012011519 A1 WO 2012011519A1
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Prior art keywords
flame retardant
cyclic amine
resin
component
amine salt
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PCT/JP2011/066534
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English (en)
Japanese (ja)
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小林　淳一
快 三輪
喜一 平田
石川　章
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丸菱油化工業株式会社
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Publication of WO2012011519A1 publication Critical patent/WO2012011519A1/fr

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    • 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
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
    • 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
    • C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
    • C07F9/1406—Esters of phosphoric acids containing P(=O)-halide groups containing the structure Hal-P(=O)-O-aryl
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/5205—Salts of P-acids with N-bases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Definitions

  • the present invention relates to a novel flame retardant and a flame retardant resin composition.
  • the present invention relates to a flame retardant containing a cyclic amine salt, a flame retardant resin composition containing the flame retardant, and a molded product thereof. More specifically, it is useful for molding injection-molded articles and extrusion-molded articles. For example, it is suitable for home appliances, OA equipment, automobile parts, wire coating materials, etc. It relates to molded products.
  • Polyolefin resins polystyrene resins, polyacrylic resins, polyamide resins, polyester resins, polyether resins, thermoplastic resins such as polycarbonate resins, thermosetting resins such as phenol resins and epoxy resins, or these Resin alloys by combination, for example, various materials in addition to building materials, electrical equipment materials, vehicle parts, automobile interior parts, household goods, etc., depending on the characteristics such as specific mechanical characteristics, thermal characteristics, moldability, etc. Widely used in industrial products.
  • halogen-based organic compounds include tetrabromobisphenol A, hexabromocyclododecane, bisdibromopropyl ether of tetrabromobisphenol A, bisdibromopropyl ether of tetrabromobisphenol S, tris 2,3-dibromopropyl isocyanurate, bistribromophenoxy
  • halogen-based organic compounds that easily generate harmful gases (hydrogen bromide) during combustion are strongly required to be self-reliant.
  • a halogen-based flame retardant For this reason, several methods for imparting flame retardancy to a synthetic resin without using a halogen-based flame retardant have been proposed.
  • One of them is a method of adding an inorganic hydroxide such as aluminum hydroxide or magnesium hydroxide.
  • the inorganic hydroxide exhibits flame retardancy due to water generated by thermal decomposition, the flame retardancy is not exhibited unless added in a considerably large amount. Due to such a large amount of addition, there is a problem that functions inherent to the resin such as processability and mechanical properties are remarkably lowered.
  • phosphates such as ammonium polyphosphate has been proposed as a non-halogen flame retardant.
  • this type of phosphates when a large amount of this type of phosphates is added, the phosphates are low in flame retardancy and inferior in moisture resistance, so the appearance and mechanical properties of the molded product are greatly reduced.
  • phosphates if a resin molded article made of this flame retardant composition is used under high humidity, phosphates bleed out on the surface, and there are also fatal defects that cause numerous blooming phenomena. .
  • Ammonium polyphosphate coated with a surface treatment agent of melamine cross-linking type, phenol cross-linking type, epoxy cross-linking type or silane coupling agent and end-capped polyethylene glycol cross-linking type with improved moisture resistance has also been proposed.
  • these have a problem that resin compatibility or dispersibility is poor and high mechanical strength cannot be obtained.
  • the coating is broken by heat and stress, and problems similar to the above (problems such as bleeding out due to moisture absorption) often occur.
  • condensed ammonium phosphate salts such as ammonium phosphate, ammonium pyrophosphate, and ammonium polyphosphate are basically water-soluble or water-absorbing substances, and therefore their addition is heat resistance and moisture resistance of the resin composition. Is a direct cause of decline.
  • organic salts such as aliphatic amine salts of aromatic phosphoric acid monoesters have been proposed (Patent Documents 5 to 7).
  • the aliphatic amine salt of the aromatic phosphoric acid monoester is a water-soluble organic salt having a very strong water absorption property although having a predetermined flame retardancy.
  • a monotolylpiperazine phosphate salt represented by the following chemical formula (1) corresponds to this.
  • This substance is an onium salt in which tolyl dihydrogen phosphate ion, which is an anionic component, and piperazine ion, which is a cation component, are alternately coordinated, and is highly water-soluble and insoluble in most organic solvents.
  • the resin compatibility is also very poor.
  • monotolylpiperazine phosphate has low heat resistance, and particularly when it is kneaded as a resin composition, a large amount of highly toxic p-cresol gas is generated by thermal decomposition at a kneading temperature of 180 to 200 ° C. It has a fatal defect that it is not practically satisfactory.
  • the main object of the present invention is to solve the problems of the prior art and to provide a flame retardant capable of imparting more excellent flame retardancy, and further to a flame retardant resin composition containing the composition and molding the same. It is to provide a molded article.
  • a flame retardant composition comprising a cyclic amine salt of an aromatic phosphate diester composed of 1) an aromatic phosphoric diester as an anionic component and 2) a cyclic amine as a cationic component, the cyclic amine salt being Formula (I) [Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent.
  • A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group.
  • Y represents an imino group.
  • Z represents an oxygen atom, a sulfur atom or an imino group.
  • n represents an integer of 1 to 10.
  • m represents an integer of 0 to 9.
  • l represents an integer of 1 to 10.
  • R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent.
  • Y represents an imino group.
  • Z represents an oxygen atom, a sulfur atom or an imino group.
  • m represents an integer of 0 to 9. ] 2.
  • the flame retardant composition according to item 1, wherein the composition ratio of the component B to the component B is an ion equivalent ratio of A component / B component 0.8 / 1.0 to 1.0 / 1.2 . 3.
  • Item 2 The flame retardant composition according to Item 1, wherein the content of the aromatic phosphoric acid monoester is 1% by weight or less in the flame retardant composition. 4).
  • Item 2 The flame retardant composition according to Item 1, further comprising at least one phosphate. 5.
  • a flame retardant composition comprising the flame retardant composition according to item 1 and a resin component, the flame retardant comprising 1 to 100 parts by weight of a cyclic amine salt of the aromatic phosphoric diester with respect to 100 parts by weight of the resin component Resin composition. 6). 5.
  • a resin composition comprising the flame retardant composition according to item 4 and a resin component, wherein 1 to 50 parts by weight of a cyclic amine salt of the aromatic phosphoric diester, 100 parts by weight of the resin component, and the phosphates
  • a flame retardant resin composition comprising 1 to 50 parts by weight. 7.
  • Item 7 The flame retardant resin composition according to Item 5 or 6, wherein the resin component is a polyolefin resin. 8).
  • Item 9 The flame-retardant resin molded article according to Item 8, which is used for electrical / electronic parts, OA equipment parts, household electrical equipment parts, automotive parts or equipment mechanism parts.
  • R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent.
  • A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group.
  • Y represents an imino group.
  • Z represents an oxygen atom, a sulfur atom or an imino group.
  • n represents an integer of 1 to 10.
  • m represents an integer of 0 to 9.
  • l represents an integer of 1 to 10.
  • IV The following general formula (IV) [Wherein R 1 to R 5 are the same or different from each other and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ] Is reacted with phosphorus oxyhalide in the presence of an amine, The following general formula (V) [Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent.
  • a method for producing a cyclic amine salt of an aromatic phosphoric diester comprising a step of synthesizing a compound represented by the general formula (I) by adding a compound represented by formula (I).
  • the flame retardant of the present invention contains a cyclic amine salt having a specific chemical structure, it can exhibit flame retardancy superior to conventional flame retardants. Therefore, the desired flame retardancy can be imparted even with a relatively small amount of addition. That is, it is possible to provide excellent flame retardancy while effectively maintaining the original characteristics of the material to be added (resin etc.).
  • the flame retardant of the present invention is excellent in moisture resistance, problems such as bleeding out and blooming due to moisture absorption, and deterioration of flame resistance due to bleeding out can be effectively suppressed or prevented.
  • the cyclic amine salt which is an active ingredient of the flame retardant of the present invention, does not contain a halogen element in the molecule, it can effectively suppress the generation of harmful gases even when the flame retardant resin and the molded product burn. it can.
  • the present invention when applied as a flame retardant such as a polyolefin resin, it is possible to exhibit excellent flame retardancy with a smaller amount of flame retardant by using phosphates together with the cyclic amine salt. it can.
  • phosphates such as polyphosphates have high water solubility or high water absorption.
  • the flame-retardant resin composition and molded product containing phosphate as a flame retardant cannot effectively suppress mold deposits and bleed-out (or blooming) of the flame retardant.
  • the flame-retardant resin composition and molded product containing the flame retardant of the present invention can highly compatibilize polyphosphates with the resin while maintaining good physical properties of various resins.
  • the flame retardant of the present invention can be suitably used as a flame retardant for adding to a material containing an organic component, for example.
  • it can be preferably used as a flame retardant for addition to a composition containing a resin component (for example, a composition containing 50% by weight or more of a resin component).
  • the flame retardant for resin of the present invention is 1) an aromatic phosphate diester as an anionic component and 2) A flame retardant comprising a cyclic amine salt of an aromatic phosphoric diester composed of a cyclic amine which is a cationic component,
  • the cyclic amine salt of the aromatic phosphoric diester is The following general formula (I) [Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent.
  • A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group.
  • Y represents an imino group.
  • Z represents an oxygen atom, a sulfur atom or an imino group.
  • n represents an integer of 1 to 10.
  • m represents an integer of 0 to 9.
  • l represents an integer of 1 to 10.
  • a cyclic amine salt of an aromatic phosphoric acid diester represented by the formula:
  • the aromatic phosphoric diester cyclic amine salt represented by the following general formula (I) (hereinafter also referred to as “the present cyclic amine salt”) functions as an active ingredient of the present flame retardant.
  • the flame retardant of the present invention contains one or more of the cyclic amine salts of the present invention.
  • the cyclic amine salt of the present invention contains an aromatic phosphate diester as an anion component (component A) and is composed of a cyclic amine as a cation component (component B).
  • component A aromatic phosphate diester
  • component B a cyclic amine as a cation component
  • a known or commercially available one can also be used.
  • the cyclic amine salt of the present invention will be described separately for component A and component B.
  • a component The aromatic phosphoric acid diester which comprises A component among cyclic amine salt of this invention is shown by the following general formula (II). [Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ]
  • R 1 to R 10 in the general formula (II) represent a hydrogen atom or a hydrocarbon group which may have a substituent. Further, each of R 1 to R 10 may be the same substituent as each other, or may be different from each other. In particular, in the present invention, R 1 to R 10 are more preferably a hydrogen atom than an optionally substituted hydrocarbon group from an economical viewpoint.
  • the hydrocarbon group is not particularly limited, and may be any of a chain (which may be either a straight chain or a branched chain) or a ring (which may be a monocyclic ring, a condensed polycyclic ring, a bridged ring or a spiro ring). Also good.
  • a cyclic hydrocarbon group having a side chain can also be used.
  • the hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group.
  • hydrocarbon group examples include an alkyl group, a cycloalkyl group, an allyl group, an aryl group, an alkylaryl group, and an arylalkyl group.
  • the total number of carbon atoms of these hydrocarbon groups is not limited, but is generally about 1 to 18, and preferably about 1 to 4. . More specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group and the like can be exemplified.
  • a substituent may be introduced into the hydrocarbon group.
  • substituents include an amino group, hydroxyl group, alkoxyl group, nitro group, cyano group, carbonyl group, aldehyde group, carboxyl group, sulfone group, and sulfhydryl group.
  • R 1 , R 3 , R 5 , R 6 , R 8 and R 10 are hydrogen atoms or methyl groups, and R 2 , R 4 , R 7 and R 9. Is a hydrogen atom.
  • aromatic phosphoric acid diester represented by the general formula (I) include compounds represented by the following formulas (1) to (5). As these compounds themselves, known or commercially available compounds can also be used.
  • the cyclic amine constituting the B component is represented by the following general formula (III).
  • A represents a cyclic amine in which one or more imino groups (—NH—) are cyclically bonded to an alkylene group.
  • Y represents an imino group.
  • Z represents an oxygen atom, a sulfur atom or an imino group.
  • m represents an integer of 0 to 9.
  • m 0, for example, piperidine, pyrrolidine and the like are applicable.
  • alkylene group examples include a methylene group, an ethylene group, a propylene group, and a butylene group.
  • an alkylene group having 2 to 6 carbon atoms is particularly preferable.
  • a cyclic amine for example, a compound in which one or more imino groups (—NH—) are cyclically bonded through an oxygen atom, a sulfur atom or an imino group and an alkylene group can be used. More preferably, a cyclic amine in which two or more imino groups are bonded cyclically via an alkylene group is used.
  • cyclic amine examples include aziridine, azetidine, pyrrolidine, piperidine, azepan, azocan, azonan, azecan, diazetidine, imidazolidine, pyrazolidine, piperazine, morpholine, thiomorpholine, 1,4,7-triazacyclononane. 1,4,7,10-tetraazacyclododecane, 1,4,7,10,13-pentaazacyclopentadecane, 1,4,7,10,13,16-hexaazacyclooctadecane and the like.
  • cyclic amine A cyclic amines or cyclic polyamines can be appropriately selected and used.
  • cyclic amines include pyrrolidine, imidazolidine, pyrazolidine, piperazine, morpholine, thiomorpholine, and the like.
  • the cyclic polyamines include cyclic polyamines in which two or more combinations of imino group (—NH—) and ethylene group (—CH 2 —CH 2 —) are linked in a cyclic manner.
  • piperazine is most preferable from the viewpoint of being inexpensive and easy to obtain.
  • cyclic amine represented by the general formula (III) include compounds represented by the following formulas (6) to (10).
  • the cyclic amine salt of the present invention those having high heat resistance during kneading or molding with a resin component can be suitably used.
  • the cyclic amine A is preferably a secondary amine or a tertiary amine rather than a primary amine.
  • a cyclic amine can be used more suitably than an aliphatic amine having low heat resistance.
  • the component ratio of the A component and the B component in the cyclic amine salt of the present invention is not particularly limited, but in order to more effectively retain flame retardancy, moisture resistance, etc., the respective ion equivalents of the A component and the B component Are preferably equal.
  • each ion equivalent By making each ion equivalent equal, the content of excess ionic components can be lowered, so that the expression of water solubility or hygroscopicity can be effectively suppressed or prevented, resulting in poor appearance of molded products, etc. In addition, deterioration of physical properties can be avoided.
  • cyclic amine salt of the present invention The role of the cyclic amine salt of the present invention in the flame retardant resin composition of the present invention and its molded article is not only to function as a flame retardant, but also to a moisture absorption inhibitor, blooming inhibitor, etc. Can exhibit various functions.
  • specific examples of the more preferred cyclic amine salt of the present invention are shown by the following formulas (11) to (16) when piperazine is selected as a preferred example of the constituent B component. Compounds.
  • the cyclic amine salt of the aromatic phosphoric acid diester obtained by a well-known manufacturing method can also be used.
  • the cyclic amine salt of the present invention can be produced by a known production method, but is particularly preferably produced by the production method of the present invention.
  • triphenyl phosphate (triester form) can be preferentially synthesized with good yield.
  • synthesis route of the above publication it is difficult to selectively synthesize preferentially only monochlorodiphenyl phosphate (diester).
  • the compound represented by the chemical formula (IV) is reacted with phosphorus oxyhalide in the presence of an amine via the compound represented by the general formula (V).
  • This is a synthetic route for producing a cyclic amine salt represented by the general formula (I).
  • the target compound can be obtained directly in one pot with higher yield. More specifically, in each process leading to the synthesis of the cyclic amine salt of the present invention which is the target compound, the intermediate product can be continuously transferred to the next process without performing the isolation and production process.
  • the production method of the present invention in the production of the cyclic amine salt of the present invention.
  • the production method of the present invention comprises: (1) The following chemical formula (IV) [Wherein R 1 to R 5 are the same or different from each other and each represents a hydrogen atom or a hydrocarbon group which may have a substituent. ] Is reacted with phosphorus oxyhalide in the presence of an amine, The following general formula (V) [Wherein R 1 to R 10 are the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group which may have a substituent.
  • a step of obtaining a compound represented by the general formula (I) by adding a compound represented by formula (I) in an organic solvent (step C) It is a manufacturing method containing.
  • Step A an amine is added to a reaction system containing phosphorus oxyhalide and the phenol derivative represented by the general formula (IV) to cause a dehydrohalogenation reaction.
  • a reaction system containing phosphorus oxyhalide and the phenol derivative represented by the general formula (IV) to cause a dehydrohalogenation reaction.
  • ) -Containing halogen-containing aromatic phosphate ester derivatives.
  • the amine added at this time functions as a catalyst that efficiently promotes the selective ester reaction.
  • the compound represented by the general formula (IV) may be reacted using commercially available phenol and phosphorus oxyhalide as raw materials.
  • phosphorus oxyhalide for example, phosphorus oxychloride, phosphorus oxybromide and the like can be used. If phosphorus oxychloride is used, the halogen atom of the compound represented by the general formula (V) becomes chlorine. If phosphorus oxybromide is used instead of phosphorus oxychloride, the halogen atom of the compound represented by the general formula (V) is bromine.
  • an amine is allowed to coexist in the reaction system as a catalyst for efficiently promoting the selective esterification reaction.
  • the type of amine is not particularly limited.
  • triethylamine, pyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] At least one of -5-nonene, 4-dimethylaminopyridine and the like.
  • triethylamine is preferable from an economical viewpoint.
  • an amine that serves as a dehydrohalogenation catalyst is added to both the phosphorus oxyhalide and the phenol derivative represented by the general formula (IV) at about room temperature (about 10 to 40 ° C.).
  • the reaction temperature is lower than 10 ° C., the reaction rate decreases, so the reaction time becomes longer.
  • the reaction temperature exceeds 40 ° C., the reaction runs away, and by-products such as triesters are generated in addition to the diesters represented by the general formula (V), resulting in a reduction in reaction yield. There is.
  • the mixing ratio of each raw material is about 0.4 to 0.6 mol, preferably about 0.45 to 0.55 mol of phosphorus oxyhalide with respect to 1 mol of the phenol derivative represented by the general formula (IV). Just do it. Further, the amount of amine is about 0.8 to 1.2 mol, preferably about 0.9 to 1.1 mol, per mol of the phenol derivative represented by the general formula (IV). When the charging ratio of the raw material is out of the above range, there is a risk that by-products such as monoesters and triesters other than the diesters represented by the general formula (V) may be generated.
  • an amine hydrogen halide salt is always generated, and therefore the above reaction is preferably carried out in a solvent.
  • the solvent include, but are not limited to, hydrocarbon solvents such as benzene, toluene, and n-hexane; ether solvents such as tetrahydrofuran and dioxane; aprotic organic solvents such as halogenated hydrocarbon solvents such as dichloromethane and chloroform.
  • a solvent etc. can be used conveniently.
  • the amine hydrohalide salt is made into an aqueous solution and separated. It is necessary to remove the aqueous hydrogen halide salt solution. Therefore, in order to perform a continuous reaction, it is more preferable to use a water-insoluble light solvent (a solvent having a specific gravity lighter than water) as the reaction solvent.
  • a water-insoluble light solvent a solvent having a specific gravity lighter than water
  • the aromatic phosphate diester represented by the general formula (II) it is preferable to continuously synthesize the aromatic phosphate diester represented by the general formula (II) in the same reaction vessel.
  • the amine hydrogen halide salt formed as a by-product in the previous reaction is made into an aqueous solution as described above and separated into layers, and the diester represented by the general formula (V) (present in the organic solvent layer) is obtained by liquid-liquid extraction.
  • the hydrolysis reaction proceeds slightly from the diester represented by the general formula (V), and is acidic in the general formula (II). Since it is considered that the phosphoric acid diester is generated and slightly moves from the organic solvent layer to the aqueous layer, the reaction yield may be lowered as a result.
  • step A the phenol derivative represented by the general formula (III) and the oxyhalogenation necessary for obtaining one equivalent of the aromatic phosphoric diester represented by the general formula (II)
  • the charging ratio of phosphorus is about 1 equivalent for the phenol derivative and about 0.5 equivalent for phosphorus oxyhalide, which is very economically advantageous because it can be synthesized without loss of stoichiometry.
  • Step B an aromatic phosphate diester is synthesized by hydrolyzing a halogen-containing aromatic phosphate ester derivative. That is, in order to obtain the aromatic phosphoric acid diester represented by the general formula (II) from the halogen-containing aromatic phosphoric acid ester derivative (aromatic halogenated phosphoric acid diester) represented by the general formula (V), Hydrolysis may be promoted by adding water to the halogen-containing aromatic phosphate ester derivative.
  • the amount of water required for the hydrolysis can be obtained by adding a stoichiometric amount of water equal to or greater than the halogen-containing aromatic phosphoric acid ester derivative (aromatic halogenated phosphoric acid diester) represented by the general formula (V). It ’s fine.
  • the reaction temperature is not critical, but the stirring is preferably performed at a temperature not lower than room temperature (particularly a temperature exceeding 40 ° C.), more preferably 80 to 120 ° C.
  • the organic solvent used in the previous reaction may be used continuously as it is, or another organic solvent may be used in addition, and after the organic solvent in the reaction system is removed under reflux. You may perform the solvent exchange which throws in another organic solvent in a reaction system.
  • the kind of solvent that can be used the same solvents as those mentioned in the above step A can be used.
  • step B the removal of excess water after hydrolysis can also remove the aromatic phosphate monoester, which is slightly by-produced, out of the reaction system.
  • Aromatic phosphoric acid monoesters are very water-soluble, so when liquid-liquid extraction is performed, the aromatic phosphoric acid monoester does not exist in the organic solvent layer and moves completely to the aqueous layer, contrary to the aromatic phosphoric acid diester.
  • the cyclic amine salt of the aromatic phosphoric acid monoester and the cyclic amine salt of the aromatic phosphoric acid diester also exhibit the above-described properties.
  • non-uniform hydrolysis of the water-insoluble organic solvent layer and the water layer not only contributes to the one-pot continuous reaction, but also increases the selectivity of the monoester and diester forms. It can be said that this is an excellent synthesis method that contributes to this.
  • the aromatic phosphate diester can be recovered in accordance with a known purification method, solid-liquid separation method, etc., so that it is prepared separately when the flame retardant is kneaded into the resin after the recovery.
  • the dry aromatic phosphate diester and the cyclic amine are dry blended, they may be added to the resin component.
  • aromatic phosphoric diesters do not have very strong water absorption, but most cyclic amines and cyclic polyamines are water-absorbing or hydrated. It is necessary to do this, and it may take much time to obtain the flame retardant of the present invention later.
  • Step C the aromatic amine represented by the general formula (I) is continuously added by adding a cyclic amine represented by the general formula (III) to the reaction system after the completion of the step B and stirring and mixing.
  • a phosphoric diester cyclic amine salt can be synthesized.
  • the amount of cyclic amine represented by the general formula (III) is represented by the general formula (II) so that the ionic equivalents of both are equal to each other in order to maintain high flame retardancy and moisture resistance as described above. It is preferable to add an equal amount of an appropriately selected cyclic amine salt with respect to the stoichiometric amount contained in the aromatic phosphate diester.
  • a known or commercially available cyclic amine may be used as the cyclic amine represented by the general formula (III).
  • the C step it can be carried out in a solvent as necessary.
  • the solvent include hydrocarbon solvents such as benzene, toluene and n-hexane; alcohol solvents such as methanol and isopropyl alcohol; halogenated hydrocarbon solvents such as dichloromethane and chloroform.
  • the cyclic amine salt of the present invention can be recovered according to a known purification method, solid-liquid separation method, or the like.
  • synthesizing the cyclic amine salt of the present invention represented by the general formula (I) by the production method of the present invention it can be produced with a very high yield and can be efficiently produced.
  • the target product can be obtained in a very high yield of 80% or more (relative to the phenol derivative) in the total process yield.
  • cyclic amine salts of the present invention for example, when diphenyl hydrogen phosphate (DPHP) is selected as the aromatic phosphate diester represented by the general formula (II), and piperazine is selected as the cyclic amine represented by the general formula (III),
  • DPHP diphenyl hydrogen phosphate
  • piperazine is selected as the cyclic amine represented by the general formula (III)
  • DPHP phosphorus
  • the flame retardant composition of the present invention contains one or more of the cyclic amine salts of the present invention. That is, it contains at least one of the cyclic amine salts shown in (1) as an active ingredient.
  • the presence of an aromatic phosphate monoester that can be mixed in the cyclic amine salt causes deterioration of the performance. Therefore, the smaller the amount of the aromatic phosphate monoester mixed in the flame retardant of the present invention, the better. That is, the content of the aromatic phosphoric acid monoester in the flame retardant of the present invention is preferably 1% by weight or less, more preferably 0.1% by weight or less, and further preferably 0% by weight. Is most preferred.
  • the abundance ratio of the aromatic phosphoric acid monoester and the aromatic phosphoric acid diester as the component A can be examined by measuring, for example, LC / MS or GC / MS. Further, by measuring 31 P-NMR, it can be easily confirmed that the chemical shift of the diester is about ⁇ -12 to -10 ppm and the chemical shift of the monoester is about ⁇ -3 to -4 ppm. it can.
  • the flame retardant of the present invention may contain additives blended with known flame retardants in addition to the cyclic amine salt of the present invention.
  • phosphates can be preferably used in the flame retardant of the present invention. Even if only phosphates are used as flame retardants, it is very difficult to simultaneously acquire flame retardancy, moisture resistance, and blooming resistance.
  • the cyclic amine salt of the present invention and phosphates should be contained at the same time. Thus, in addition to highly enhancing the flame retardancy and moisture resistance, it is possible to obtain an effect of more effectively preventing the blooming phenomenon.
  • phosphates are basically difficult to mix with the synthetic resin and difficult to stabilize.
  • the cyclic amine salt of the present invention is superior to the prior art in that it functions as a dispersion stabilizer and / or a compatibilizer in the synthetic resin with respect to phosphates. is there.
  • phosphates For example, 1) Inorganic condensed ammonium phosphate salts, such as ammonium polyphosphate, 2) Inorganic condensed ammonium phosphate salts, such as coated ammonium polyphosphate, 3) Phosphoric acid, pyrroline Examples thereof include at least one of organic salts composed of an acid or condensed phosphoric acid and a triazine derivative.
  • inorganic condensed ammonium phosphate such as ammonium polyphosphate
  • examples of commercially available products of inorganic condensed ammonium phosphates such as C component 1) inorganic condensed ammonium phosphate such as ammonium polyphosphate include product names “Exorit AP422”, “Exorit AP700” (both manufactured by Clariant), and product names “Terrage S”. -10 ",” Terrage S-20 “(all manufactured by Chisso Corporation), and the product name” Sumisafe P "(manufactured by Sumitomo Chemical Co., Ltd.).
  • the coated inorganic condensed ammonium phosphate salt such as ammonium polyphosphate coated with component C may be microencapsulated with a thermosetting resin to compensate for the disadvantages of the ammonium polyphosphate salt that is easily hydrolyzed by moisture absorption. Further, surface treatment such as coating is performed by melamine cross-linking, and surface treatment of granules is performed by a surfactant, a silicon compound, or the like. Examples of these commercially available products are product names “Exorit AP462” (manufactured by Clariant), product names “Terrage C-30”, “Terrage C-60”, “Terrage C-70”, “Terrage C-80” ( All of them are manufactured by Chisso Corporation).
  • organic salts composed of 3) phosphoric acid, pyrophosphoric acid or condensed phosphoric acid of the C component and an amine composed of a triazine derivative include melamine, guanamine, methylguanamine, ethylguanamine, benzoguanamine, benzylguanamine, Guanidine, guanidine, phosphates of triazine derivatives such as 2,4-diamino-6-morpholino-1,3,5-triazine, 2,4-diamino-6-thiomorpholino-1,3,5-triazine, pyrroline An acid salt, and a polyphosphate condensed with three or more molecules of phosphoric acid.
  • a flame retardant composition containing at least one phosphate among the C components is mixed with various resin components to make a synthetic resin composition and the like highly advanced.
  • the flame retardant of the present invention is a char-forming phosphorus / nitrogen flame retardant, but typical char-forming flame retardants include red phosphorus, polyphosphate amine salts, most phosphate esters, and triazine derivatives. Susceptible to moisture. That is, characteristics of phosphorus compounds that are fatal defects as flame retardants, such as generation of phosphine (PH 3 ) gas derived from red phosphorus, occurrence of blooming phenomenon derived from polyphosphate amine salt, hydrolysis of phosphate ester Defects such as coloring derived from decomposition, generation of amine (nitrogen) -based decomposition gas, resin coloring and molecular weight reduction are caused by moisture caused by moisture absorption and active radicals derived from moisture.
  • phosphine (PH 3 ) gas derived from red phosphorus occurrence of blooming phenomenon derived from polyphosphate amine salt
  • hydrolysis of phosphate ester Defects such as coloring derived from decomposition, generation of amine (nitro
  • the most important performance in practical use as a char-forming phosphorus-based flame retardant is to impart high flame resistance to the synthetic resin and at the same time have high moisture absorption resistance.
  • Some flame retardants composed of phosphate esters have excellent resin compatibility, but most liquids have a low melting point and low thermal decomposition starting temperature, so the plasticity is too strong and the moldability is low. In many cases, the flame retardancy may be lowered, and high flame retardancy may not be imparted to the molded product.
  • the cyclic amine salt of the present invention alone is a non-hygroscopic flame retardant, but the cyclic amine salt of the present invention is also contained in the resin even when a C component having hygroscopicity is added at the same time in order to further enhance the flame retardancy. Since it acts as a kind of protective buffer that can stably disperse or compatibilize the components, it suppresses hygroscopicity and also maintains dispersion uniformity in the resin of the flame retardant composition. Transferability to the product surface, blooming phenomenon, or surface roughness of the molded product can be suppressed at the same time.
  • Flame retardant resin composition containing the flame retardant of the present invention (the composition of the present invention)
  • Flame Retardant Resin Composition is a resin composition comprising the flame retardant of the present invention and a resin component, and comprises 1 to 100 parts by weight of the cyclic amine salt of the present invention per 100 parts by weight of the resin component. Includes flammable resin composition.
  • the resin component is not particularly limited, and can be selected from, for example, known synthetic resins. More specifically, polyolefin resins, polystyrene resins, polyvinyl resins, polyamide resins, poly-meaning clock resins, polyester resins, polyether resins, polycarbonate resins, polyacetal resins, polyether ether ketone resins. , Thermoplastic resins such as polyphenylene / sulfide resin, polyamide / imide resin, polyether / sulfone resin, polysulfone resin, polymethyl / pentene resin, urea resin, melamine resin, epoxy resin, polyurethane resin, phenol resin, etc. And resin alloys by homopolymers or copolymers alone or in combination thereof.
  • Suitable polyolefin resins in the composition of the present invention include homopolymers of ⁇ -olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and the above ⁇ - Resins such as random or block copolymers of olefins and mixtures thereof, and polyolefin resins such as resins obtained by copolymerizing these with vinyl acetate or maleic anhydride can be suitably used.
  • ⁇ -olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and the above ⁇ - Resins such as random or block copolymers of olefins and mixtures thereof, and polyolefin resins such as resins obtained by copolymerizing these with vinyl acetate or maleic anhydride can be suitably used.
  • polypropylene resins such as propylene homopolymer, propylene-ethylene random copolymer, propylene-ethylene block copolymer, propylene-ethylene-butene copolymer, low density ethylene homopolymer
  • polyethylene resins such as high-density ethylene homopolymer, ethylene- ⁇ -olefin random copolymer, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer.
  • a polyethylene-based synthetic rubber, a polyolefin-based synthetic rubber, or the like can be blended as necessary.
  • polystyrene resin examples include polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, and the like.
  • polyvinyl resin examples include homopolymers of vinyl monomers such as alkyl acrylates, alkyl methacrylates, vinyl acetate, vinyl alcohol and the like, and copolymers of these vinyl monomers and the aforementioned ⁇ -olefins. Etc.
  • polyamide-based resin examples include polyamide 6, polyamide 6 • 6, polyamide 11, polyamide 12, polyamide 6 • 3, polyamide 6 • 4, polyamide 4 • 6, polyamide 6 • 10, and the like.
  • polyester resin examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, poly (1,4-cyclohexanedimethylene terephthalate), and the like.
  • polyether resins examples include polyphenylene ether and polyethylene ether.
  • polycarbonate resin examples include aromatic polycarbonate, aliphatic polycarbonate, aliphatic-aromatic polycarbonate, and the like.
  • bisphenol such as 2,2-bis (4-hydroxyphenyl) alkane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, etc.
  • Polymers or copolymers consisting of the above are mentioned.
  • alloy resins include polypropylene / polyamide, polypropylene / polybutylene terephthalate, acrylonitrile / butadiene / styrene copolymer / polybutylene terephthalate, acrylonitrile / butadiene / styrene copolymer / polyamide, and polycarbonate / acrylonitrile / butadiene / styrene copolymer.
  • a modified product of the above-described synthetic resin for example, a synthetic resin is obtained by unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, etc.)
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, etc.
  • the combination of the polyolefin resin and the flame retardant of the present invention is particularly preferred from the viewpoint that a molded product having higher versatility, lower cost, and balance of various physical properties can be obtained.
  • a flame retardant resin composition containing at least one of a polypropylene homopolymer, an ethylene-propylene random copolymer, and an ethylene-propylene block copolymer and the flame retardant of the present invention has moldability, heat resistance, and moisture absorption resistance. With regard to the properties and particularly high flame retardancy, it is more preferable because it can exhibit particularly excellent performance that has not been achieved in the past.
  • the blending ratio of the cyclic amine salt of the present invention is not particularly limited, and a blending amount sufficient to maintain various physical properties and flame retardancy may be added.
  • the cyclic amine salts 1 to 100 of the present invention are added to 100 parts by weight of the resin component in order to keep the kneading stability and moldability, and to give the molded article moisture resistance and high flame retardancy. What is necessary is just to mix
  • the char forming ability characteristic of the composition of the present invention is enhanced by the effect of promoting carbonization by foaming (phosphorus such as amine, triazine and melamine).
  • phosphorus such as amine, triazine and melamine
  • the blending ratio is 1 to 50 parts by weight of the cyclic amine salt of the present invention and 1 to 50 parts by weight of the C component with respect to 100 parts by weight of the resin component.
  • the cyclic amine salt of the present invention is preferably 10 to 30 parts by weight, and the C component is more preferably 10 to 30 parts by weight.
  • composition of the present invention can be appropriately blended with known or commercially available additives as necessary within the range not impeding the effects of the present invention.
  • antioxidants such as phenol compounds, phosphine compounds, thioether compounds, UV absorbers or light stabilizers such as benzophenone compounds, benzotriazole compounds, salicylate compounds, hindered amine compounds; cationic compounds, anions Compounds, nonionic compounds, amphoteric compounds, metal oxides, ⁇ -based conductive polymer compounds, carbon and other antistatic agents and conductive agents; fatty acids, fatty acid amides, fatty acid esters, fatty acid metal salts and other lubricants; benzylidene sorbitols Nucleating agents such as compounds; in addition to fillers such as talc, calcium carbonate, barium sulfate, mica, glass fiber, glass beads, low melting glass, metal deactivators, colorants, antiblooming agents, surface modifiers, Anti-
  • polytetrafluoroethylene-containing mixed particle powder having fibril forming ability can be added as the drip control agent of the composition of the present invention. Addition of polytetrafluoroethylene-containing mixed particle powder having fibril-forming ability enables drip of test pieces during combustion in a flammability test of a flame retardant resin composition, particularly in a UL standard vertical combustion test (UL94V) The prevention performance can be further increased.
  • UL94V UL standard vertical combustion test
  • polytetrafluoroethylene-containing mixed particle powder having a fibril-forming ability examples include polytetrafluoroethylene and a tetrafluoroethylene-based copolymer, and polytetrafluoroethylene (PTFE) is preferable.
  • PTFE polytetrafluoroethylene
  • the average particle size of the powder is not limited, but it is usually about 0.1 to 1000 ⁇ m.
  • the addition amount can be appropriately set according to the desired drip prevention performance and the like, but is generally preferably about 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin component.
  • composition of the present invention can be obtained by uniformly mixing the above components. Preferably, it can manufacture by melt-kneading said each component.
  • the kneading order in that case is not particularly limited, either may be mixed at the same time, or several types may be mixed in advance and the rest may be mixed later.
  • the mixing method is not limited.
  • a high-speed stirrer such as a tumbler type V-type blender, a Henschel mixer, or a ribbon mixer, a single-screw or twin-screw continuous kneader, or a method that uses a roll mixer alone or in combination. Can be adopted.
  • a synthetic resin and a high-concentration composition can be prepared using several types of master batches in advance, and then further mixed and diluted with the resin to obtain a predetermined resin composition.
  • the composition of the present invention achieves excellent flame retardancy and can effectively suppress bleed, and therefore can be suitably used as a molded product. That is, the flame retardant resin composition of the present invention can be suitably used as a resin composition for producing a molded product. Thereby, the molded article excellent in the flame retardance can be provided.
  • the present invention includes a flame retardant resin molded article obtained by molding the flame retardant resin composition of the present invention.
  • the molding method is not particularly limited, and known molding methods such as injection molding and extrusion molding can be used.
  • known molding methods such as injection molding and extrusion molding can be used.
  • a method using an extrusion molding machine, a sheet once prepared, a method using secondary processing such as vacuum molding and press molding, a method using an injection molding machine, and the like can be mentioned, but the present invention is highly versatile.
  • injection molding is preferred.
  • a molded product can be manufactured not only by a normal cold runner injection molding method but also by a hot runner method that enables runnerless operation.
  • gas assist injection molding, injection compression molding, ultra-high speed injection molding, or the like can be employed.
  • the molded article made of the flame-retardant resin composition of the present invention can be applied to uses that require flame retardancy in home appliances, OA products, automobile fields, and the like.
  • insulation coating materials such as electric wires and cables or various electric parts, meter boxes, lamp housings, corrugated tubes, electric wire coating materials, various automobiles such as battery parts, ships, aircraft parts, wash basin parts, toilet parts,
  • Various bathroom equipment parts, floor heating parts, lighting fixtures, various housing equipment parts such as air conditioners, roofing materials, ceiling materials, wall materials, flooring materials, TVs, radios, recording / recording equipment, washing machines, refrigerators, cleaning It is suitably used for home appliances such as a machine, rice cooker, and lighting equipment.
  • a calcium chloride tube was attached to the upper end of the condenser to prevent moisture in the air from entering the reaction system, and stirring was then started in a nitrogen atmosphere while maintaining the flask at 30 ° C. in a constant temperature water bath. After the start of stirring, triethylamine was dropped from the dropping funnel over 2 hours so that the temperature of the reaction product did not exceed 40 ° C. After the reaction ripening for 1 hour from the end of the dropwise addition, the reaction product was sampled and GC / MS was measured. As a result, the purity of the obtained reaction intermediate of the slightly yellow transparent liquid was 98% or more.
  • reaction product was converted to a diphenyl hydrogen phosphate piperazine salt represented by the above formula (19) ( DHPPP).
  • phenyl dihydrogen phosphate piperazine salt (PDHPP) 110.85 g (0.64 mol) of phenyl dihydrogen phosphate and 998 g of methanol were charged into a four-necked flask equipped with a stirrer equipped with a condenser, a dropping funnel with a side tube and a thermometer. To the dropping funnel with a side tube, 86.14 g (0.64 mol) of piperazine previously dissolved in 494 g of methanol was added. After the start of stirring, the piperazine solution was dropped from the dropping funnel over 1 hour at room temperature, and further stirring was continued for 1 hour after completion of the dropping, whereby a white cotton-like product was precipitated.
  • PDHPP phenyl dihydrogen phosphate piperazine salt
  • a flame retardant synthetic resin composition was prepared using the cyclic amine salt obtained in each of the above synthesis examples.
  • the component which comprises a flame-retardant synthetic resin composition consists of a synthetic resin and a flame retardant, and shows each component below.
  • the following components were dry blended according to the blending ratio (parts by weight) described in Tables 1 and 2, and then melt-mixed and extruded and kneaded in a twin-screw extruder, cut into strands, and pellets.
  • a flame retardant resin composition was obtained.
  • Flammability Evaluation of flammability is based on the UL94 vertical combustion test method, and 1.6 mm (1/16 inch) thickness and 0.8 mm (1/32 inch) thickness UL test pieces are prepared and a combustion test is performed. went. As a result of the UL94 vertical combustion test, a four-level evaluation of “V-0”, “V-1”, “V-2”, and “impossible” was performed.
  • Bleed test A black flat plate test piece (with 1 phr of carbon black added) having a thickness of 2 mm / 3 mm was prepared and heated at 150 ° C. for 7 days, and then the test piece was aged for 48 hours at 23 ° C. and 50% Rh.
  • test piece was subjected to an aging treatment for 48 hours under the conditions of 23 ° C. and 50% Rh, and then the presence or absence of a flame retardant or the like on the surface of the test piece was visually observed.
  • the results of the moisture resistance test are “ ⁇ (no seepage)”, “ ⁇ (some exudation is seen)”, “ ⁇ (significant seepage or blooming is observed). It was evaluated in three stages.
  • the aromatic phosphate diester when the aromatic phosphate diester, aromatic phosphate monoester and ammonium polyphosphate are used in combination, the aromatic phosphate diester has high moisture absorption, so that the aromatic phosphate diester has moisture resistance and bleed resistance. Inhibited (Comparative Examples 13 to 14).

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Abstract

L'invention divulgue un agent ignifuge pour une résine, qui ne contient pas d'halogène, présente d'excellentes propriétés ignifuges et supprime les problèmes de résistance à l'humidité et liés aux efflorescences. L'invention divulgue en particulier : un agent ignifuge contenant un sel d'amine cyclique présentant une structure chimique particulière ; et une composition de résine ignifuge qui contient ledit agent ignifuge et un composant de résine, et qui contient 1-100 parties en poids dudit sel d'amine cyclique pour 100 parties en poids de composant de résine.
PCT/JP2011/066534 2010-07-22 2011-07-21 Agent ignifuge contenant un sel d'amine cyclique, et composition de résine ignifuge WO2012011519A1 (fr)

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US9873145B2 (en) 2012-02-09 2018-01-23 Universal Can Corporation Can-manufacturing device
JP5243653B1 (ja) * 2012-09-26 2013-07-24 株式会社フジクラ 難燃性樹脂組成物、及び、これを用いた成形体
CN104804039A (zh) * 2015-04-07 2015-07-29 上海大学 有机磷系阻燃剂代谢物的合成方法

Citations (6)

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Publication number Priority date Publication date Assignee Title
GB675779A (en) * 1949-12-08 1952-07-16 Roche Products Ltd A process for the manufacture of substituted phosphorus oxyacids
JPH01143881A (ja) * 1987-11-27 1989-06-06 Lion Corp リン酸ジエステルの製造方法
JPH10175985A (ja) * 1996-12-17 1998-06-30 Tosoh Corp 含窒素有機リン酸化合物及びそれを配合してなる難燃性樹脂組成物
JP2002080633A (ja) * 2000-09-08 2002-03-19 Tokuyama Corp 難燃剤
JP2004115796A (ja) * 2002-09-25 2004-04-15 Clariant Gmbh 難燃性熱硬化性材料
JP2005120021A (ja) * 2003-10-16 2005-05-12 Asahi Denka Kogyo Kk 高純度ピロリン酸ピペラジン及びその製造方法

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GB675779A (en) * 1949-12-08 1952-07-16 Roche Products Ltd A process for the manufacture of substituted phosphorus oxyacids
JPH01143881A (ja) * 1987-11-27 1989-06-06 Lion Corp リン酸ジエステルの製造方法
JPH10175985A (ja) * 1996-12-17 1998-06-30 Tosoh Corp 含窒素有機リン酸化合物及びそれを配合してなる難燃性樹脂組成物
JP2002080633A (ja) * 2000-09-08 2002-03-19 Tokuyama Corp 難燃剤
JP2004115796A (ja) * 2002-09-25 2004-04-15 Clariant Gmbh 難燃性熱硬化性材料
JP2005120021A (ja) * 2003-10-16 2005-05-12 Asahi Denka Kogyo Kk 高純度ピロリン酸ピペラジン及びその製造方法

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BAKER, ROBERT J. ET AL.: "A Study of the Reactivity of Secondary Phosphanes with Radical Sources: A New Dehydrocoupling Reaction", HELVETICA CHIMICA ACTA, vol. 93, no. 6, 15 June 2010 (2010-06-15), pages 1081 - 1085 *

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