Classifications

• • 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
  • C09K21/14—Macromolecular materials
• • 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 System
  • C07F9/02—Phosphorus compounds
  • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
  • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
  • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
  • C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
  • C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
• • 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 System
  • C07F9/02—Phosphorus compounds
  • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
  • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
  • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
  • C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
  • C07F9/65817—Cyclic phosphazenes [P=N-]n, n>=3 n = 4
• • 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 System
  • C07F9/02—Phosphorus compounds
  • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
  • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
  • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
  • C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
  • C07F9/65818—Cyclic phosphazenes [P=N-]n, n>=3 n > 4
• • 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
  • C08K5/5399—Phosphorus bound to nitrogen
• • 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

Definitions

• TECHNICAL FIELD A cyclic phosphazene, a method for producing the same, a flame retardant containing the same as an active ingredient, a resin composition containing the same, and a molded article
• the present invention relates to a cyclic phosphazene, a method for producing the same, a flame retardant containing the same as an active ingredient, and a resin composition and a molded article containing the same.
• n is an integer of 30.
• n is an integer from: to 20.
• JP-A-58-219190 discloses a polyhydroxyphenyl ester of phospho-tolylic acid having a phenolic hydroxyl group, which is characterized by containing substantially no polycondensate or residual chlorine, and A manufacturing method is disclosed.
• the isolated cyclic chlorophosphazene is used as a raw material.However, a large amount of cyclic cyclophosphazenes can be industrially produced from a mixture of cyclic and linear cyclophosphazenes. Attempting to do so would result in the production of large amounts of halogen gas, which could significantly contaminate the environment, and would result in poor workability. In addition, even when the cyclic phosphazenes separated and purified are reacted with phenols, the cyclic phosphazenes are cleaved during the reaction to form chain phosphazenes or unsubstituted chlorine.
• the desired cyclic aryloxyphosphazene cannot be obtained, for example, a phosphazene having a residual phosphazene remains or a cyclic phosphazene is hydrolyzed during post-treatment to form a chain phosphazene.
• the obtained phosphonitrile phenolic ester was obtained by cleaving cyclic phosphazenes and was formed by chain phosphazenes. Since it contains phosphazene containing substituted chlorine, it is not a solid but a yellow viscous liquid and cannot be purified.
• phosphazenes having a smaller halogen content than conventional methods can be obtained, but the halogen content is still as high as about 100 ppm.
• cyclic halogenated phosphazenes are used as raw materials, part of the cyclic phosphazenes is inevitably cleaved during the reaction to form chain phosphazenes.
• the reaction is carried out by using 1.1 times of Na salt of monomethoxyphenol with respect to 1 chlorine of phosphonitrile halide.
• the reaction is not completed and unsubstituted organic halogen compounds remain.
• the phosphazene represented by the general formula (1) does not contain a halogen in its structural formula, it is not always possible to convert all of the substituents into an aryloxy group, Some compounds of the product are in a state where halogen remains in the structural formula. In particular, it is difficult to replace the last one halogen remaining in the compound, and it is not possible to completely replace the halogen even after a reaction time of about 250 hours.
• the phosphazene represented by the general formula (1) is cyclic in its structural formula, but the conventional production method cannot always maintain the cyclic structure of the general formula (1), and a part of the product is The state changes to a chain compound.
• resin additives there are flame retardants, ultraviolet absorbers, antioxidants, plasticizers, nucleating agents, etc., but these have not only their own effects, but also stability during molding and contamination of the mold, If you do not satisfy various factors, such as the condition of the molded product, especially the absence of bleed-out on the resin surface, it will not work.
• halogen-containing compounds which have been the main substances in conventional flame-retarding of electric wires and cables, are used alone or in combination with antimony compounds such as antimony oxide to form a flame retardant, which is then incorporated into the resin.
• Flame-retardant resin compositions are mainly used, but these generate halogen-based gases during combustion or molding. It is a problem to do it. Furthermore, it is said that the generation of these gases often impairs the electrical and electrical characteristics. Therefore, a flame-retardant resin composition that does not generate these halogen-based gases at the time of combustion or molding has been required.
• metal hydrates and phosphorus-based flame retardants (phosphate esters, ammonium polyphosphate, phosphazenes, etc.) have been used as non-halogen flame retardants to meet these requirements.
• metal hydrates such as aluminum hydroxide and magnesium hydroxide
• the endothermic reaction of dehydration pyrolysis at the resin combustion temperature occurs in the temperature range that overlaps with the thermal decomposition and combustion start temperatures of the resin, increasing the flame retardant effect.
• metal hydrate alone does not have a significant effect of imparting flame retardancy, it must be blended in a large amount, and this has the disadvantage of adversely affecting the mechanical strength of the resulting molded article. Has occurred.
• phosphorus-based flame retardants have not only the flame-retardant effect but also excellent properties such as working as a plasticizer or an antioxidant when added to resin.
• triaryl phosphates such as triphenyl phosphate / tricredinolephosphate and cresyldiphenylenophosphate have a low boiling point, so they volatilize during molding, contaminate the mold, and have drawbacks such as bleeding out onto the resin surface.
• the condensation type phosphate ester solves the above disadvantages, if the catalyst used during production remains in this phosphate ester, not only the phosphate ester but also the resin will be decomposed at the time of molding, resulting in lower performance. It is known to cause or sometimes become gel-like, and significantly reduce productivity.
• Ammonia polyphosphate has disadvantages in that heat stability is poor and processing conditions are limited, and low phosphorus content requires a large amount of blending.
• An object of the present invention is to solve the above-mentioned drawbacks of the prior art, to obtain a cyclic phosphazene having a very low content of lipogen and a low content of chain phosphazene without repeating purification.
• An object of the present invention is to provide a method, a flame retardant containing the same as an active ingredient, a resin composition, and a molded article. Disclosure of the invention
• the present inventors have conducted intensive studies on the reaction conditions and purification conditions that do not substantially contain chain phosphazenes in the product in the production of phosphazene.
• a cyclic aryloxyphosphazene mixture is obtained, which is separated and purified by crystallization to obtain a halogen-containing phosphazene in which the linear phosphazenes are unsubstituted.
• cyclic phosphazenes having an extremely low halogen content and an extremely low content of chain phosphazenes can be obtained by acting as an excellent crystallization solvent for dissolving.
• the present inventors have found that cyclic phosphazenes have a greater flame retardant effect than cyclic phosphazene mixtures containing chain phosphazenes. It has been led to completion.
• a first aspect of the present invention is the following general formula (1)
• Q is a halogen and / or aryloxy group, and n is an integer of 1 to 20.
• a second aspect of the present invention is that the content of the chain phosphazenes is 5.0% by weight. Is below C relating to the cyclic phosphazenes according to claim 1
• a third aspect of the present invention is to provide the following general formula (1)
• Q is a halogen and / or aryloxy group, and n is an integer of 1 to 20.
• a cyclic phosphazene represented by the general formula (1) obtained by separation and purification from a phosphazene composition comprising a chain phosphazene represented by the formula:
• a fourth aspect of the present invention relates to the cyclic phosphazenes according to any one of claims 1 to 3, wherein Q in the general formula (1) is an aryloxy group and contains substantially no halogen.
• a fifth aspect of the present invention relates to the cyclic phosphazenes according to claim 4, wherein the halogen content is 50 ppm or less.
• a sixth aspect of the present invention provides the following general formula (1)
• Q is a halogen and Z or aryloxy group, and n is an integer of 1 to 20.
• a cyclic phosphazene represented by the general formula (1) is separated and purified by crystallization from a phosphazene composition comprising a chain phosphazene represented by the formula: and the cyclic phosphazenes according to any one of claims 1 to 5. And a method for producing the same.
• a seventh aspect of the present invention is to provide the following general formula (1)
• Q is a halogen and / or aryloxy group, and n is an integer of 1 to 20.
• the cyclic phosphazenes represented by the general formula (1) are separated and purified by crystallization from a phosphazene composition comprising a chain phosphazene represented by the following formula (1) to produce the cyclic phosphazenes according to the claim 4 or 5.
• a phosphazene composition comprising a chain phosphazene represented by the following formula (1) to produce the cyclic phosphazenes according to the claim 4 or 5.
• An eighth aspect of the present invention relates to a flame retardant containing a cyclic phosphazene according to any one of claims 1 to 5 as an active ingredient.
• a ninth aspect of the present invention relates to a resin composition containing the cyclic phosphazenes according to any one of claims 1 to 5.
• a tenth aspect of the present invention relates to a molded article comprising the resin composition according to claim 9.
• the cyclic phosphazenes of the present invention are cyclic phosphazene compounds represented by the general formula (1) and mixtures thereof, and are characterized by being substantially free of chain phosphazenes represented by the general formula (2). It is assumed that.
• the mixture of cyclic and chain aryloxyphosphine used in the present invention can be obtained by reacting a mixture of cyclic and chain halogenated phosphazene with phenols by a known method.
• a solution of a mixture of cyclic and chain phosphazene halides or a solution of cyclic halogenated phosphazenes is added dropwise to a slurry of an alkali metal phenolate, followed by reaction.
• the mixture of cyclic and chain phosphazene which is used as a raw material for producing the mixture of cyclic and chain aryloxyphosphazenes used in the present invention, is, for example, a cyclic compound represented by the general formula (3).
• the mixture is not particularly limited as long as it is a mixture of the halogenated phosphazenes and the chain halogenated phosphazenes represented by the general formula (4).
• the mixture of cyclic and chain aryloxyphosphazenes obtained here depends substantially on m and n in the compounds of the general formulas (3) and (4) as the raw materials.
• the mixture of cyclic and linear aryloxyphosphazenes is crystallized in a solvent containing an aromatic non-polar solvent, whereby the halogen content is extremely low and the linear aryloxyphosphazene is crystallized.
• a cyclic aryloxyphosphazene having an extremely low content of phosphazenes can be obtained. Refining the cyclic aryloxyphosphazene in a similar manner does not reduce the halogen content. This suggests that the chain aryloxyphosphazene acts as a solvent for selectively dissolving the halogen-containing aryloxyphosphazenes, resulting in an excellent purification effect.
• the purification method of the present invention involves the use of cyclic and linear halogenated phosphazene mixtures. This is a very effective method for obtaining cyclic aryloxyphosphazenes having a very low halogen content from a phosphazene mixture in which the condensation reaction with phenols is not completed and the halogen component remains. is there.
• a mixture of cyclic and chain-like aryloxyphosphazenes is crystallized in a solvent containing an aromatic non-polar solvent to form a cyclic and chain-like aryloxyphosphazene having a very low content of chain-like aryloxyphosphazenes. Allyloxyphosphazene is obtained.
• a conventional decoloring treatment such as an activated carbon treatment or a clay treatment may be performed.
• aryloxy group examples include unsubstituted or halogen, methyl, ethyl, n-propyl, iso-propyl, tert-butyl, tert-octyl, 2,3-dimethyl, 2,4-dimethyl Group, 2,5-dimethyl group, 2,6-dimethyl group, 3,5-dimethyl group, hydroxy group, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, phenyl group, etc. And a phenyloxy group.
• the alkali metal phenols may be used alone or in combination of two or more. When two kinds are used in combination, it is natural that there are two kinds of aryloxy groups in the product.
• tetramethylammonium chloride tetraethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydroxide, tetrabutylammonium-ammonium sulfate, trilaurylmethylammonium- Demyl chloride, di-hardened tallow alkyl dimethyl ammonium acetate, trimethylphenylammonium chloride, benzinoletrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, distearyldimethylammonium chloride And the like.
• the flame retardant according to the present invention can be expected to have a further effect when the phosphazenes are mixed and used, or when another flame retardant is used in combination.
• flame retardant may be added to the flame retardant according to the present invention.
• Other flame retardants include metal hydroxide compounds, silicates, organosilicon compounds, fluororesins, inorganic flame retardants, phosphorus flame retardants, halogen flame retardants and nitrogen flame retardants. Flame retardants may be used, and these may be used in combination.
• the metals of the hydroxyl group metal compound which may be added to the flame retardant of the present invention include Group 2 and Group 13 of the Periodic Table of the Elements (Group 2 out of Groups 1 to 18 of the new IUPAC format, Metal belonging to Group 13 and corresponding to the conventional Periodic Tables IIa and IIIb) and zinc, and preferably magnesium and aluminum.
• hydroxyl compounds may be the metal hydroxide compound alone, but may be an organic compound such as a higher aliphatic carboxylic acid, a hydrogenated oil or a higher aliphatic carboxylic acid, periodic table group 1 , 2nd, 12th or 13th group (New I UPAC format 1st, 2nd, 12th or 13th group of 1st to 18th, and the conventional periodic table Ia, IIa, lib or (Corresponding to the Illb family).
• the gold hydroxide The genus compounds, especially magnesium hydroxide, are Kismer 5A, 5B, 5E, 5J (trade name, manufactured by Kyowa Chemical), Madashizu N-3, N_l, water mug 200, 10 and 10A , Starmag UM, M, L, S, C, CY (trade name, manufactured by Kamishima Chemical), FR-200 (trade name, Bromochem., Manufactured by FIRST), etc. May be.
• silicates examples include sodium silicate, sodium metasilicate, sodium orthosilicate, water glass, magnesium silicate, potassium silicate, potassium magnesium silicate, calcium silicate, aluminum silicate, and silicate.
• Three-dimensional silicates such as mica and clay minerals include silicon dioxide, feldspar and zeolite.
• fluororesin examples include polytetrafluoroethylene resin (PTFE), tetrafluoroethylene-hexafluoropropene.
• PTFE polytetrafluoroethylene resin
• FEP tetrafluoroethylene-hexafluoropropene.
• FEP tetrafluoroethylene-perfluoroalkylvinyl alcohol copolymer resin
• ETFE tetrafluoroethylene-ethylene copolymer resin
• CFE polytrifluoroethylene chloride resin
• PVDF polyvinylidene fluoride resin
• Examples of the inorganic flame retardant that may be added to the flame retardant of the present invention include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, zinc borate, magnesium oxide, calcium oxide, and the like. .
• Examples of the phosphorus-based flame retardant that may be added to the flame retardant of the present invention include red phosphorus, ammonium polyphosphate, triphenyl phosphate, triethyl phosphate, trimethinole phosphate, tricresyl phosphate, and trixylenolinole.
• Phosphate cresinolephenyl phosphate, tris (3-hydroxypropyl) phosphinoxide, glycidyl-1- ⁇ -methyl-] 3-dibutoxyphosphinylpropionate, dibutylhydroxymethylphosphonate, dibutyl Butoxyphosphinylpropylamide, dimethylmethylphosphonate, di (polyoxyethylene) -hydroxymethylphosphonate, aromatic condensed phosphate, and the like.
• Red phosphorus may be used alone, or may be coated with an appropriate inorganic compound or organic compound, or may be diluted with a non-halogen organic polymer composition.
• Commercial products of the red phosphorus include Nova Red 120, 120 UF, 120 UFA, Nova Excel ST, W, MG, RX series, Nova Palettes (trade name, manufactured by Rin Kagaku), Hishigard CP, CP-15, UR-15 , TP-10, Safe TP-10 (manufactured by Nippon Chemical), RP-120 (manufactured by Suzuhiro Chemical), etc. are commercially available and can be used as they are.
• nitrogen-based flame retardant examples include guanidine sulfamate, guanidine phosphate, guanyl urea phosphate, melamine phosphate, dimelamine phosphate, melamine borate, and melamine cyanurate.
• Hindered amine flame retardants TI NUV IN 123, TI NUV INXT, TI NUV IN NOR 371, Flame stab NOR 116, TI NUV IN 770, TI NUV IN 622, CH I MAS SORB 944, CH I MAS SORB 119 and CH I MAS SORB 2020.
• the flame retardant according to the present invention may further contain, for example, a conventional additive, for example, a filler, a plastic reinforcing agent, a lubricant and the like.
• fillers examples include calcium carbonate, titanium oxide, clay, calcined clay, silane-modified clay, talc, myriki, silica, wollastonite, bentonite, Diatomaceous earth, silica sand, pumice powder, slate powder, alumina white, aluminum sulfate, barium sulfate, lithium, calcium sulfate, molybdenum disulfide, surface treatment filler, recycled rubber, rubber powder, ebonite powder, shellac, etc. .
• plastic reinforcing agent examples include, for example, mica powder, graphite, glass fiber, glass sphere, hollow volcanic glass, carbon fiber, hollow carbon, anthracite powder, artificial cryolite. , Silicone resin powder, silica spherical particles, polyvinyl alcohol fiber, aramide fiber, alumina fiber, high-strength polyac Related fibers and the like.
• Lubricants that may be added to the flame retardant according to the present invention include, for example, paraffin wax, liquid paraffin, paraffin-based synthetic wax, polyethylene wax, composite wax, montan wax, silicone oil, stearic acid, lithium stearate, stearic acid Sodium, Magnesium stearate, Potassium stearate, Aluminum stearate, Calcium stearate, Zinc stearate, Hydroxiestearic acid, Magnesium 12-hydroxyxiestearate, Calcium 12-hydroxyxiestearate, 12-Hydroxystearin Acid palm, zinc 12-hydroxyxiestearate, calcium laurate, lauric acid, potassium laurate, zinc laurate, etc., coconut oil, palm kernel oil, disin oil, cod liver oil, Examples include whale oil, palm oil, cottonseed oil, olive oil, peanut oil, soybean oil, linseed oil, castor oil, and hydrogenated hydrogenated oils.
• the resin composition according to the present invention may further contain, for example, conventional additives.
• the resin composition may contain an antioxidant, a light stabilizer, and a metal deactivator.
• Various fillers, conductive powders and the like may be contained.
• examples of the acid proofing agent which may be added include, for example, 2,6-di-tert-butyl-14-methinolephenolene, 2-tert-butyl-1,4 6-dimethylphenol, 2,6-di-tert-butyl 4-enotinolephenore, 2,6-di-tert-butynole 4-n-butynolepheno, 2,6-di-tert-butyl 4-isobutylphenol, 2,6-dicyclopentyl-4-methylinophenol, 2- ( ⁇ -methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4 , 6-Tricyclohexylphenol, 2,6-Dinonyl-4-methylphenol, 2,6-Ditert-butynole_4—Methoxymethinolephenol, 2,4-Dimethyl-1-6
• Light stabilizers which may be added in addition to the phosphazene composition according to the present invention include, for example, 2_ ⁇ 2'-hydroxy-5'-methylphenyl) benzotriazonone, 2- (3 ', 5'-di-1 tert-butynole-1-hydroxyphenyl, benzotriazonole, 2- (5'-tert-butyl-2'-hydroxyphen-nor) benzotriazole, 2- ⁇ 2'-hydroxy-5 '-(1,1,1, 3,3-tetramethylbutyl) phenyl] benzotriazole, 2 _ (3 ', 5'-di-tert-butynole 2'-hydroxypheninole) 1-5-cyclobenzotriazonole, 2- 3'-tert-butyl-2'-hydroxy-1 5'-methinolephenyl) -1-5-benzobenzotriazole, 2- ⁇ 2'-hydroxy-1 4'-octoxyphenyl) benzotriazole
• the metal deactivator which may be added in addition to the phosphazene yarn composition of the present invention includes, for example, N, ⁇ '-diphenyldioxalate diamide, ⁇ ⁇ -saltyl-N'-salicyloylhydrazine, N , N'-bis (salicyloyl) hydrazine, ⁇ , N'-bis (3,5-di-tert-butyl-14-hydroxyphenylpropioel) hydrazine, 3-salicyloylamino-1,2 , 3-triazole, bis (benzylidene) oxalic acid hydrazide, isophthalic acid dihydrazide, N, N '-diacetal monoadipate dihydrazide, N, ⁇ '-bissalicyloyl oxalic acid dihydrazide, ⁇ , N 'bis Salicyloylthiopropionate dihydrazi
• Examples of the resin constituting the resin composition containing the phosphazene composition according to the present invention include, for example, polyethylene, polypropylene, ethylene-propylene copolymer, polybutylene, polymethylpentene, ethylene monoacetate copolymer, and ethylene-methyl acrylate.
• (Ethyl) copolymer AS resin, ABS resin, PC resin, PC. ABS alloy, polystyrene, PET, PC. PET alloy, polyphenylene ether resin, polyphenylene sulfide resin, polybutadiene resin, polybutylene terephthalate resin
• Methacrylic resin polyamide resin, epoxy resin, diaryl phthalate resin, silicone resin, unsaturated polyester, and the like.
• the resin composition of the present invention is used for various molded articles, and produces a coating, particularly a fire protection coating for electric wires, cables, electric components, mechanical components, plugs, mounts, casings, covers, and exteriors. It is useful as a material for performing BEST MODE FOR CARRYING OUT THE INVENTION
• Halogen contained in the obtained phosphazenes was analyzed by coulometric titration.
• the obtained phosphazene was thermally decomposed, captured as a hydrogen halide in an absorbing solution, and when the silver equivalent to the halogen was electrolyzed into silver halide, the amount of halogen was determined from the amount of electricity.
• the reaction was carried out in the same manner as in Example 1. After completion of the reaction, 20 OmL of water was added to the flask to dissolve the inorganic salt, and then the organic layer was separated using a separating funnel. The organic layer was neutralized with 75% sulfuric acid, washed with water, and the toluene was distilled off to obtain 113.4 g of hexafenoxyphosphazenes as pale yellow crystals.
• Kisa phenoxyethanol phosphazene compound to that obtained was subjected to purity analysis by HP LC, the hexa phenoxyethanol phosphazene 94.44 wt 0/0, chain phenoxyethanol phosphazene 5.56 weight 0 /. Met.
• the obtained phenoxyphosphazene composition was analyzed for chlorine by coulometric titration, the halogen content was 60 ppm.
• Tetrahydrofuran and 42.0 g (1.05 mol) of 60% NaH were added to a flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel, followed by stirring at room temperature.
• a solution obtained by diluting 98.8 g (1.05mo 1) of phenol with 180 mL of tetrahydrofuran was gradually dropped from a dropping funnel. After completion of the dropwise addition, the mixture was heated and stirred at 40 ° C. for 30 minutes. Next, the temperature was returned to room temperature.
• the obtained solution of the Na salt of phenol in tetrahydrofuran was directly used in the next reaction.
• Example 2 The reaction was performed under the same conditions as in Example 2 except that 13.5 g of p-cresol was used instead of 98.8 g of phenol. As a result, 105.8 g of a cyclic p-tolyloxyphosphazene composition was obtained. The purity of the obtained phosphazene was analyzed by HP LC. Hexa p-tolyloxyphosphazene 73.44% by weight and octa p-tolyloxyphosphazene 22.98% by weight. /.
• Example 1 ring obtained in full We Roh carboxymethyl phosphazene 10.0 wt 0/0, polypropylene 90.0 wt 0/0 was inserted into the mixer as a polyolefin-in system ⁇ was kneaded at 180 ° C. The obtained mixture was molded by a compression molding machine (185 ° C, 3 minutes), and the obtained sheet was used to evaluate the flame retardancy. The results are shown in Table 1.
• Example 6 In the same manner as in Example 6, the phosphazene compositions obtained in Examples 2 to 5 were used in place of the phenoxyphosphazene obtained in Example 1 to evaluate the flame retardancy. The results are shown in Table 1. Comparative Example 4
• Example 6 In the same manner as in Example 6, the phosphazene composition obtained in Comparative Example 1 was used in place of the phenoxyphosphazene obtained in Example 1, and the flame retardancy was evaluated. The results are shown in Table 1.
• oxygen index in a given test conditions, say the value of minimum oxygen concentration necessary for a material to sustain combustion (capacity 0/0). For example, if there is a sample with an oxygen index of 25.0, this means that if the oxygen concentration is ignited at 25.0% or more, it will burn, and if it is less than 25.0%, it will self-extinguish (the same applies hereinafter). . Considering that the oxygen concentration in the atmosphere is about 20.9%, if the oxygen index is higher than 20.9, it means self-extinguishing under natural environment, and the flame retardant. It is clear that the effect is great.
• Example 1 It annular full obtained in Example 2 Roh carboxymethyl phosphazene compound 3.2 weight 0/0, hydroxide mug Neshiumu 32.3 wt 0/0, polypropylene 64.5% by weight was inserted into the mixer as a polyolefin resin, Kneaded at 180 ° C. Flame retardants were evaluated using sheets obtained by molding with a compression molding machine (185 ° C, 3 minutes) using the obtained mixture. The results are shown in Table 2.
• Example A Hydroxide Maguneshiumu 32.3 wt 0/0, down 64.5 wt% annularly Hue down 3.2% by weight of their respective obtained in Example 2 (Sample A), an annular Fuenokishiho obtained in Comparative Example 1 2% by weight (sample B) It was inserted into a mixer, and a sheet was prepared in the same manner as in Example 11 to obtain a test piece. The prepared test piece was burned under the following test conditions in which dioxin is easily generated, and the amount of dioxin contained in the exhaust gas was measured (based on JI SK 03111). The results are shown in Table 3.
• the phenoxyphosphazene of the present invention can be said to be an environmentally friendly flame retardant because the amount of dioxin generated is very small even under dioxin generation and combustion conditions.
• the toxic equivalents (TEQ) in the table are the toxic equivalents of 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-Te CDD). 3, 7, 8—The value converted to the toxicity of Te CDD.
• PCDDs are polychlorodibenzo-p-dioxins
• PCDFs are polychlorodibenzofurans, both of which are dioxins. The invention's effect
• the present invention provides substantially halogen-free cyclic phosphazenes having a halogen content of 50 ppm or less, even though a material containing halogen is used as a raw material. I was able to. Therefore, dioxins are not generated even when resins that use this as a flame retardant are burned.
• a high-purity cyclic phosphazene having a chain phosphazenes content of 5.0% by weight or less, preferably 1.0% by weight or less, and particularly preferably 0.1% by weight or less can be provided without repeating purification.

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• 2002
  • 2002-06-05 EP EP02736007A patent/EP1403273A4/en not_active Withdrawn
  • 2002-06-05 US US10/479,235 patent/US7317046B2/en not_active Expired - Fee Related
  • 2002-06-05 WO PCT/JP2002/005554 patent/WO2002098886A1/ja active Application Filing

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