JP2007091606A - Organic phosphorus compound, flame retardant and flame-retardant organic polymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel organic phosphorus compound, a flame retardant mainly composed of the same and a flame-retardant organic polymer composition comprising the same while containing no halogen. <P>SOLUTION: The novel organic phosphorus compound is represented by general formula 1. The flame retardant is mainly composed of the same. The flame-retardant polymer composition comprises the same. In formula 1, R is an anilino group, indolyl group, indolinyl group, diphenylamino group, carbazolyl group, phenothiazino group, benzohydryl group or 9-fluorenyl group, each optionally bearing a substituent group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an organic phosphorus compound, a flame retardant, and a flame retardant organic polymer composition. More specifically, the present invention relates to a novel organic phosphorus compound, a flame retardant containing the same as a main component, and a flame retardant organic polymer composition containing the same and not containing an organic halogen compound.

  Conventionally, as organic flame retardants for organic polymer compounds, organic halogen compounds are attractive because of their great flame retardant effect, wide range of applicable organic polymer compounds, ease of application or low cost, etc. Organic halogen compounds have been widely applied to organic polymer compounds as flame retardants. Chlorine or bromine compounds have been put to practical use as organic halogen compounds, and various types of compounds have been used in large quantities as flame retardants depending on the purpose.

  However, recently, an organic polymer composition containing an organic halogen compound as a flame retardant generates a toxic gas in the event of a fire and causes damage to the human body. Furthermore, it is clear that polymer compositions containing halogen-based flame retardants not only generate acid gases that corrode incinerators during their incineration, but also discharge harmful substances with high environmental pollution. Has been. Therefore, the industry that uses flame retardants dislikes the use of such halogen flame retardants, and there is an active movement to replace halogen flame retardants with other flame retardants, especially organophosphorus compounds. Recently, it has attracted particular attention.

  However, while halogen-based flame retardants are effectively applied to a wide range of organic polymer compounds, conventional organic phosphorus compounds are effective as flame retardants such as polyphenylene oxide, phenol resin, polycarbonate resin, epoxy resin. Or it is limited to the organic polymer compound which can produce | generate a carbide | carbonized_material comparatively easily at the time of combustion like cellulose. Therefore, in many organic polymer compounds in which the organophosphorus compound cannot function effectively as a flame retardant, it is still difficult to switch the halogen-based flame retardant to another flame retardant.

  It is understood that the difference in effect between the organic halogen compound-based flame retardant and the organophosphorus compound-based flame retardant is a difference in the mechanism of flame retardant. According to many literatures, the flame retardant mechanism of organic halogenated flame retardants is explained as a fire extinguishing action of flame, that is, a stable halogen radical generated in a high-temperature gas phase, and is generally supported. Has been. And it can also be understood as an explanation of the reason why it is effective as a flame retardant for many kinds of organic polymer compounds that burn and raise a flame. On the other hand, the flame retardant mechanism of organophosphorus compound-based flame retardants is that the thermal energy of the fire source or air is shielded by the carbide film containing phosphorus that forms on the surface during combustion due to the promotion of carbonization of organic polymer compounds by phosphorus compounds. Any organic polymer compound that is effective as an organophosphorus compound-based flame retardant is relatively easy to form a carbide film during combustion, and the organophosphorus compound itself contains phosphorus during combustion. This fact is well supported by the fact that the more easily the surface film is formed, the higher the flame retardant effect.

  Some documents other than those based on organic halogen compound flame retardants have been discovered in which the flame retardant mechanism is considered to be a radical extinguishing action of the flame. For example, in Patent Document 1 and Patent Document 2, 2,3-dimethyl-2,3-diphenylbutane is used simultaneously with the organic phosphorus compound, and in Patent Document 3, 2,3-dimethyl-2,3-diphenylbutane is used together with the bromine compound. Therefore, synergistic flame retardancy due to the generation of radical pairs in the flame of this compound is expected. Patent Document 4 and Patent Document 5 disclose specific flame retardant effects of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-benzyl-10-oxide. The specificity of this compound cannot be found in ordinary organophosphorus compounds, and it is also excellent in non-carbonized organic polymer compounds in which other organophosphorus compounds hardly function as flame retardants. An effect has been found. This is the fire extinguishing action of the flame by the radical pair of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl radical and the benzyl radical which it produces in the flame. It is not difficult to infer. And nonpatent literature 1 has description as a flame retardant of bi-9-fluorenyl, and it is also inferring that this flame-retardant effect will be a fire extinguishing action by the 9-fluorenyl radical produced | generated in a flame. Not difficult. Furthermore, Patent Document 6 uses an organic peroxide having a relatively high decomposition temperature, such as dicumyl peroxide or cumene hydroperoxide, as a flame retardant aid for expanded polystyrene. The synergistic fire extinguishing action of the radical is implied.

However, at present, there are very few literature examples or practical examples of flame retardants having a flame retardant mechanism by radicals other than halogen radicals, and this seems to be a technical field that needs to be greatly developed in the future.
JP2003-34749A JP2004-115763A JP2000-1563A JP2002-275473A JP2004-292495A JPH11-130898A Lattimer & Kroenko: J. Polymer Sci. , 26, 1191 (1981)

  The object of the present invention is to provide a novel organophosphorus compound having a high flame retardant effect, a flame retardant containing the same as a main component, and a flame retardant organic polymer composition containing the same and not containing an organic halogen compound Is to provide.

  According to the present invention, there are provided a novel organophosphorus compound represented by the general formula 1, a flame retardant containing the same as a main component, and a flame retardant organic polymer composition containing the same.

(In formula 1, R represents an anilino group, indolyl group, indolinyl group, diphenylamino group, carbazolyl group, phenothiazino group, benzhydryl group or 9-fluorenyl group which may have a substituent.)

  Here, the anilino group which may have a substituent is an anilino group, o-toluidino group, m-toluidino group, p-toluidino group, o-anisidino group, p-anisidino group, o-phenetidino group, p- Phenethidino group, 1-naphthylamino group, N-methylanilino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-allylanilino group and the like are indicated.

  As predicted from its chemical structure, a high degree of flame retardant effect on a wide range of organic polymer compounds possessed by the organophosphorus compound represented by general formula 1 (hereinafter referred to as general formula 1) It is thought that this is a fire extinguishing action by a stable radical pair generated by splitting at This is similar to the flame retardant mechanism of halogen compounds. However, splitting into radical pairs such as halogen molecules and peroxides is homolytic and easy, whereas splitting of the organophosphorus compound of the present invention into radical pairs is heterolytic. Nevertheless, the reason why the splitting is very smooth is thought to be because the unpaired electrons of the radical pair generated by the splitting are stabilized by the π electrons of the benzene ring adjacent to both. Therefore, the general formula 1 is characterized in that a phosphorus atom and another radical atom predicted to be split, that is, a radical atom of R are both bonded to at least one benzene ring, and this is also the technical idea of the present invention. This is also the reason for limiting the structure of general formula 1.

  The splitting temperature of compounds that are easy to split into radical pairs, such as organic peroxides with a homolytic splitting mode or some azo compounds, is generally below 150 ° C and is too low for use as a flame retardant. Temperature. On the other hand, the general formula 1 is a heterolytic splitting mode of a compound having a chemical structure capable of splitting into a stable radical pair, and the splitting temperature into the radical pair is higher than 200 ° C. It is suitable for use as a flame retardant. Incidentally, the splitting method is so easy that the two radical pairs generated by splitting are more stable together and is preferable for use as a flame retardant. Assuming that the group corresponding to the R position in the general formula 1 is a methyl group, a benzyl group, a benzhydryl group, or a 9-fluorenyl group, the 9,10-dihydro-9-oxa-10-phos generated by these splits. The stability of radicals paired with phafenathlen-10-oxide-10-yl radicals is in the order of methyl << benzyl <benzhydryl <9-fluorenyl, and the most unstable methyl group is split into radical pairs. It is difficult, and the radical flame retardant effect is hardly expected. On the other hand, the benzhydryl radical and the 9-fluorenyl radical are stabilized by two benzene rings, and the splitting into radical pairs is smoother, and the flame retardant effect in the flame is the case of the benzyl group. Higher than. This is similar to the fact that the stability of halogen radicals is in the order of F << Cl <Br <I, and the magnitude of the flame retardant effect is also in this order.

  The flame retardant mainly composed of the organophosphorus compound according to the present invention is also an organic polymer compound having a small molecular weight and a large volatility, like a polymer additive such as a plasticizer, an antioxidant or an ultraviolet absorber. It is not preferable because it not only pollutes the work environment by volatilizing at the high temperature mixing or molding process, but also gradually evaporates during the long-term use of the organic polymer composition and gradually reduces the effect of addition. . For example, 2,3-dimethyl-2,3-diphenylbutane is known to split into two cumyl radicals in a flame, but its molecular weight is very small at 238.37, and the flame retardant effect is sufficiently exerted. If an amount to be added is added to the organic polymer compound and mixed or molded at a high temperature, it will volatilize much during the process, making the working environment extremely uncomfortable. On the contrary, if the molecular weight is too large, it is less likely to volatilize during combustion, and therefore, the formation of radical pairs in the flame is small, so that the addition effect is not fully exhibited and is not preferable.

  The volatility of an organic compound is not dependent only on its molecular weight, but when comparing similar compounds, its molecular weight can be used as a measure of volatility. Of the general formula 1, organophosphorus compounds that do not form hydrogen bonds have high volatility, and the molecular weight is most preferably in the range of 320 to 430 for the purpose of use of the present invention. The volatility of the compound that forms a hydrogen bond is smaller than that, and the molecular weight is most preferably in the range of 300 to 400. However, these preferred molecular weight ranges are merely guidelines obtained from many experiences of the present inventors. By the way, 9,10-dihydro-9-oxa-10-phosphaphenalene-10-benzyl-10-oxide does not form a hydrogen bond, and its molecular weight is slightly smaller as 306.3. It is known that it volatilizes during the molding process and emits its unique unpleasant odor.

  Ordinary organophosphorus compounds have the effect of promoting the formation of carbides during the burning of organic polymer compounds, which is effective as a flame retardant for some organic polymer compounds. However, although the general formula 1 is a kind of organophosphorus compound, it is different from other organophosphorus compounds, and the carbonization promoting action during combustion of the organic polymer compound is not large. Therefore, other organic phosphorus compounds, such as polycarbonate resins, epoxy resins, phenol resins, polyphenylene oxide resins or celluloses, which are effective in organic carbide compounds, which are relatively easy to produce carbides, are included together with the general formula 1 of the present invention. If the organophosphorus compound is added, a synergistic effect of radical extinguishing action and carbonization promoting action is brought out, and higher flame retardancy is given.

  Among other organic phosphorus compounds, those having one phosphorus atom in the molecule include triphenyl phosphate, tricresyl phosphate, diphenyl xylyl phosphate, phenyl dixylyl phosphate, diphenyl-o-xenyl phosphate or diphenyl. Examples thereof include phenylphosphonates, which are already known and their production methods are also known. Organic phosphorus compounds having two or more phosphorus atoms in the molecule are described in JPH5-1079A, JPH6-306277A, JPH8-277344A, JPH8-301844A, JPH10-45774A, JPH11-343382A, JP2004-115763A, etc. The manufacturing method is also clarified. For the purpose of giving a synergistic effect to the present invention, other organic phosphorus compounds which are particularly preferably used are those having two phosphorus atoms in the molecule.

  The organic polymer compounds to which the flame retardant of the present invention is applied are wide-ranging and include polyolefins, polybutadiene, polystyrene, acrylonitrile / butadiene copolymer, acrylonitrile / styrene copolymer, styrene / butadiene copolymer, acrylonitrile / butadiene / Styrene graft copolymer (ABS resin), polymethyl methacrylate, methyl methacrylate / butadiene / styrene graft copolymer (MBS resin), polyisoprene, butadiene / styrene graft polymer, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycarbonate resin, polycarbonate resin / ABS resin polymer alloy, polyamides, polyurethanes, phenol resin, melamine resin, epoxy resin, unsaturated poly Examples include conventional resins such as polyolefins, polystyrene, ABS resin, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyamides, polycarbonate resin, or polycarbonate resin / ABS resin polymer alloy. The application of the phosphorus compound flame retardant to an organic polymer compound having a relatively small flame retardant effect is the most characteristic of the effect of the present invention.

  The flame retardant organic polymer compound according to the present invention is often put into practical use mainly as a film or an extruded product. Usually, an organic polymer compound and a flame retardant are melt-mixed to form a film or an extruded product. Polyethylene terephthalate and polyamides are sometimes used as films or molded articles, but are often used as textiles in textiles. As a method for producing flame retardant fibers, a method in which a flame retardant is melt-mixed with polyethylene terephthalate or polyamide and then spinning is performed, and in particular, fibers or fabrics that do not contain a flame retardant in polyethylene terephthalate contain a flame retardant. After treating with a solution or water-based emulsion, two methods can be employed: a method of producing a flame-retardant fiber or woven fabric by heat-treating at 100 ° C. or higher to fix the flame retardant inside the fiber. In addition to general molded products, polystyrene is often used as expanded polystyrene. As shown in JPH-137276A, a method for producing a flame retardant expanded polystyrene is to add a foaming agent and a flame retardant fine particle to an aqueous suspension of polystyrene and impregnate them with polystyrene particles. A method of obtaining a flame retardant product through a process is adopted, and this method is also used in the present invention.

  Usually, when general formula 1 is added as a flame retardant to an organic polymer compound, the amount added is 0.5 to 25% by weight, more preferably 1 to 20% by weight and most preferably 2 to 15% by weight. Other organophosphorus compounds used simultaneously with general formula 1 can be optionally added, but if necessary, 2 to 15% by weight, more preferably 3 to 14% by weight and most preferably 5 to 12% by weight. Added. When the amount of the former added is 0.5% by weight or less, a sufficient flame retardant effect or a synergistic effect thereof cannot be obtained, and when the amount added is 25% by weight or more, a further effect cannot be obtained. This is not preferable because the physical properties of the resin deteriorate. Further, if the latter addition amount is 2% by weight or less, a sufficient synergistic effect with the former is not expected, and if it is 15% by weight or more, further improvement of the synergistic effect is not expected.

  As is clear from the examples and comparative examples, it was clarified that the flame retardant and the flame retardant organic polymer compound according to the present invention do not contain any halogen and have an excellent flame retardant effect, and It has been proven that it is easily implemented on an industrial scale. It should be noted that Example 13-3 and Reference Example 1 show that polyamide and triallyl isocyanurate form a crosslinked structure by radiation treatment in the presence of general formula 1 and the heat resistance thereof is improved. Value was suggested.

  General formula 1 is divided into two types in terms of its manufacturing method.

  One of them is an organophosphorus compound having a nitrogen atom, which is a substituent at the 10-position of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, that is, R in the general formula 1 Is an anilino group, indolyl group, indolinyl group, diphenylamino group, carbazolyl group, or phenothiazino group which may have a substituent. These are 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-halogeno-10-oxide and optionally substituted aniline, indole, indoline, diphenylamine, carbazole or phenothiazine. It is produced by carrying out a condensation reaction in the presence or absence of a base. Here, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-halogeno-10-oxide is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Of 9,10-dihydro-9-oxa-10-phosphaphenanthrene, which is a reaction of benzene with halogen or a precursor of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide It can be prepared by an oxidation reaction of -10-chloride. In particular, the latter method has a simple preparation process and is industrially advantageous over the former. The general formula 1 produced by the above method is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-anilino-10-oxide (hereinafter referred to as “10-anilino”). 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- (N-methylanilino) -10-oxide {hereinafter referred to as “10- (N-methylanilino)”. }, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- (N-ethylanilino) -10-oxide {hereinafter referred to as “10- (N-ethylanilino)”. }, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-diphenylamino-10-oxide (hereinafter referred to as “10-diphenylamino”), 9,10-dihydro-9- Examples thereof include oxa-10-phosphaphenanthrene-10-carbazolyl-10-oxide (hereinafter referred to as “10-carbazolyl”).

  The other is an organophosphorus compound having no nitrogen atom, wherein the substituent at the 10-position of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is a benzhydryl group or 9- What is a fluorenyl group is illustrated. These are obtained by subjecting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and benzhydryl halide or 9-halogenofluorene directly to a dehydrohalogenation condensation reaction. Manufactured. As general formula 1 prepared by the above method, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-benzhydryl-10-oxide (hereinafter referred to as “10-benzhydryl”). And 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- (9-fluorenyl) -10-oxide {hereinafter referred to as “10- (9-fluorenyl)”. }.

  The organic polymer compound that is preferably applied as a flame retardant of the general formula 1 is as described above. Further, as described above, the organic polymer compound that is most preferable to be applied of the general formula 1 is also described. Polyolefins, polystyrene, ABS resin Polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyamides, polycarbonate resin or polycarbonate resin / ABS resin polymer alloy. These are all thermoplastic organic polymer compounds, and are likely to cause dripping during combustion. As a method for preventing this undesirable dripping, addition of carbon fiber or glass fiber is recommended.

  Examples of polyolefins include polyethylene, polypropylene, polybutene, and polymethylpentene. It is preferable to add an inorganic compound such as magnesium hydroxide, aluminum hydroxide or clay together with the general formula 1 to these polyolefins because a higher flame retardant effect can be obtained.

  The polystyrene includes a styrene homopolymer and a graft polymer (high impact polystyrene) of styrene to polybutadiene. For these, addition of “10- (N-methylanilino)”, “10- (N-ethylanilino)”, “10-diphenylamino”, “10-carbazolyl” or “10-benzhydryl” is effective. In expanded polystyrene, “10- (N-methylanilino)” or “10- (N-ethylanilino)” has a low melting point, and their addition is the smoothest and most effective in the treatment process.

  In general, what is called ABS resin is basically composed of a polymer of butadiene, acrylonitrile and styrene, and various types are produced depending on the production method and the ratio of constituent monomers. Although all of the general formula 1 is preferably used for the ABS resin, the addition of “10-anilino”, “10- (N-methylanilino)” or “10- (N-ethylanilino)” is particularly difficult. A flame effect is obtained. Moreover, although the gel component of ABS resin may increase at the time of mixing or molding at a high temperature, if this is disliked, addition of a small amount of a hindered phenol polymerization inhibitor is recommended.

  Polymethyl methacrylate is an organic polymer compound having a high softening point and excellent transparency, is called acrylic glass, and is widely used as a structural material. This is one of the organic polymer compounds that are difficult to be flame retardant with other organic phosphorus compounds. Of the general formula 1, all except “10-anilino” are used preferably without harming their high softening point and high transparency. In addition, if transparency can be sacrificed, the use with magnesium hydroxide or aluminum hydroxide is expected to have a synergistic effect.

  Polyethylene terephthalate and polybutylene terephthalate are polycondensates of terephthalic acid and ethylene glycol or 1,4-butanediol, and are widely used as molded articles, film products, or textile products. General formula 1 can be mixed in a molten state in a molded article, film product or fiber product of polyethylene terephthalate or polybutylene terephthalate. At this time, the addition of “10-benzhydryl” or “10- (9-fluorenyl)” is recommended. In addition, in the textile product, as described above, the addition of the flame retardant can be performed by a method of treating with the solution or water suspension. General formula 1 suitable for this method includes “10-anilino”, “10- (N-methylanilino)”, “10- (N-ethylanilino)”, “10-diphenylamino”, “10-benzhydryl” and the like. Is mentioned.

  Examples of polyamides include nylon-6, nylon-6,6, nylon-6,10, nylon-11, nylon-12, copolymer nylon, nylon-MXD, 6, nylon-4,6, and the like. Among the general formula 1, those which are preferably added to the polyamides include “10- (N-methylanilino)”, “10- (N-ethylanilino)”, “10-diphenylamino”, “10-carbazolyl” or “10-benzhydryl” and the like can be mentioned, and it is recommended to add an inorganic compound such as magnesium hydroxide, aluminum hydroxide or clay at the same time.

  Polycarbonate resin is an organic polymer compound having excellent transparency, and usually refers to a polycondensate of bisphenol-A and phosgene, but 4,4′-biphenol, bisphenol-F or 3,4 together with bisphenol-A. 3'-dimethyl-4,4'-biphenol, and phenol, p-tertiarybutylphenol, p-cumylphenol or p-phenylphenol as a terminal group may be copolymerized. Polycarbonate resin is one of the organic polymer compounds in which other organophosphorus compounds are effective as flame retardants. If other organophosphorus compounds and general formula 1 are used at the same time, the addition of flame retardants is possible due to their synergistic effect. Since the amount can be reduced, the reduction in the thermal and mechanical strength of the resin is mitigated.

  Polycarbonate resin / ABS resin polymer alloy is widely used for the purpose of avoiding the difficulty of flame retardancy with ABS resin alone. As with the polycarbonate resin, Formula 1 and other organophosphorus compounds may be added.

  To these organic polymer compounds, a flame retardant mainly composed of the general formula 1 and, if necessary, other organic phosphorus compounds are added, and further, a plasticizer, an antioxidant, an ultraviolet absorber, an ultraviolet stabilizer, and an antistatic agent. An agent, a colorant, a lubricant, a foaming agent or an inorganic filler can be added. Examples of the plasticizer include adipic acid ester, sebacic acid ester, phthalic acid ester, trimellitic acid ester, diethylene glycol ester, triethylene glycol ester or high molecular weight esters, carboxylic acid esters, phosphoric acid esters or sulfonamides. used. As the antioxidant, a hindered phenol-based, sulfur-based or phosphorus-based one is used. As the ultraviolet absorber, a salicylic acid-based, benzophenone-based, or benzotriazole-based one is used. As the antistatic agent, colorant, lubricant, or foaming agent, a commercially available product may be used. As the inorganic filler, glass fiber, carbon fiber, silicic anhydride, clay, talc, mica, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum oxide, zinc oxide, tin oxide or antimony oxide are used. . It is known that if the inorganic filler is added in an amount of 20% by weight or more, the heat resistance and flame retardancy of the organic polymer composition are improved. In particular, other organophosphorus compounds, magnesium hydroxide and aluminum hydroxide have a synergistic effect when used simultaneously with the general formula 1, and exhibit a high flame retardant effect. is there.

  Next, in order to further clarify the present invention, specific examples, comparative examples, and reference examples will be described. In the examples, “%” represents wt% and “parts” represents parts by weight. However, the following examples do not limit the present invention.

Example 1-1 Preparation of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-bromo-10-oxide
9,10-Dihydro-9-oxa-10-phosphaphenanthrene was added to a 2,000 ml hard glass five-necked flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and gas inlet. 324.3 g (1.5 mol) of -10-oxide and 1,000 g of chlorobenzene were charged. The flask was heated while nitrogen gas was blown from the gas blowing port, and the temperature of the contents was raised to 100 ° C. Since the contents were melted, the temperature of the contents was cooled to 80 ° C. while stirring vigorously. Here, 239.7 g (1.5 mol) of bromine was slowly dropped from the dropping funnel. The reaction was exothermic and the flask was cooled to maintain the temperature of the contents at 70-80 ° C. Hydrogen bromide generated by the reaction was treated by being guided outside from the top of the reflux condenser. The reaction was completed simultaneously with the end of dropping. Here, a chlorobenzene solution of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-bromo-10-oxide was prepared.

Example 1-2 (Production of “10-anilino”)
158 g of aniline (1.7 mol) and 152 g of triethylamine (1.5 mol) were added to a 10,000 ml hard glass five-necked flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and gas inlet. And 4,000 g of toluene were charged. 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-bromo-10 obtained in Example 1-1 from the dropping funnel and kept warm while nitrogen gas was blown from the gas blowing port. -A chlorobenzene solution of oxide was added dropwise. The dripping took 3 hours at 70 ° C. After completion of dropping, the temperature was kept at 70 ° C. for 1 hour. To this was added 1,000 g of water, stirred at 80 ° C. for 30 minutes, and allowed to stand for 30 minutes. The aqueous layer was removed, 1,000 g of water was further added, stirred at 80 ° C. for 30 minutes, and allowed to stand for 30 minutes to remove the aqueous layer. After repeating this operation once more, a water separator was attached to the lower part of the reflux condenser, the flask was heated to remove water azeotroped with toluene, and 3,500 g of toluene was further removed. This was filtered while hot and then cooled to 0 ° C. to precipitate crystals. The crystals were filtered and washed with 600 g of cooled toluene and dried. 410 g of white crystals having a melting point of 206 ° C. were obtained. The crystals were found to be 99% pure by liquid chromatogram (LC) analysis. This infrared absorption spectrum (IR) was as shown in FIG. 1, and ¹ H NMR was as shown in FIG. The results of elemental analysis were as follows: carbon was 70.41% (theoretical value: 70.36%), hydrogen was 4.58% (theoretical value: 4.592%), and nitrogen was 4.57% (theoretical value: 4). .559%) and phosphorus was 10.10% (theoretical value: 10.08%), which was confirmed to be “10-anilino”.

Example 2 {Production of "10- (N-methylanilino)"}
A white color having a melting point of 173 ° C. was exactly the same as Example 1-2 except that 158 g (1.7 mol) of aniline used in Example 1-2 was replaced with 182 g (1.7 mol) of N-methylaniline. 400 g of crystals were obtained. The crystals were found to be 99% by LC analysis. This IR was as shown in FIG. 3, and ¹ H NMR was as shown in FIG. As a result of elemental analysis, carbon was 71.0% (theoretical value: 71.02%), hydrogen was 5.03% (theoretical value: 5.020%), and nitrogen was 4.38% (theoretical value: 4). 360%) and phosphorus was 9.65% (theoretical value: 9.639%), which was confirmed to be “10- (N-methylanilino)”.

Example 3 {Production of "10- (N-ethylanilino)"}
Except for replacing 158 g (1.7 mol) of aniline used in Example 1-2 with 206 g (1.7 mol) of N-ethylaniline, white color having a melting point of 82 ° C. was exactly the same as Example 1-2. 380 g of crystals were obtained. However, the temperature of the solution was cooled to −10 ° C. during crystallization. The crystals were found to be 99% by LC analysis. This IR was as shown in FIG. 5, and ¹ H NMR was as shown in FIG. As a result of elemental analysis, carbon was 71.65% (theoretical value: 71.63%), hydrogen was 5.42% (theoretical value: 5.409%), and nitrogen was 4.17% (theoretical value: 4). .178%) and phosphorus was 9.23% (theoretical value: 9.236%), which was confirmed to be “10- (N-ethylanilino)”.

Example 4 (Production of “10-Diphenylamino”)
490 g of white crystals having a melting point of 147 ° C. were obtained in the same manner as in Example 1-2, except that 158 g (1.7 mol) of aniline used in Example 1-2 was replaced with 271 g (1.6 mol) of diphenylamine. It was. The crystals were found to be 99% by LC analysis. Further, IR was as shown in FIG. 7, and ¹ H NMR was as shown in FIG. The results of elemental analysis showed that carbon was 75.3% (theoretical value: 75.19%), hydrogen was 4.75% (theoretical value: 4.732%), and nitrogen was 3.63% (theoretical value: 3). .654%) and phosphorus was 8.11% (theoretical value: 8.08%), and these analysis results confirmed that this was "10-diphenylamino".

Example 5 (Production of “10-carbazolyl”)
520 g of white crystals having a melting point of 205 ° C. were obtained in the same manner as in Example 1-2 except that 158 g (1.7 mol) of aniline used in Example 1-2 was replaced with 267.6 g (1.6 mol) of carbazole. was gotten. The crystals were found to be 99% by LC analysis. This IR was as shown in FIG. 9, and ¹ H NMR was as shown in FIG. The results of elemental analysis are as follows: carbon is 75.7% (theoretical value: 75.59%), hydrogen is 4.20% (theoretical value: 4.229%), and nitrogen is 3.66% (theoretical value: 3). 674%) and phosphorus was 8.13% (theoretical value: 8.122%), which was confirmed to be “10-carbazolyl”.

Example 6 (Production of “10-Benzhydryl”)
9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in a glass four-necked flask with an internal volume of 3,000 ml equipped with a stirrer, thermometer, gas inlet and reflux condenser 335 g (1.55 mol), benzhydryl chloride 304 g (1.5 mol) and orthodichlorobenzene 200 g were charged. Nitrogen gas was blown in from the gas blowing port little by little. The flask was heated and gradually raised to 100 ° C. As the flask contents melted, the agitator was moved. Furthermore, the temperature of the contents was gradually raised. Since hydrogen chloride gas flowed out from the upper part of the reflux condenser when the temperature of the contents reached 170 ° C., it was led to the outside and processed. Further, the temperature of the contents was gradually increased and maintained at 210 ° C. for 6 hours. Generation of hydrogen chloride gas was stopped, and as a result of LC analysis, benzhydryl chloride as a raw material was not detected. The temperature of the contents was set to 110 ° C., and 1,300 g of toluene and 500 g of boiling water were added. After stirring for 30 minutes, the aqueous layer was removed by allowing to stand for 30 minutes. 500 g of water was added, and the mixture was stirred at 80 ° C. for 30 minutes and then allowed to stand for 30 minutes to remove the aqueous layer. This operation was repeated once more. This was dehydrated azeotropically, then filtered while hot, and the filtrate was gradually cooled to precipitate crystals. After cooling to 0 ° C., the mixture was filtered, and the crystals were washed with 400 g of cooled toluene. The dried crystals were white and had a melting point of 177 ° C., yielding 510 g. LC analysis showed that it was 99% pure. The IR of this is shown in FIG. 11 and the ¹ H NMR is as shown in FIG. 12. The results of elemental analysis show that carbon is 78.50% (theoretical value: 78.52%) and hydrogen is 5.02% (theoretical value: 5). 0.008%) and phosphorus was 8.11% (theoretical value: 8.100%). From these analysis results, it was confirmed that this was “10-benzhydryl”.

(Example 7-1)
To 100 parts of polymethylpentene (TPX) manufactured by Mitsui Chemicals, Japan, 30 parts of short glass fiber, 25 parts of magnesium hydroxide and 15 parts of “10- (N-methylanilino)” obtained in Example 2 were added. The mixture was heated and mixed, and a test piece having a thickness of 1/16 inch meeting the UL-94 combustion test standard was prepared by an extrusion molding machine. The results of the combustion test are shown in Table-1.

(Example 7-2)
The same as Example 7-1, except that 15 parts of “10- (N-methylanilino)” used in Example 7-1 were replaced with 15 parts of “10- (N-ethylanilino)” obtained in Example 2. A test piece was prepared. The results of the combustion test are shown in Table-1.

(Comparative Example 1)
A test piece was prepared in the same manner as in Example 7-1 except that 15 parts of “10- (N-methylanilino)” used in Example 7-1 was replaced with 15 parts of triphenyl phosphate (hereinafter referred to as TPP). did. The results of the combustion test are shown in Table-1.

(Example 8-1)
Add 100 parts of commercially available polystyrene to 30 parts of short glass fibers, 25 parts of magnesium hydroxide and 12 parts of “10- (N-methylanilino)” and mix them by heating. A 16-inch test piece was prepared. The results of the combustion test are shown in Table-1.

(Example 8-2)
A test piece was prepared in the same manner as in Example 8-1, except that 12 parts of “10- (N-methylanilino)” used in Example 8-1 were replaced with 12 parts of “10- (N-ethylanilino)”. . The results of the combustion test are shown in Table-1.

(Example 8-3)
A test piece was prepared in the same manner as in Example 8-1, except that 12 parts of “10- (N-methylanilino)” used in Example 8-1 were replaced with 15 parts of “10-diphenylamino”. The results of the combustion test are shown in Table-1.

(Comparative Example 2)
A test piece was prepared in the same manner as in Example 8-1, except that 12 parts of “10- (N-methylanilino)” used in Example 8-1 was replaced with 12 parts of TPP. The results of the combustion test are shown in Table-1.

(Example 9-1)
Add 100 parts of ABS resin made by Toray Industries, Japan, 30 parts of short glass fiber, 20 parts of clay, and 15 parts of “10- (N-methylanilino)” and mix by heating to meet UL-94 combustion test standards. A test piece having a thickness of 1/16 inch was prepared. The results of the combustion test are shown in Table-1.

(Example 9-2)
A test piece was prepared in the same manner as in Example 9-1 except that 15 parts of “10- (N-methylanilino)” used in Example 9-1 were replaced with 15 parts of “10- (N-ethylanilino)”. . The results of the combustion test are shown in Table-1.

(Example 9-3)
A test piece was prepared in the same manner as in Example 9-1 except that 15 parts of “10- (N-methylanilino)” used in Example 9-1 were replaced with 15 parts of “10-anilino”. The results of the combustion test are shown in Table-1.

(Comparative Example 3)
A test piece was prepared in the same manner as in Example 9-1 except that 15 parts of “10- (N-methylanilino)” used in Example 9-1 was replaced with 15 parts of TPP. The results of the combustion test are shown in Table-1.

(Example 10-1)
15 parts of “10- (N-methylanilino)” was added to 100 parts of commercially available polymethyl methacrylate and mixed to prepare a test piece having a thickness of 1/16 inch meeting the UL-94 combustion test standard. The results of the combustion test are shown in Table-1. The test piece was transparent.

(Example 10-2)
A transparent test piece was prepared in the same manner as in Example 10-1, except that 15 parts of “10- (N-methylanilino)” used in Example 10-1 were replaced with 15 parts of “10- (N-ethylanilino)”. Created. The results of the combustion test are shown in Table-1.

(Example 10-3)
A transparent test piece was prepared in the same manner as in Example 10-1, except that 15 parts of “10- (N-methylanilino)” used in Example 10-1 were replaced with 15 parts of “10-carbazolyl”. The results of the combustion test are shown in Table-1.

(Comparative Example 4)
A transparent test piece was prepared in the same manner as in Example 10-1, except that 15 parts of “10- (N-methylanilino)” used in Example 10-1 was replaced with 15 parts of TPP. The results of the combustion test are shown in Table-1.

(Example 11-1)
30 parts of short glass fiber, 20 parts of magnesium hydroxide and 15 parts of “10-diphenylamino” are added to 100 parts of commercially available polyethylene terephthalate, heated and mixed, and a thickness of 1/16 that meets the UL-94 combustion test standard. Inch specimens were made. The results of the combustion test are shown in Table-1.

(Example 11-2)
A test piece was prepared in the same manner as in Example 4 except that 15 parts of “10-diphenylamino” used in Example 11-1 were replaced with 15 parts of “10-benzhydryl”. The results of the combustion test are shown in Table-1.

(Comparative Example 5)
An attempt was made to create a test piece by replacing 15 parts of “10-diphenylamino” used in Example 11-1 with 15 parts of TPP, but the molecular weight of polyethylene terephthalate was significantly reduced, making it impossible to produce the test piece. It was. Although other organophosphorus compounds were tried, no test piece was obtained.

(Example 12-1)
30 parts of short glass fiber, 20 parts of magnesium hydroxide and 15 parts of “10-carbazolyl” are added to 100 parts of commercially available polybutylene terephthalate, heated and mixed to a thickness of 1/16 that meets the UL-94 combustion test standard. Inch specimens were made. The results of the combustion test are shown in Table-1.

(Example 12-2)
A test piece was prepared in the same manner as in Example 4 except that 15 parts of “10-carbazolyl” used in Example 12-1 was replaced with 15 parts of “10-benzhydryl”. The results of the combustion test are shown in Table-1.

(Comparative Example 6)
A test piece was prepared in the same manner as in Example 12-1, except that 15 parts of “10-carbazolyl” used in Example 12-1 was replaced with 15 parts of TPP, but the molecular weight of polybutylene terephthalate was significantly reduced. Thus, a test piece could not be created.

(Example 13-1)
Nylon-6,6 made by Asahi Kasei Co., Ltd., Japan Add 30 parts of short glass fiber, 20 parts of clay and 15 parts of “10- (N-methylanilino)” and mix by heating to meet UL-94 combustion test standards. Matching 1/16 inch thick specimens were made. The results of the combustion test are shown in Table-1.

(Example 13-2)
A test piece was prepared in the same manner as in Example 13-1, except that 15 parts of “10- (N-methylanilino)” used in Example 13-1 were replaced with 15 parts of “10- (N-ethylanilino)”. did. The results of the combustion test are shown in Table-1.

(Example 13-3)
Nylon-6,6 made by Asahi Kasei Co., Japan, 30 parts of short glass fiber, 20 parts of clay, 15 parts of “10- (N-ethylanilino)”, 3 parts of triallyl isocyanurate and triethylene glycol-bis-3 -0.03 g of (3-tertiarybutyl-4-hydroxy-5-methylphenyl) propionate was added and mixed by heating to prepare a test piece having a thickness of 1/16 inch meeting the UL-94 flame test standard. . The results of the combustion test are shown in Table-1.

(Comparative Example 7)
A test piece was prepared in the same manner as in Example 13-1, except that 15 parts of “10- (N-methylanilino)” used in Example 13-1 was replaced with 15 parts of TPP. The results of the combustion test are shown in Table-1.

(Reference Example 1)
The test piece obtained in Example 13-3 was irradiated with γ-rays of 40 kGy from cobalt 60. The untreated specimen was greatly deformed at 300 ° C., but the specimen treated with γ-ray did not deform even at 300 ° C. Note that V-0 was maintained as a result of the combustion test.

(Example 14-1)
Add 100 parts of commercially available polycarbonate resin, 30 parts of short glass fiber, 10 parts of clay, 5 parts of “10- (N-methylanilino)” and 3 parts of TPP, and mix by heating. Thickness that meets UL-94 combustion test standards A 1/16 inch test piece was prepared. The results of the combustion test are shown in Table-1.

(Example 14-2)
A test piece was prepared in the same manner as in Example 14-1, except that 5 parts of “10- (N-methylanilino)” used in Example 14-1 were replaced with 5 parts of “10- (N-ethylanilino)”. did. The results of the combustion test are shown in Table-1.

(Example 14-3)
A test piece was prepared in the same manner as in Example 14-1, except that 5 parts of “10- (N-methylanilino)” used in Example 14-1 was replaced with 5 parts of “10-benzhydryl”. The results of the combustion test are shown in Table-1.

(Comparative Example 8)
A test piece was prepared in the same manner as in Example 14-1, except that 5 parts of “10- (N-methylanilino)” and 3 parts of TPP used in Example 14-1 were replaced with 8 parts of TPP. The results of the combustion test are shown in Table-1. In addition, the heat resistance of the test piece was reduced by about 15 ° C. as compared with Example 14-1.

(Example 15-1)
Add 100 parts of short glass fiber, 30 parts, 10 parts of clay and 9 parts of “10- (N-methylanilino)” to 100 parts of commercially available ABS resin / polycarbonate resin polymer alloy, heat mix, and meet UL-94 combustion test standards. Matching 1/16 inch thick specimens were made. The results of the combustion test are shown in Table-1.

(Example 15-2)
A test piece was prepared in the same manner as in Example 15-1, except that 9 parts of “10- (N-methylanilino)” used in Example 15-1 were replaced with 9 parts of “10- (N-ethylanilino)”. did. The results of the combustion test are shown in Table-1.

(Example 15-3)
A test piece was prepared in the same manner as in Example 15-1, except that 9 parts of “10- (N-methylanilino)” used in Example 15-1 were replaced with 9 parts of “10-anilino”. The results of the combustion test are shown in Table-1.

(Comparative Example 9)
A test piece was prepared in the same manner as in Example 15-1, except that 9 parts of “10- (N-methylanilino)” used in Example 15-1 was replaced with 9 parts of TPP. The results of the combustion test are shown in Table-1.

It is an infrared absorption spectrum (IR) figure of the compound obtained in Example 1-2. ¹ is a ¹ H NMR diagram of the compound obtained in Example 1-2. FIG. 2 is an infrared absorption spectrum (IR) diagram of the compound obtained in Example 2. FIG. 2 is a ¹ H NMR diagram of the compound obtained in Example 2. FIG. 2 is an infrared absorption spectrum (IR) diagram of the compound obtained in Example 3. FIG. 2 is a ¹ H NMR diagram of the compound obtained in Example 3. FIG. 2 is an infrared absorption spectrum (IR) diagram of the compound obtained in Example 4. FIG. 2 is a ¹ H NMR diagram of the compound obtained in Example 4. FIG. 2 is an infrared absorption spectrum (IR) diagram of the compound obtained in Example 5. FIG. ¹ is a ¹ H NMR diagram of the compound obtained in Example 5. FIG. 2 is an infrared absorption spectrum (IR) diagram of the compound obtained in Example 6. FIG. 2 is a ¹ H NMR diagram of the compound obtained in Example 6. FIG.

Claims (13)

An organophosphorus compound represented by the general formula 1.

(In formula 1, R represents an anilino group, indolyl group, indolinyl group, diphenylamino group, carbazolyl group, phenothiazino group, benzhydryl group or 9-fluorenyl group which may have a substituent.)   An organophosphorus compound characterized in that, in general formula 1, R is an anilino group, an N-methylanilino group, an N-ethylanilino group, a diphenylamino group, a carbazolyl group or a benzhydryl group.   A flame retardant comprising one or more organic phosphorus compounds represented by general formula 1 as a main component.   A flame retardant organic polymer composition, characterized in that the organic polymer compound contains 0.5 to 25% by weight of an organic phosphorus compound represented by the general formula 1.   The flame retardant organic polymer composition according to claim 4, wherein the organic polymer compound is a polyolefin.   The flame retardant organic polymer composition according to claim 4, wherein the organic polymer compound is polystyrene.   The flame retardant organic polymer composition according to claim 4, wherein the organic polymer compound is an ABS resin.   The flame retardant organic polymer composition according to claim 4, wherein the organic polymer compound is methyl polymethacrylate.   The flame retardant organic polymer composition according to claim 4, wherein the organic polymer compound is polyethylene terephthalate.   The flame retardant organic polymer composition according to claim 4, wherein the organic polymer compound is polybutylene terephthalate.   The flame retardant organic polymer composition according to claim 4, wherein the organic polymer compound is a polyamide.   The flame retardant organic polymer composition according to claim 4, wherein the organic polymer compound is a polycarbonate resin.   The flame retardant organic polymer composition according to claim 4, wherein the organic polymer compound is a polycarbonate resin / ABS resin polymer alloy.

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