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WO2001077088A1 - Melam d'acide methanesulfonique, son procede de production et composition de resine polyamide ignifuge - Google Patents

Melam d'acide methanesulfonique, son procede de production et composition de resine polyamide ignifuge Download PDF

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Publication number
WO2001077088A1
WO2001077088A1 PCT/JP2001/002501 JP0102501W WO0177088A1 WO 2001077088 A1 WO2001077088 A1 WO 2001077088A1 JP 0102501 W JP0102501 W JP 0102501W WO 0177088 A1 WO0177088 A1 WO 0177088A1
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WO
WIPO (PCT)
Prior art keywords
melam
methanesulfonic acid
weight
flame
melamine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2001/002501
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English (en)
Japanese (ja)
Inventor
Masaaki Ozawa
Yuuko Furuya
Akira Yoshida
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Nissan Chemical Corp
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Nissan Chemical Corp
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Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Publication of WO2001077088A1 publication Critical patent/WO2001077088A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C09K21/10—Organic materials containing nitrogen
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof

Definitions

  • the present invention relates to melam methanesulfonate, a method for producing the same, and a flame-retardant polyamide resin composition using the same.
  • Melam methanesulfonate is suitably used as a flame retardant for synthetic resins, especially polyamide resins.
  • Japanese Patent Application Laid-Open No. H08-231151 discloses a water-resistant aminotriazine sulfate composition containing melamine and sulfuric acid.
  • the method describes a method for producing a melamin sulfate composition characterized in that the reaction is carried out at a molar ratio of 1: 0.1 to 1.
  • the calcined products of sulfuric acid and melamin see the American Chemical Society Symposium Series No. 425 “Fire and Polymers” (ACS Symposium Series No.
  • WO98 / 93936 As a salt of a 1,3,5-triazine derivative containing melam and an inorganic acid, WO98 / 93936 (corresponding Japanese Patent Application Publication: Japanese Patent Application Laid-Open No. 10-306801) ), The reaction product obtained by mixing melamine and phosphoric acid at a molar ratio of 1: 2.0 to 4.0 is calcined at 340 to 450 ° C to obtain polylinol. A method for producing the acid melamin 'Melam' melem double salt is described.
  • W09 839 9307 (corresponding Japanese Patent Application Publication: Japanese Patent Application Laid-Open No. 10-36082) discloses that melamin, phosphoric acid and sulfuric acid are mixed at a specific ratio. Baking the resulting reaction product at 340 to 400 ° C to produce melamin melam, a polyacid composed of phosphorus, zeolite and oxygen Is disclosed.
  • WO 96/16 948 Japanese Patent Application Laid-Open No. 10-511409 discloses a process for producing melam, which is one of the condensed products of melamin, by using melamine. And a method of heating a mixture of paratoluenesulfonic acid, which is one of the organic acids, at 250 to 350 ° C. to obtain a melam salt of the acid and purifying the melam salt.
  • the para-toluenesulfonic acid melam salt obtained in the heating stage of this method exhibits a strong dark brown color, which limits the toning when used as an additive in synthetic resins, for example.
  • Melam methanesulfonic acid obtained by calcining the reaction product of melamine and methanesulfonic acid has not been reported so far.
  • Flame retardation of polyamide resin is generally performed by a method of adding a halogen compound or a nitrogen compound.
  • a halogen-based compound when used, the mold may be corroded due to the generation of corrosive gas during molding, and there is also a problem that toxic halogenated gas is generated during combustion. Therefore, a flame retardant that does not use a halogenated compound has attracted attention.
  • the nitrogen-based flame retardants disclosed in the above prior art are not sufficiently flame-retardant, especially with reinforced polyamide resins, and are liable to be decomposed and sublimated during molding to cause a foaming phenomenon and mold contamination. However, it is difficult to use it effectively as a flame retardant.
  • An object of the present invention is to solve the above-mentioned drawbacks of the prior art, and to use methanesulfone as a starting material, which is made of melamin and methanesulfonic acid, which can withstand a wide range of uses as a flame retardant for polyamide resins.
  • an acid melam and a method for producing the same.
  • the present invention provides a flame-retardant polyamide resin composition containing melam methanesulfonate. The method for producing melamne methanesulfonate of the present invention will be described.
  • step (b) baking the reaction product obtained in the step (a) at a temperature of 300 to 400 ° C. for 0.1 to 30 hours,
  • the methanesulfonic acid melan of the present invention has the general formula (1)
  • C represents a carbon atom
  • H represents a hydrogen atom
  • S represents a sulfur atom
  • N represents a nitrogen atom
  • X and y represent positive numbers, 0.90 yZx x 1.
  • the melam is represented by the chemical formula C 6 H 9 Ni] (N—4,6-diamino;!, 3,5-triazine-12-yl) -11,3,5- Triazine 1, 2, 4, 6—Tri It is a family. This is a 1,3,5-triazine derivative in which one molecule of ammonia is desorbed and condensed from two molecules of melamin.
  • a flame-retardant polyamide resin composition comprising 1 part by weight and 300 parts by weight of an inorganic filler.
  • FIG. 1 is a differential thermal analysis diagram of melam methanesulfonate obtained in Example 1. Explanation of symbols:
  • Methanesulfonic acid may be used as it is, or may be used as an aqueous solution having a methanesulfonic acid concentration of 50% by weight or more.
  • the reaction product can be obtained by mixing in a slurry state in the presence of excess water, and filtering and drying the reaction product.
  • a mixing / stirring device such as an automatic mortar, a universal mixer, a Henschel mixer, a Reedige mixer, and a homogenizer can be used.
  • a Henschel mixer or a Lödige mixer having a shearing force is preferable.
  • melamin and methanesulfonic acid are mixed in a ratio of 2.0 to 3.0 mol of melamin to 1 mol of methanesulfonic acid.
  • Methanesulfonic acid 1 If the ratio of melamin is less than 2.0 moles relative to moles, it is not preferred because the acid of the calcined product obtained in the subsequent calcining step becomes excessive and the acidity becomes too strong. On the other hand, if the ratio of melamin exceeds 3.0 moles per mole of methanesulfonic acid, on the other hand, the residual amount of melamine in the final calcined product becomes too large or the volatilization of melamine during calcination becomes large. It is not preferable because it becomes too much.
  • the temperature at the time of mixing melamine and methanesulfonic acid may be 0 to 200 ° C. In the case of removing moisture in the semi-dry mixing, the temperature is preferably 70 to 150 ° C. for efficient removal of moisture. Mixing under reduced pressure while suctioning with a suction pump or the like enables more efficient removal of water. The total time of mixing and stirring depends on the intensity of mixing, but is usually 10 minutes to 2 hours.
  • colloidal silica may be added at the time of mixing for the purpose of preventing caking during the subsequent firing or preventing adhesion to the firing machine, if necessary.
  • the amount of colloidal silica powder is preferably 10 to 10 parts by weight based on the total amount of melamine and methanesulfonic acid of 100 parts by weight. It may be added in a ratio.
  • step (b) of the present invention the mixed reaction product of melamine and methanesulfonic acid is mixed at a temperature of 300 to 400 ° C, preferably 320 to 380 ° C, for 0.1.
  • melane methansulfonate can be obtained.
  • the methanesulfonic acid melam obtained by the present invention is a white or slightly yellowish powder.
  • melamin in the mixed reaction product undergoes a deammonification reaction to form melam, and finally from 0.90 to 1.3 per mole of sulfur atom.
  • a melam methanesulphonate having a ratio of 0 mol is obtained. If the firing temperature is less than 300 ° C The melaninization reaction of melamine in the mixed reaction product is slowed down, and unreacted melamine tends to remain in the baked product. If the temperature exceeds 400 ° C., it is not preferable because methanesulfonic acid melam is decomposed. If the calcination time is less than 0.1 hour, the production of the target melamethane methanesulfonate is insufficient, and it may be longer than 30 hours, but if it exceeds 30 hours, it is not economical .
  • an electric furnace, a hot-air dryer, a single-tally kiln, a double-shaft-type stirring-type firing machine, a double-shaft-type kneader-type firing machine, a fluidized-flow firing furnace, or the like is used alone or in combination.
  • the melamin can be efficiently converted to melam. Therefore, sintering with a porcelain-alumina sagger with a lid is preferred.
  • More preferable is a baking furnace of the type that can be agitated for uniform baking.
  • the sublimate of melamine is used. It is more preferable because it can be fired while returning the ammonia inside and discharging the generated ammonia to the outside of the system.
  • the firing may be performed by either a batch method or a continuous method.
  • the desired melamine methanesulfonate can be obtained by the above calcination.However, when applied as a flame retardant for polyamide resin, the calcination product contains It is preferable not to leave unreacted melamine as much as possible.
  • Melam methanesulfonate contains several weight percent of methanesulfonic acid salt of melem, which is formed by condensation of two molecules of melamine, which is a by-product, depending on the firing conditions. It may be done.
  • the melane methansulfonate obtained by the present invention has an extremely low solubility in water (25 ° C.) of 0.01 to 0.10 g Z 100 m 1, and thus has excellent water resistance. . It is characterized by having a pH of 3.0 to 7.0 as a 10% by weight aqueous slurry (at 25). Further, as shown in Example 1 later, according to TGZDTA analysis, it hardly decomposes up to 400 ° C, and is characterized by extremely excellent heat resistance.
  • Melamethane methanesulfonate which is the calcined product of the present invention, may be used, if necessary, with a dry pulverizer such as a mixer, a pin disk mill, a ball mill, a dittoizer or the like.
  • a dry pulverizing classifier such as a centrifugal mill or an inomaizer
  • a preferred average particle diameter (median diameter) is 2 ⁇ m or less, more preferably an average particle diameter (median diameter) 10. It can be a fine powder of ⁇ m or less.
  • a pulverized product of the above calcined product is used, and 25% by weight of an inorganic substance such as silica powder / an inorganic basic substance is added to 100 parts by weight of melam methanesulfonate of the present invention.
  • the pulverized product added and adjusted below can be used (the addition may be performed at room temperature to 400 ° C. That is, the addition may be performed before the completion of the above-described firing, or may be performed after the completion of the firing.
  • a mixing device having a shearing force such as a Henschel mixer, a Lodige mixer, a homogenizer, a homomixer, etc., but a V-type mixer or a universal mixer
  • a pulverizer such as a pin disk mill, a jet atomizer, a ball mill, a counter jet mill, or an inomaizer.
  • the above-mentioned inorganic substance is a substance which is insoluble or has low solubility in water, for example, preferred examples include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, and calcium silicate. , Magnesium silicate, calcium carbonate, silica powder, talc, zinc oxide, etc.
  • Commercially available inorganic substances can be used.
  • the calcined product of the present invention and the inorganic substance described above can be used.
  • the flame-retardant polyamide resin composition of the present invention comprises the above-mentioned methanesulfonic acid melam in an amount of 1 to 100 parts by weight, preferably 3 to 80 parts by weight, based on 100 parts by weight of the polyamide resin. It is a compounded product. Further, based on 100 parts by weight of the polyamide resin, 1 to 100 parts by weight, preferably 3 to 80 parts by weight of the above methanesulfonic acid melan, and 1 to 300 parts by weight of the inorganic filler. Parts by weight.
  • the amount of melam methanesulfonate is 1 If the amount is less than 10 parts by weight, the flame-retardant effect is not sufficient. If the amount is more than 100 parts by weight, the flame-retardant effect is not increased any more, and the moldability is rather lowered.
  • the flame-retardant polyamide composition of the present invention has a high degree of flame retardancy, and extremely hardly causes a dripping phenomenon in a UL-94 vertical combustion test. Further, there is almost no generation of decomposition gas or foaming during kneading, and contamination of the mold during molding is eliminated.
  • polyamide resin used in the present invention examples include ⁇ -force prolactam, aminocapronic acid, enanthactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, and 9-amido.
  • polyamide resins Two or more of these polyamide resins may be used in combination, and other thermoplastic resins such as polyolefin resins, polystyrene resins, ABS resins, AS resins, polycarbonate resins, polyphenylene ether resins, It may contain a modified polyphenylene ether resin, polyester resin, polyacetal resin, polysulfone resin, polyphenylene sulfide resin, polyimide resin, etc.
  • the inorganic filler used in the present invention Known materials can be used, for example, glass fiber, carbon fiber, talc, my strength, silica, kaolin, clay, wollastonite, glass beads, glass flake, potassium titanate, and the like.
  • Examples include calcium carbonate, magnesium sulfate, and titanium oxide.
  • the shape of the agent may be any of fibrous, granular, plate-like, needle-like, spherical, powder, etc.
  • a flame retardant other than melam methansulfonate as a flame retardant other than melam methansulfonate.
  • Known flame retardants such as phosphorus-based flame retardants, inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide, and silicone-based flame retardants, and nitrogen-based flame retardants can also be used in combination.
  • heat stabilizer, light stabilizer, antioxidant It can be used in combination with those usually used in the production of general synthetic resins such as antistatic agents, pigments, fillers, lubricants, plasticizers, and coupling agents.
  • the melane sulfonic acid melam of the present invention may be a resin other than a polyamide resin, for example, a thermosetting resin such as a phenol resin, an epoxy resin, a polyurethane resin, or an unsaturated polyester resin, or a polyolefin such as PE, PP, EVA, or EEA.
  • a thermosetting resin such as a phenol resin, an epoxy resin, a polyurethane resin, or an unsaturated polyester resin
  • a polyolefin such as PE, PP, EVA, or EEA.
  • Resin PS, HIPS, AS, ABS, etc., polystyrene resin, vinyl chloride resin, polycarbonate resin, polyphenylene ether resin, modified polyphenylene ether resin, polyester resin, polyacetal resin, It is useful as a flame retardant for a wide range of resins such as thermoplastic resins such as polysulfone resin, polyphenylene sulfide resin and polyimide resin, and their copolymers and alloys. It is also useful as a flame retardant for these resin molded products, resin-containing paints and adhesives, fibers and textile products. Further, the melane methansulfonate of the present invention can be used not only as a flame retardant but also as a resin stabilizer.
  • the sample evaluation method in the present invention is as follows.
  • the measurement was carried out using an elemental analyzer vario EL (manufactured by Elemental).
  • Detection method UV detection method (230 nm) After dissolving the sample solution prepared sample 5 mg to Ol preparative-phosphate concentration S 5 weight 0/0 of ortho-phosphate solution 4 9 g, preparing a measurement sample solution was diluted to 5 0 0 ml with pure water I do.
  • N 0.5 A filter paper from which the undissolved sample was collected was placed in a Petri dish weighed precisely, and the Petri dish was placed in a hot air dryer preheated to 105 ° C and dried. . Then, the petri dish was immediately placed in a desiccator and allowed to cool.
  • the solubility (g / 100 ml) was determined by the following formula: 100 ⁇ (a— ⁇ ⁇ ⁇ ).
  • the 50% volume diameter (median diameter) was defined as the average particle diameter.
  • the 50% volume diameter (median diameter) was measured with a laser diffraction type particle size analyzer PRO-70000S (manufactured by Seishin Enterprise Co., Ltd.). (Measurement conditions)
  • the measurement was carried out using a differential thermal analyzer TGZDT A320 [manufactured by Seiko Electronics Co., Ltd.].
  • the average particle size of the obtained pulverized product was 4.
  • This calcined product had a pH of 5.1 as a 10% by weight aqueous slurry (25 ° C.).
  • the solubility in water (25 ° C) showed a very small value of 0.04 gZl 00 ml.
  • FIG. 1 shows the result of differential thermal analysis (TGZDTA) of the fired product.
  • the average particle size of the obtained pulverized product was 5. O ⁇ m.
  • This calcined product had a pH of 5.0 as a 10% by weight aqueous slurry (25 ° C).
  • the solubility in water (25 ° C) was as low as 0.05 gZ100m1.
  • test piece was 1 to 8 inches.
  • 30% glass fiber reinforced nylon 66 (manufactured by Toray Industries, Inc .: trade name C ⁇ 301-G30) shows the methane sulfonic acid melam (MMS-1) produced in Example 1 in Table 1.
  • the mixture was mixed with a mixer at the ratio shown, and the mixture was kneaded using a twin-screw extruder (manufactured by Kurimoto Iron Works) at a cylinder temperature of 275 ° C and extruded into a strand. After cooling, it was cut and dried to obtain pellets.
  • the obtained pellets were molded using an injection molding machine [manufactured by Nissei Plastic Industry Co., Ltd.] to obtain test pieces for a combustion test. Table 1 shows the evaluation results of these materials.
  • Example 6 Examples 6, 7, 8 Examples 3, 4, and 5 except that methanesulfonic acid melam (MMS-2) produced in Example 2 was used instead of methanesulfonic acid melam (MMS-1) produced in Example 1. The same was done. Table 1 shows the evaluation results of these materials.
  • Melam methanesulfonate obtained by the present invention is excellent in heat resistance and water resistance, and is extremely useful as a flame retardant especially for polyamide resins. Further, by using the melam methanesulfonate, it is possible to achieve flame retardancy of the synthetic resin without using a halogen-based flame retardant.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

L'invention porte sur un melam d'acide méthanesulfonique qui peut être utilisé de manière avantageuse comme agent ignifuge dans les résines synthétiques, notamment les résines polyamides. L'invention porte également sur une composition de résine polyamide ignifuge contenant le mélame d'acide méthanesulfonique. On obtient le melam d'acide méthanesulfonique par combustion d'un produit de la réaction de mélamine avec un acide méthanesulfonique à une température comprise entre 300 et 400 °C pendant une 0,1 à 30 heures. Cet acide a une solubilité dans l'eau (25 °C) comprise entre 0,01 et 0,10 g/100 ml, fournit une suspension aqueuse de 10 % en poids dont le pH (25 °C) est compris entre 3,0 et 7,0 et contient un melam dans une quantité comprise entre 0,90 et 1,30 mole par mole d'atomes de soufre.
PCT/JP2001/002501 2000-04-06 2001-03-27 Melam d'acide methanesulfonique, son procede de production et composition de resine polyamide ignifuge Ceased WO2001077088A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2000104396A JP4569721B2 (ja) 2000-04-06 2000-04-06 メタンスルホン酸メラム、その製造法及びそれを用いた難燃性ポリアミド樹脂組成物
JP2000-104396 2000-04-06

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* Cited by examiner, † Cited by third party
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US7498368B2 (en) 2003-05-26 2009-03-03 Polyplastics Co., Ltd. Flame-retardant resin composition
JP4996843B2 (ja) * 2005-10-28 2012-08-08 ポリプラスチックス株式会社 難燃性樹脂組成物

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996016948A1 (fr) * 1994-12-01 1996-06-06 Dsm N.V. Procede de preparation de produits de condensation de melamine

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* Cited by examiner, † Cited by third party
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JPH09137032A (ja) * 1995-11-15 1997-05-27 Nippon Steel Chem Co Ltd 熱安定性の改良された難燃性樹脂組成物

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996016948A1 (fr) * 1994-12-01 1996-06-06 Dsm N.V. Procede de preparation de produits de condensation de melamine

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JP2001288361A (ja) 2001-10-16

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