WO2016104263A1 - Ignifugeant, et composition de résine ignifuge le contenant - Google Patents

Ignifugeant, et composition de résine ignifuge le contenant Download PDF

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Publication number
WO2016104263A1
WO2016104263A1 PCT/JP2015/085139 JP2015085139W WO2016104263A1 WO 2016104263 A1 WO2016104263 A1 WO 2016104263A1 JP 2015085139 W JP2015085139 W JP 2015085139W WO 2016104263 A1 WO2016104263 A1 WO 2016104263A1
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Prior art keywords
resin
flame retardant
compound
flame
reaction
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PCT/JP2015/085139
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English (en)
Japanese (ja)
Inventor
翔 橋本
勝一 大槻
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大八化学工業株式会社
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Priority to JP2016566144A priority Critical patent/JP6635944B2/ja
Publication of WO2016104263A1 publication Critical patent/WO2016104263A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids

Definitions

  • the present invention relates to a flame retardant and a flame retardant resin composition containing the flame retardant. More specifically, the present invention can exhibit excellent flame retardancy as an additive-type flame retardant for resin flame retardant, particularly polyurethane foam, and can give excellent foamability and physical properties to polyurethane foam.
  • the invention relates to a flame retardant containing an organic phosphorus compound as a main component and a flame retardant resin composition containing the flame retardant.
  • a method of adding a flame retardant during the preparation of a resin molded product is employed.
  • the flame retardant include an inorganic compound, an organic phosphorus compound, an organic halogen compound, and a halogen-containing organic phosphorus compound.
  • the organic halogen compound and the halogen-containing organic phosphorus compound exhibit excellent flame retarding effects.
  • organic phosphorus compounds, particularly organic phosphate esters and halogen-containing organic phosphate esters are widely used as flame retardants that can provide good flame retardant effects.
  • polyurethane foams are flammable and have limited applications. In recent years, various studies have been made to make them flame retardant, but they are not sufficient. Conventionally, as a flame retardant for polyurethane foam, tris (2-chloroethyl) phosphate, squirrel (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate and the like have been used.
  • Lis (2-chloroethyl) phosphate and tris (dichloropropyl) phosphate when blended in flexible polyurethane foam, exhibit a flame retardant effect in the initial stage, but the flame retardant effect significantly decreases with time and fogging resistance
  • VOC volatile organic compounds
  • Tris (2,3-dibromopropyl) phosphate is excellent in terms of flame retardancy and durability, but is inferior in heat resistance. When added to flexible polyurethane foam, scorch is produced during foam production. It is not preferable. In addition, tris (2,3-dibromopropyl) phosphate has been used as a flame retardant for polyester fibers, but is not currently used due to suspected carcinogenic properties.
  • 2,2-bis (chloromethyl) trimethylenebis bis (2-chloroethyl) phosphate
  • Patent Document 2 2,2-bis (chloromethyl) trimethylenebis (bis (2-chloroethyl) phosphate)
  • tetrakis (2-chloroethyl) ethylene diphosphate for example, see Japanese Patent Publication No. 49-43272: Patent Document 2
  • these compounds must use chlorine gas at the time of production, have problems in production, and are not sufficient in terms of flame retardancy and sustainability.
  • the halogen-containing condensed phosphate ester of Patent Document 5 contains, as an impurity, a phosphorus compound having one hydroxyl group in the molecule, which is by-produced during the production thereof.
  • a halogen-containing condensed phosphate ester containing such a phosphorus compound having a hydroxyl group is added to a resin as a flame retardant, there is a problem that a transesterification reaction occurs with a terminal molecule of the resin and the molecular weight of the resin is lowered.
  • the resin when the resin is polyurethane foam, it reacts with isocyanate at the time of foaming to become the end of the polyurethane molecule, which hinders the increase in the molecular weight of the polyurethane, resulting in a decrease in the physical properties of the polyurethane foam. There is.
  • the present invention provides an excellent flame retardancy as an additive-type flame retardant for resin flame retardant, particularly when polyurethane foam is made flame retardant, and can give excellent foamability and physical properties to polyurethane foam. It is an object to provide a flame retardant containing a phosphorus compound as a main component and a flame retardant resin composition containing the flame retardant.
  • an organic phosphorus compound having one hydroxyl group in the molecule and a polyphosphate type organic phosphorus having a reduced phosphate ester monomer content.
  • the present inventors have found that the compound is an excellent flame retardant that satisfies most of the various conditions of a flame retardant for resins, particularly polyurethane foams, and has completed the present invention.
  • R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a monochloroalkyl group
  • Y is an alkylene group having 3 to 6 carbon atoms, or —CH 2 CH 2 (OCH 2 CH 2 ) z OCH 2 CH 2- (z is an integer of 0 to 3), and n is an integer of 0 to 10]
  • a flame retardant containing an organic phosphorus compound represented by When the flame retardant is measured by gel permeation chromatography (GPC), the general formula (II):
  • a flame retardant resin composition containing the above flame retardant and a resin.
  • an organic flame retardant that exhibits excellent flame retardancy as an additive-type flame retardant for resin flame retardants, particularly polyurethane foams, and that can impart excellent foamability and physical properties to polyurethane foams.
  • a flame retardant containing a phosphorus compound as a main component and a flame retardant resin composition containing the flame retardant can be provided.
  • the flame retardant of the present invention further exhibits the above excellent effects when the organic phosphorus compound is phosphoric acid oxydi-2,1-ethanediyltetrakis (2-chloro-1-methylethyl) ester.
  • the flame retardant resin composition of the present invention has any one of the following requirements:
  • the resin is a resin selected from polyurethane resin, acrylic resin, phenol resin, epoxy resin, vinyl chloride resin, polyamide resin, polyester resin, unsaturated polyester resin, styrene resin and synthetic rubber;
  • the polyurethane resin is a polyurethane foam, and the flame retardant resin composition satisfies the above-described excellent condition when it contains a flame retardant at a ratio of 1 to 40 parts by mass with respect to 100 parts by mass of the resin, More effective.
  • Flame retardant The flame retardant of the present invention has the general formula (I):
  • R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a monochloroalkyl group
  • Y is an alkylene group having 3 to 6 carbon atoms, or —CH 2 CH 2 (OCH 2 CH 2 ) z OCH 2 CH 2- (z is an integer of 0 to 3), and n is an integer of 0 to 10]
  • a flame retardant containing an organic phosphorus compound hereinafter also referred to as “compound (I)” as a main component, When the flame retardant is measured by gel permeation chromatography (GPC), the general formula (II):
  • the content of the compound represented by (hereinafter also referred to as “compound (II)”) is 4 area% or less.
  • the flame retardant of the present invention contains the compound (I) as a main component and contains a small amount of impurities by-produced in the production process, and strictly means a flame retardant composition.
  • the “main component” means having a content of 50% by area or more of the flame retardant of the present invention.
  • the content (area%) of compound (I) can be 55, 60, 65, 70, 75, or 80, but is preferably 80 area% or more as described later.
  • the content of compound (II) in GPC measurement is “4 area% or less” means that the content is “over 0 area% and 4 area% or less”.
  • the content (area%) of the compound (II) in specific GPC measurement is 0.0001, 0.0005, 0.001, 0.005, 0.01, 0.05, 0.1, 0.00. 2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.
  • the lower limit is preferably 0.01 area%, more preferably 0.001 area%, still more preferably 0.0001 area%, and the upper limit is preferably 3.8 area%, more preferably 3 .5 area%, more preferably 3.4 area%.
  • Compound (II) is a compound (also referred to as “half-ester”) that is produced by hydrolysis (by-product) when compound (I) is produced, and has one hydroxyl group in the molecule. For this reason, when it is added to a resin as a flame retardant, it causes a transesterification reaction with a terminal molecule of the resin, thereby reducing the molecular weight of the resin. In particular, when the resin is a polyurethane foam, it reacts with isocyanate at the time of foaming to become the end of the polyurethane molecule, thereby inhibiting the foaming of the polyurethane and the increase in the molecular weight, resulting in a decrease in the physical properties of the polyurethane foam.
  • the flame retardant of the present invention does not contain the compound (II).
  • the compound (II) in the GPC measurement can be prevented.
  • Content must be 4 area% or less.
  • the content of the compound (I) in GPC measurement is preferably 80 area% or more, more preferably 85 area% or more, and further preferably 90 area% or more.
  • the content (area%) of compound (I) in specific GPC measurement is 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 90.5, 91, 91. 5, 92, 92.5, 93, 93.5, 94, 94.5, 95, 95.5, 96, 96.5, 97, 97.5, 98, 98.5, 99 and 99.5, etc. It is.
  • the upper limit of the content is theoretically 100 area%, preferably 98 area%, more preferably 96 area%, and still more preferably 95 area%.
  • the flame retardant of the present invention is measured by gel permeation chromatography (GPC), the general formula (III): [Wherein, R has the same meaning as in formula (I). ]
  • the content of the compound represented by (hereinafter also referred to as “compound (III)”) is preferably 7 area% or less, and more preferably 6 area% or less.
  • the content of the compound (III) in GPC measurement is “7 area% or less” means that the content is “over 0 area% and 7 area% or less”.
  • the content (area%) of the compound (III) in specific GPC measurement is 0.0001, 0.0005, 0.001, 0.005, 0.01, 0.05, 0.1, 0.00. 5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5 and 7.0 or the like.
  • the lower limit thereof is preferably 0.01 area%, more preferably 0.001 area%, still more preferably 0.0001 area%, and the further preferable upper limit thereof is 5 area%, more preferably 4 area%. More preferably, it is 3 area%.
  • Compound (III) is a monomer phosphate ester produced (by-product) when producing Compound (I), and has a small molecular weight and easily volatilizes. For this reason, when it adds to a resin as a flame retardant, content of a volatile organic compound (VOC) will increase and fogging resistance will worsen. Therefore, it is most preferable that the flame retardant of the present invention does not contain the compound (III). However, since the by-product in the production process of the compound (I) cannot be completely prevented, the compound (III) in the GPC measurement can be prevented. ) Content is desirably 7% by area or less.
  • the substituent R in the general formula (I) is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a monochloroalkyl group.
  • the alkyl group having 1 to 4 carbon atoms may be linear or branched, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl groups.
  • a methyl group and an ethyl group are preferable in that the phosphorus content in the compound (I) is high, and a methyl group is more preferable.
  • the monochloroalkyl group having 1 to 4 carbon atoms may be linear or branched, and examples thereof include chloromethyl, chloroethyl, chloropropyl and chlorobutyl groups. Among these, a chloromethyl group and a chloroethyl group are preferable, and a chloromethyl group is more preferable in that the phosphorus content in the compound (I) is increased.
  • the substituent R is preferably a hydrogen atom, methyl, ethyl, chloromethyl, or chloroethyl group, more preferably a hydrogen atom, methyl group, or chloromethyl group, and particularly preferably a hydrogen atom or methyl group.
  • the substituent Y in the general formula (I) is represented by an alkylene group having 3 to 6 carbon atoms or —CH 2 CH 2 (OCH 2 CH 2 ) z OCH 2 CH 2 — (z is an integer of 0 to 3). It is a group.
  • the alkylene group having 3 to 6 carbon atoms may be linear or branched, and examples thereof include trimethylene, propylene, butylene, pentylene, and hexamethylene groups. Of these, trimethylene and propylene groups are preferred in that the phosphorus content in compound (I) is high.
  • a group represented by —CH 2 CH 2 (OCH 2 CH 2 ) z OCH 2 CH 2 — (z is an integer of 0 to 3) is a residue of oxyalkylene glycol, specifically, by a coefficient z, —CH 2 CH 2 OCH 2 CH 2 —, —CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 —, —CH 2 CH 2 (OCH 2 CH 2 ) 2 OCH 2 CH 2 —, —CH 2 CH 2 ( OCH 2 CH 2 ) 3 OCH 2 CH 2 —.
  • —CH 2 CH 2 OCH 2 CH 2 — and —CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 — are preferable in view of increasing the phosphorus content in the compound (I), and —CH 2 CH 2 OCH 2 CH 2 — is more preferred.
  • substituent Y trimethylene, a propylene group, and —CH 2 CH 2 OCH 2 CH 2 — are particularly preferable.
  • the coefficient n in the general formula (I) is an integer of 0 to 10.
  • the coefficient n exceeds 10, the flame retardancy does not change, and the handling becomes difficult only by increasing the viscosity, which is not preferable.
  • the coefficient n increases, the molecular weight of the compound (I) tends to increase and the viscosity tends to increase. Therefore, depending on the type of resin to be added, the physical properties of the resin to be obtained, the difficulty in manufacturing the compound (I), etc.
  • the coefficient n may be appropriately determined, but is usually preferably 0 to 5, and more preferably 0 to 3.
  • Examples of the compound (I) that is the main component of the flame retardant of the present invention include phosphoric acid oxydi-2,1-ethanediyltetrakis (2-chloroethyl) ester, phosphoric acid oxydi-2,1-ethanediyltetrakis (2 -Chloro-1-methylethyl) ester, oxy-2,1-ethanediylbis [10-chloro-7- (2-chloroethoxy) -7-oxide-3,6,8-trioxa-7-phosphadec-1 -Yl] bis (2-chloroethyl) ester, poly [oxy [(2-chloro-1-methylethoxy) phosphinylidene] oxy-1,2-ethanediyloxy-1,2-ethanediyl], ⁇ - (2-chloro -1-methylethyl) - ⁇ -[[bis (2-chloro-1-methyle
  • the flame retardant of the present invention can be obtained, for example, by the following two-stage reaction production method.
  • Y and n are the same as in general formula (I)).
  • hydrogen chloride is generated by an exothermic reaction.
  • the raw material phosphorus oxychloride remains unreacted in the system.
  • This remaining phosphorus oxychloride reacts with alkylene oxide or chloroalkylene oxide in the second reaction of the next step to produce a low molecular weight phosphate ester monomer, which reduces fogging and flame retardancy.
  • the produced hydrogen chloride and unreacted phosphorus oxychloride remaining in the system are removed under reduced pressure. That is, in the first reaction, phosphorus oxychloride and alkylene glycol or oxyalkylene glycol are in a molar ratio of 1.5 to 3.0: 1.0, preferably the phosphorus oxychloride is mol to alkylene glycol or oxyalkylene glycol
  • the reaction is carried out by continuously feeding the reaction vessel in an amount less than an equivalent amount, specifically, in a molar ratio of 1.7 to 2.0: 1.0.
  • the reaction temperature is 0 to 50 ° C., preferably 15 to 20 ° C., and the generated heat is removed by passing a refrigerant through a jacket or coil attached to the reaction vessel.
  • the produced condensed phosphorodichloridate is unstable to heat, and it is required to remove hydrogen chloride and remaining phosphorus oxychloride in as short a time as possible and in a short time. Therefore, hydrogen chloride and phosphorus oxychloride are removed at a temperature of 15 to 20 ° C., a degree of vacuum of 1 to 7 kPa, and then a temperature of 20 ° C. or less and a degree of vacuum of 0.1 to 1 kPa.
  • the residual amount of hydrogen chloride and phosphorus oxychloride in the first reaction solution can be minimized within a temperature range of 16 to 20 ° C. and a vacuum level of 0.1 to 1 kPa. it can.
  • the alkylene glycol used in the reaction is 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,3-butylene.
  • Examples include glycol, 1,6-hexanediol, 2,4-hexanediol, and 2,5-hexanediol, but are not limited thereto.
  • Examples of the oxyalkylene glycol include diethylene glycol, triethylene glycol, and tetraethylene glycol, but are not limited thereto.
  • the condensed phosphorodichloridate When the condensed phosphorodichloridate is reacted with alkylene oxide or chloroalkylene oxide, this reaction is also exothermic, as in the first reaction. Since the condensed phosphorodichloridate is weak and unstable to heat, the second reaction is preferably a continuous reaction rather than a batch reaction in which the heat receiving time is long. When the heat receiving time is increased, the condensed phosphorodichloridate is thermally decomposed, which is accompanied by an undesirable side reaction.
  • the heat receiving time of the condensed phosphorodichloridate is shortened, and the occurrence rate of thermal decomposition and undesirable side reactions is significantly reduced compared to the batch system. That is, it is preferable that the alkylene oxide or chloroalkylene oxide corresponding to the reaction product is supplied and gradually reacted while quantitatively supplying the reaction product of the first reaction containing the condensed phosphorodichloridate. Specifically, it is preferable to react both products while supplying the reaction product of the first reaction and the alkylene oxide or chloroalkylene oxide with a tube-type metering pump and a flow meter.
  • alkylene oxide used in the reaction examples include, but are not limited to, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and the like. Among these, ethylene oxide and propylene oxide are preferable, and propylene oxide is more preferable.
  • chloroalkylene oxide examples include epichlorohydrin and the like, but are not limited thereto.
  • Theoretical usage (g) (A ⁇ B ⁇ C) / (100 ⁇ 35.5) [Wherein A is the mass (g) of condensed phosphorodichloridate, B is the chlorine content (% by mass) of condensed phosphorodichloridate, C is the molecular weight of alkylene oxide or chloroalkylene oxide, 35.5 is It is the atomic weight of chlorine]
  • the actual amount of alkylene oxide or chloroalkylene oxide used is 10% by mass excess, preferably 2-6% by mass excess of the theoretical usage amount to the theoretical usage amount.
  • An excess amount of more than 6% by mass of alkylene oxide or chloroalkylene oxide has an advantage that the aging (retention) time required for completion of the reaction can be shortened, but it is economically disadvantageous for increasing the amount of use.
  • the reaction temperature is 40 to 90 ° C, preferably 50 to 70 ° C. At temperatures below 40 ° C, the progress of the reaction becomes very slow and impractical. At temperatures above 90 ° C, phenomena such as coloring of the reaction liquid and an increase in by-products occur, resulting in a high-quality product. Can not be.
  • the reaction time required to complete the reaction is in the range of 5 to 30 hours, preferably 10 to 20 hours, on an industrial scale reaction using raw materials economically.
  • condensed phosphorodichloridate When a continuous reaction is carried out at a reaction temperature of 55 to 60 ° C. with an excess of 5% by mass of propylene oxide, the residence time for obtaining a product with good quality is preferably 10 to 20 hours. Is 12-15 hours.
  • the reaction mixture is discharged from the reactor and commercialized through a washing and dehydration process as a purification process.
  • the washing step is generally performed by a known method, and can be performed by either a batch method or a continuous method. Specifically, the reaction mixture is washed with a mineral acid solution such as sulfuric acid and hydrochloric acid, then washed with an alkali and water, and dehydrated under reduced pressure. Alternatively, the reaction mixture is washed with an alkali without washing with a mineral acid, and the formed water-insoluble titanium compound (catalyst component) is removed by filtration or centrifugation, washed with water, and dehydrated under reduced pressure.
  • a mineral acid solution such as sulfuric acid and hydrochloric acid
  • the temperature of the washing step is 95 ° C. or less, preferably 85 ° C. or less, more preferably 70 ° C. or less, and further preferably 55 to 65 ° C.
  • the dehydration step is preferably performed under reduced pressure.
  • the temperature of the dehydration step is 120 ° C. or less, preferably 110 ° C. or less, more preferably 95 to 105 ° C., and the pressure is 10 kPa or less, preferably 1 to 5 kPa.
  • the product may be subjected to a purification step in order to completely remove low-boiling components.
  • a purification step steam distillation under reduced pressure is preferable.
  • the temperature is 120 ° C. or lower, preferably 110 ° C. or lower, more preferably 95 to 105 ° C., and the pressure is 10 kPa or lower, preferably 1 to 5 kPa.
  • the flame retardant resin composition of the present invention comprises the flame retardant of the present invention and a resin.
  • the flame retardant of the present invention has high purity and high quality, and can be used as a flame retardant for various thermoplastic resins and thermosetting resins.
  • thermoplastic resin examples include polyethylene resin, chlorinated polyethylene resin, polypropylene resin, polybutadiene resin, styrene resin, vinyl chloride resin, polyphenylene ether resin, polyphenylene sulfide resin, polycarbonate resin, ABS (acrylonitrile-butadiene-styrene) resin, Saturated or unsaturated polyester resins such as impact-resistant styrene resin, rubber-modified styrene resin, SAN (styrene-acrylonitrile) resin, ACS resin, polyamide resin, polyimide resin, PET (polyethylene terephthalate) resin and PBT (polybutylene terephthalate) resin Acrylic resin, polymethacrylic resin, polyetheretherketone resin, polyethersulfone resin, polysulfone resin, polyarylate resin, polyester Examples include ether ketone resins, polyether nitrile resins, polythioether sulfone resins, polybenzimidazole
  • thermosetting resins examples include epoxy resins, polyurethane resins, polyimide resins, phenolic resins, novolac resins, resole resins, polyetherimide resins, melamine resins, urea resins, unsaturated polyester resins, diallyl phthalate resins, and the like. These 1 type can be used individually or in mixture of 2 or more types.
  • polyurethane resins acrylic resins, phenol resins, epoxy resins, vinyl chloride resins, polyamide resins, polyester resins, unsaturated polyesters can be used as the resins that the flame retardant composition of the present invention can sufficiently perform its functions.
  • Resins selected from resins, styrene resins and synthetic rubbers are preferred, polyurethane resins are more preferred, and polyurethane foams are particularly preferred.
  • the synthetic rubber means a resin (elastomer) having rubber elasticity obtained by addition polymerization or copolymerization among the thermoplastic resins, and examples thereof include polybutadiene, nitrile, and chloroprene.
  • the amount of flame retardant added may be appropriately set depending on the type of resin to be added, the desired degree of flame retardant, etc., and the flame retardant composition of the present invention is usually based on 100 parts by mass of the resin. 1 to 40 parts by mass of a flame retardant is preferably contained. If the amount of the flame retardant added is less than 1 part by mass, it may not be possible to impart sufficient flame retardancy to the resin. On the other hand, when the amount of the flame retardant added exceeds 40 parts by mass, the physical properties of the resin itself, particularly the mechanical physical properties, may be deteriorated.
  • the amount of flame retardant added (parts by mass) relative to 100 parts by mass of specific resin is 1, 5, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23. 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40. A more preferable amount of the flame retardant added is 1 to 35 parts by mass, and particularly preferably 1 to 30 parts by mass.
  • the flame retardant resin composition of the present invention may be added with known resin additives, that is, other flame retardants and other additives other than the flame retardant, as long as they do not adversely affect the physical properties of the resin. May be included. These addition amounts may be set as appropriate depending on the type of resin and the desired physical properties.
  • flame retardants include, for example, non-halogen phosphate ester flame retardants such as triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, resorcinol-tetraphenyl bisphosphate, bisphenol A-tetraphenyl bisphosphate; -Including bis (chloromethyl) -1,3-propanebis (chloroethyl) diphosphate, tetrakis (2-chloroethyl) ethylene diphosphate, (poly) alkylene glycol halogen-containing polyphosphate, tris (tribromo) neopentyl phosphate, etc.
  • non-halogen phosphate ester flame retardants such as triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, resorcinol-tetraphenyl bisphosphate, bisphenol A-tetraphenyl bisphosphate;
  • Halogen phosphate ester flame retardants brominated flame retardants such as decabromodiphenyl ether, tetrabromobisphenol A, 1,2-bis (pentabromophenyl) ethane; antimony trioxide, Inorganic flame retardants such magnesium oxide; ammonium polyphosphate, such as nitrogen-based flame retardant such as melamine phosphate and the like.
  • additives besides flame retardants include antioxidants, fillers, lubricants, modifiers, fragrances, antibacterial agents, pigments, dyes, heat-resistant agents, weathering agents, antistatic agents, UV absorbers, stabilizers, Strengthening agents, anti-drip agents, anti-blocking agents, wood flour, starch and the like.
  • the flame retardant of the present invention exhibits an excellent flame retardancy particularly as an additive-type flame retardant when making a polyurethane foam flame retardant, and an organophosphorus compound having excellent polyurethane foam foaming properties and physical properties.
  • a flame retardant as a main component and a flame retardant resin composition containing the flame retardant can be provided.
  • the flame retardant of the present invention has a very low volatility of the main component compound (I), and exhibits an excellent flame retardant effect when added to a resin, particularly by adding to a polyurethane foam component before foaming according to a predetermined formulation. .
  • the obtained polyurethane foam exhibits excellent flame retardancy and foamability by a flammability test method such as MVSS-302. That is, the flame-retardant polyurethane foam is superior in flame retardancy and durability as compared with a polyurethane foam flame-retarded with an existing organic phosphorus compound-based flame retardant, and further has excellent fogging resistance.
  • a method for producing a polyurethane foam is already known, and a flame retardant polyurethane foam to which the flame retardant of the present invention is added can also be produced by a known method.
  • 1 to 40 parts by mass, preferably 1 to 30 parts by mass of the flame retardant of the present invention is mixed with 100 parts by mass of polyol including polyester polyol, polyether polyol and the like.
  • a foam stabilizer, a catalyst, a foaming agent, etc. to the obtained mixture and stirring, when an organic polyisocyanate is added and reacted, a flame-retardant polyurethane foam is obtained.
  • the polyol is not particularly limited as long as it is generally used as a raw material for forming polyurethane, but a polyester polyol and a polyether polyol having about 2 to 8 hydroxyl groups per molecule and having a molecular weight of about 250 to 6500. Polyols such as are preferably used. When the molecular weight is smaller than 250, the activity is strong and not suitable for forming urethane foam, and when the molecular weight is larger than 6500, the viscosity is increased and workability may be deteriorated.
  • polyols examples include diols; triols; and polyols obtained by polymerizing ethylene oxide and / or propylene oxide using initiators such as sorbitol, sucrose, or ethylenediamine as initiators.
  • diols such as polyoxyethylene glycol and polyoxypropylene glycol; polyoxyethylene glycerol, polyoxypropylene glycerol, poly (oxyethylene) poly (oxypropylene) glycerol, polyoxyethylene neohexanetriol, polyoxypropylene Triols such as pentaneohexanetriol, poly (oxyethylene) poly (oxypropylene) neohexanetriol, poly (oxypropylene) 1,2,6-hexanetriol, and polyoxypropylenealkanol; poly (oxyethylene) poly (oxy Propylene) ethylenediamine; hexol such as polyoxyethylene sorbitol, polyoxypropylene sorbitol; polyoxyethylene sucrose
  • polyol and a phosphorus-containing polyol in which melamine or ammonium polyphosphate, which is commercially available as a special grade, is dispersed are also included.
  • Preferred polyols include polyether polyols with poly (oxyethylene / oxypropylene) triols having an average molecular weight in the range of about 250 to about 6500.
  • organic polyisocyanates include, but are not limited to, butylene diisocyanate, phenylene diisocyanate, xylene diisocyanate, biphenyl diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, cyclopentane diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentane Examples include methylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene diisocyanate.
  • foam stabilizer examples include silicone foam stabilizers (silicone oils) such as siloxane-oxyalkylene block copolymers.
  • silicone foam stabilizers such as siloxane-oxyalkylene block copolymers.
  • Specific examples include NIAX SILICON L-580, L-590, L-620, L-638, L-638J, L-680, L-682, and L-690 manufactured by Momentive Performance Materials. .
  • the catalyst examples include triethylenediamine, dimethylethanolamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N ′, N′-trimethylaminoethylpiperazine, Examples thereof include amine catalysts such as N-ethylmorpholine; tin catalysts such as stannous octoate and dibutyltin dilaurate.
  • dispersant nonionic surfactants such as ether type, ether ester type, and ester type can be used.
  • alkyl methyl, ethyl, propyl, butyl, amyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl
  • aryl phenyl, tolyl, xylyl, biphenyl, naphthyl
  • alkylaryl formaldehyde examples include condensed polyoxyethylene ether, polyoxyethylene ether of glycerin ester, polyethylene glycol fatty acid ester, propylene glycol ester, polyglycerin, sorbitan ester, fatty acid monoglyceride, and mixtures thereof.
  • the acid value (KOHmg / g) of the obtained product was measured according to JIS K0070 neutralization titration method.
  • the viscosity (mPa ⁇ s) of the obtained product was measured under the condition of a temperature of 25 ° C. using an Ubbelohde viscometer according to JIS Z8803.
  • the reaction product obtained in the second reaction was subjected to a purification step batchwise.
  • a washing step 100 g of sulfuric acid having a concentration of 0.1% by mass was added to the reaction solution at a temperature of 60 ° C. and stirred for 30 minutes, and then 3 g of sodium carbonate and 150 g of water were added to the reaction solution and stirred for 30 minutes. Summed and allowed to settle to separate the aqueous phase. Thereafter, the oil phase was washed with 250 g of water at the same temperature.
  • the obtained reaction product was subjected to a vacuum dehydration step at a temperature of 100 ° C. and a pressure of 4 kPa.
  • part means “part by mass”
  • a polyol, a foam stabilizer, a catalyst, a foaming agent, and a flame retardant were blended, and the blend was uniformly mixed by stirring for 1 minute at 3000 rpm using a stirrer. Thereafter, further isocyanate was added, and the mixture was stirred at a rotational speed of 3000 rpm for 5 to 7 seconds.
  • the formulation was then immediately poured into a cube (about 200 mm high) cardboard box with a square bottom (about 200 mm on each side). Foaming occurred immediately and reached the maximum volume after a few minutes. Next, the obtained foam was allowed to stand for 30 minutes in a furnace at a temperature of 120 ° C. to be cured.
  • Example 3 As a flame retardant control test, a foam was produced and evaluated in the same manner as in Example 1 except that no flame retardant was added (Comparative Example 3). The obtained foam had a white soft open-cell type cell structure. The obtained results are shown in Table 2 together with a part of the formulation (the amount of flame retardant and isocyanate used).
  • the flame retardant of the present invention and the flame retardant resin composition containing the flame retardant exhibit excellent flame retardancy among the required conditions, and are excellent in the foamability and physical properties of the polyurethane foam.
  • the air permeability and compressive residual strain were greatly changed as compared with the foams of Examples 1 to 3. This is because the compound (II) is a monofunctional compound, so it reacts with isocyanate faster than a polyfunctional and high molecular weight polyol, and the usual urethane foam formation reaction stops halfway. It is thought that the formation of the urethane foam was inhibited and the physical properties of the urethane foam were affected.

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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)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un ignifugeant contenant en tant que composant principal un composé organique du phosphore représenté par la formule générale (I) : (dans la formule, R représente un atome d'hydrogène ou un groupe alkyle en C1-4 ou un groupe monochloroalkyle, Y représente un groupe alkylène en C3-6 ou un groupe représenté par la formule -CH2CH2(OCH2CH2)zOCH2CH2- (z représente un nombre entier de 0 à 3), n représente un nombre entier de 0 à 10). L'ignifugeant possède une quantité contenue d'un composé représenté par la formule générale (II) : (dans la formule, R, Y, et n sont définis de la même façon que dans la formule générale (I)) d'au plus 4 % en aire lorsque l'ignifugeant est mesuré par chromatographie par perméation de gel (CPG) ; et une composition de résine ignifuge contenant cet ignifugeant et une résine.
PCT/JP2015/085139 2014-12-24 2015-12-16 Ignifugeant, et composition de résine ignifuge le contenant WO2016104263A1 (fr)

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JP2018090731A (ja) * 2016-12-06 2018-06-14 大八化学工業株式会社 難燃性木質材料及びその製造方法
JP2021500430A (ja) * 2017-10-18 2021-01-07 アセンド・パフォーマンス・マテリアルズ・オペレーションズ・リミテッド・ライアビリティ・カンパニーＡｓｃｅｎｄ Ｐｅｒｆｏｒｍａｎｃｅ Ｍａｔｅｒｉａｌｓ Ｏｐｅｒａｔｉｏｎｓ Ｌｌｃ ハロゲン含有難燃性ポリアミド組成物
JP2021050257A (ja) * 2019-09-20 2021-04-01 三菱ケミカル株式会社 リン酸エステル系難燃剤、（メタ）アクリル系樹脂組成物及び樹脂成形体
CN113637254A (zh) * 2021-09-18 2021-11-12 包头稀土研究院 聚烯烃组合物的制备方法及哌嗪类化合物的用途
CN116496469A (zh) * 2023-03-13 2023-07-28 广州光通科技有限公司 含磷阻燃树脂及其制备方法和应用

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JPS4998092A (fr) * 1972-12-26 1974-09-17
DE2302843A1 (de) * 1973-01-20 1974-07-25 Bayer Ag Verfahren zur herstellung von biseckige klammer auf di(-halogenalkyl)phosphorsaeure eckige klammer zu -polyaethylenglykolestern
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018090731A (ja) * 2016-12-06 2018-06-14 大八化学工業株式会社 難燃性木質材料及びその製造方法
JP2021500430A (ja) * 2017-10-18 2021-01-07 アセンド・パフォーマンス・マテリアルズ・オペレーションズ・リミテッド・ライアビリティ・カンパニーＡｓｃｅｎｄ Ｐｅｒｆｏｒｍａｎｃｅ Ｍａｔｅｒｉａｌｓ Ｏｐｅｒａｔｉｏｎｓ Ｌｌｃ ハロゲン含有難燃性ポリアミド組成物
JP7135083B2 (ja) 2017-10-18 2022-09-12 アセンド・パフォーマンス・マテリアルズ・オペレーションズ・リミテッド・ライアビリティ・カンパニー ハロゲン含有難燃性ポリアミド組成物
JP2021050257A (ja) * 2019-09-20 2021-04-01 三菱ケミカル株式会社 リン酸エステル系難燃剤、（メタ）アクリル系樹脂組成物及び樹脂成形体
JP7352906B2 (ja) 2019-09-20 2023-10-02 三菱ケミカル株式会社 リン酸エステル系難燃剤、（メタ）アクリル系樹脂組成物及び樹脂成形体
CN113637254A (zh) * 2021-09-18 2021-11-12 包头稀土研究院 聚烯烃组合物的制备方法及哌嗪类化合物的用途
CN113637254B (zh) * 2021-09-18 2023-03-03 包头稀土研究院 聚烯烃组合物的制备方法及哌嗪类化合物的用途
CN116496469A (zh) * 2023-03-13 2023-07-28 广州光通科技有限公司 含磷阻燃树脂及其制备方法和应用
CN116496469B (zh) * 2023-03-13 2024-01-26 广州光通科技有限公司 含磷阻燃树脂及其制备方法和应用

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