CN1351642A - Flame-retarding composition and process for the preparation thereof - Google Patents
Flame-retarding composition and process for the preparation thereof Download PDFInfo
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- CN1351642A CN1351642A CN00807657A CN00807657A CN1351642A CN 1351642 A CN1351642 A CN 1351642A CN 00807657 A CN00807657 A CN 00807657A CN 00807657 A CN00807657 A CN 00807657A CN 1351642 A CN1351642 A CN 1351642A
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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
- C09K21/14—Macromolecular materials
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
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Abstract
The invention also relates to a flame-retarding composition comprising: 10 - 90 wt. % melem, 0.01 - 30 wt. % melam, 0.01 - 15 wt. % melamine, 0.1 - 65 wt. % higher condensation products of melamine and/or melem, the volatiles content being lower than 3 wt. % and the sum of the individual components amounting to 100 wt. %. Also a process for the preparation of a flame-retarding composition comprising 10 - 90 wt. % melem, 0.01 - 30 wt. % melam, 0.01 - 15 wt. % melamine and 0.1 - 65 wt. % higher condensation products of melamine and/or melem, the volatiles content being lower than 3 wt. %, by heating melamine-containing starting product fo r more than 0.1 second, for example by passing it through a heating zone, at a temperature of 350 - 800 ~C and a pressure of between 1 KPa and 50 Mpa. The invention also relates to polymer compositions containing the flame-retardin g composition.
Description
The present invention relates to fire-retardant combination and preparation method thereof.
In the open JP59-45352 of Japanese Patent, described the example of a kind of fire-retardant combination and preparation method thereof, prepared melamine condensation products melem and melon in this example and used as the fire retardant of daiamid composition.In the disclosure, melem prepares by heating several hrs under 400-500 ℃ temperature.Melon does not prepare till having ammonia to discharge by heating melamine down at 500-550 ℃.JP59-45352 proposes the decomposition temperature of melem more than 500 ℃, and the decomposition temperature of melon is more than 600 ℃.This means that melem and melon have good especially thermostability.According to JP59-45352, the nitrogen content of two kinds of compounds is higher than 60%, and consequently these two kinds of materials are the non-combustible material.JP59-45352 also proposes other known fire retardant such as melamine, cyanuric acid, cyanuric acid melamine or melam also can use with melem or melon.JP 59-45352 does not mention the composition of the product that obtains.
Melamine and its condensation product all have feature thermal destruction curve.This means melamine and its condensation product formation nitrogen-containing products of degrading at a certain temperature.These nitrogen-containing products that discharge in thermal destruction have played vital role in flame retardant properties.In order in polymkeric substance, to obtain excellent flame-retardant performance, with the form combination of single composition have the flame retardance element of different degraded features such as melam, melem and more the condensation product of high-grade melamine and/or melem may be useful.Its advantage is regardless of the temperature under most of situation in the fire, the component existence of degrading under general temperature is almost always arranged and produce the nitrogen component that enough has flame retardant effect.But, if fire-retardant combination contains volatile constituent such as urea and/or water, when said composition is used for dystectic polymkeric substance such as polyester and resembles polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) or polymeric amide, just will have a negative impact to processing characteristics.This negative impact can be when extrusion molding the foaming or on the mould of injection molding, form settling.If fire-retardant combination contains very the melamine of high density and/or the more senior condensation product of melem, composition will be yellow, and this is non-required under the situation of processing (not painted) polymer composition.In polymkeric substance, use pure melamine condensation products such as pure melam or melem or melon as fire retardant and improper, because it is relatively more difficult and uneconomical usually to prepare pure compound, and pure component has only a kind of degradation model and therefore only plays the best use of in limited temperature range.
Applicant is found can be by using a kind of fire-retardant combination to obtain excellent processing characteristics and excellent flame-retardant and color characteristics in polymer composition, and described fire-retardant combination comprises:
The melem of 10-90% (weight),
The melam of 0.01-30% (weight),
The melamine of 0.01-15% (weight),
The summation that the more senior condensation product of 0.1-65% (weight) melamine and/or melem, the concentration of volatile constituent are lower than 3% (weight) and each component is 100% (weight).
The concentration of volatile constituent is defined herein as to be measured in (TGA=thermo-gravimetric analysis) weight that occurs with the speed of 200 ℃ of per minutes fire-retardant combination when room temperature is heated to 300 ℃ at TGA and reduces.
The applicant has also found the melem of a kind of 10-90% of comprising (weight), the melam of 0.01-30% (weight), the melamine of 0.01-15% (weight), the summation that the more senior condensation product of 0.1-65% (weight) melamine and/or melem and the concentration of volatile constituent are lower than 3% (weight) and each component is the preparation method of the fire-retardant combination of 100% (weight), heating contains the raw material of melamine exactly, for example raw material is passed through 350-800 ℃, preferred 375-600 ℃ temperature and 1KPa are to 50MPa, preferred normal pressure is to 30MPa, especially normal pressure is to the heating zone of the pressure of 15MPa more than 0.1 second, preferred 1 second to 400 minutes, especially time of 2 seconds to 300 minutes.
The example of heating zone has at extruding machine such as single screw rod and Bitruder, autoclave, turbo mixer, plough blade mixer, drum tumbler, turbulent flow mixing tank, ribbon blender, squeezes the heating zone of visible type in refining machine, continuous and interrupted kneader, the rotary drum baking oven etc.
Melamine, melem, melam and more the mixture of the condensation product of high-grade melamine and/or melem can choose wantonly by further processing heating product and obtain, the fire-retardant combination that is obtained comprises that the summation that the concentration of the more senior condensation product of melamine, 0.1-65% (weight) melamine and/or melem of melam, 0.01-10% (weight) of melem, the 0.01-30% (weight) of 10-90% (weight) and volatile constituent is lower than 1% (weight) and each component is 100% (weight).This further processing is preferably to wash with water dissolves and removes a part of melamine and/or other water soluble ingredient in the fire-retardant combination.
As raw material of the present invention, can use the higher melamine of purity, for example from the melamine of the operate continuously gas-phase melamine device by crystallization process purifying melamine.A kind of vapor phase process prepares the method for melamine can be referring to for example US-A-3210352.But this high purity there is no need.The melamine that is mixed with melam and/or melem and/or melamine and/or the more higher amines condensation product reined in of honey can randomly be used as raw material, for example can use product or this class melamine that before crystallization purifying, in the gas-phase melamine device, prepares of the production of melamine device initial period or be mixed with melam and/or melem and/or melamine and/or melem with the melamine of the more senior condensation product of certain other approach formation.The melamine that also can use the liquid phase method acquisition is as raw material.A kind of liquid phase method of known preparation melamine is the method described in the US-A-4565867, and the purity of the melamine of known this method preparation is lower than vapor phase process, and specifically the content of its melam is higher.Also may there be pollutent such as residual catalyst, urea groups melamine and/or Guanidinium carbonate undoubtedly.Also may exist undoubtedly and contain oxygen triaizine compounds such as cyanurodiamide, cyanuramide and/or cyanuric acid to 5% (weight).Also may there be other raw material such as urea and/or the Dyhard RU 100 that are used to prepare melamine; The amount of Dyhard RU 100 can be gone up to 10% (weight), and melamine can comprise to the urea of 30% (weight).The raw material that the inventive method is used also can comprise and comprise urea, contains the oxygen triaizine compounds, the pollutent of the mixture of Dyhard RU 100, Guanidinium carbonate, urea groups melamine and residual catalyst.
In a preferred embodiment of the invention, fire-retardant combination contains the melamine raw material and prepares by heating in autoclave or extruding machine.Preferred pressure be normal pressure to 20MPa, temperature is 350-625 ℃, the residence time is 0.1 second to 360 minutes.The heating that more preferably contains the melamine raw material is carried out in extruding machine, and the residence time in extruding machine is 0.1 second to 60 minutes.
The present invention also relates to flame retardant compositions, it comprises following component:
A, 65-95% (weight) contain the composition of polymkeric substance
B, 5-35% (weight) fire-retardant combination of the present invention.
Fire-retardant combination of the present invention need to be specially adapted to the polymer composition of heat-proof combustion-resistant agent, for example polymeric amide, polyimide, polyester, contain styrene polymer, Resins, epoxy, unsaturated polyester resin and urethane.
The example of polymeric amide has and comes from diamines and dicarboxylic acid and/or come from aminocarboxylic acid or the polymeric amide of corresponding lactam and copolyamide, as (being total to) polymeric amide of polymeric amide 4, polyamide 6, polyamide 6/6,6/10,6/9,6/12,4/6,66/6,6/66, polymeric amide 11, polymeric amide 12, part fragrance, as has the polymeric amide of aromatic diamines and hexanodioic acid; With the alkylene diamines and and/or the polymeric amide of terephthalic acid preparation and its copolyamide, copolyether amide, copolyesteramide or the like.
The example of polyester has and comes from dicarboxylic acid and dibasic alcohol and/or come from hydroxycarboxylic acid or the polyester of corresponding lactone such as polyethylene terephthalate, polybutylene terephthalate, poly--1,4-hydroxymethyl-cyclohexane terephthalate, poly-hydroxybenzoate, polycaprolactone and its copolyesters, copolyether ester etc.
The example that contains cinnamic polymkeric substance has polystyrene, acrylonitritrile-styrene resin, acrylonitrile-styrene-butadienecopolymer and its mixture.
Described fire-retardant combination is preferred in polyester such as polyethylene terephthalate and/or the polybutylene terephthalate (being particularly preferred for polybutylene terephthalate), or is used in polymeric amide such as nylon 6, nylon 6,6 or the nylon 4,6.
" composition that contains polymkeric substance " is understood that also can to comprise toughener and/or filler, fire-retardant combination had other flame retardance element beyond the compound of synergism, the fire-retardant combination of the present invention and adds the composition of conventional additives except polymkeric substance.
If toughener and/or filler are used for polymer composition of the present invention, their concentration can have big variation, depends in part on people and wishes the mechanical property levels that reaches.Usually, no more than 50% (weight) of enhancer concentration in the flame retardant compositions of strengthening.The preferred flame retardant compositions of strengthening comprises the toughener of 5-50% (weight), more preferably comprises the toughener of 15-45% (weight).Described toughener can be selected from inorganic strengthening agent such as mica, clay, talcum or glass fibre, perhaps Kevlar and/or carbon fiber.But preferred glass fibers.
The flame retardant effect of fire-retardant combination of the present invention can be by having synergistic effect with it the existence of compound strengthen, the example of this compound has the carbonific that comprises or do not comprise the catalyzer that promotes that carbon forms.The common like this fire-retardant combination of selecting to use lower concentration.
In principle, the known substance of all enhancing fire-retardant combination effects all can serve as carbon compound.Example has resol, Resins, epoxy, melamine resin, Synolac, allylic resin, unsaturated polyester resin, silicone resin, urethane resin, acrylate resin, polyphenylene oxide, polycarbonate, starch, glucose and contains the compound of at least two hydroxyls.The example that contains the compound of at least two hydroxyls has alcohols such as tetramethylolmethane, dipentaerythritol, tripentaerythritol and its mixture that contains at least two hydroxyls.In whole polymer composition and fire retardant have the concentration of carbonific of synergistic effect generally between 0-30% (weight), preferred 1-20% (weight).
As the catalyzer that promotes into carbon, can use metal-salt, tungsten and a kind of metalloid complex acid oxide compound of wolframic acid for example, salt, Ammonium sulfamate and/or its dimer of stannic oxide.The metal-salt of wolframic acid is preferably an alkali metal salt of wolframic acid, particularly sodium wolframate." tungsten and a kind of metalloid complex acid oxide compound " is meant complex acid oxide compound such as silicotungstic acid or the phospho-wolframic acid that is formed by a kind of metalloid such as silicon or phosphorus and tungsten.It is 0.1-5% (weight) that the promotion that is used for whole polymer composition becomes the amount of the catalyzer of carbon, is preferably 0.1-2.5% (weight).
The flame retardant effect of fire-retardant combination of the present invention can strengthen by using one or more other flame retardance elements.In principle, all known fire retardants can be used as described other flame retardance element.Example has and halogen compounds blended sb oxide such as ANTIMONY TRIOXIDE SB 203 99.8 PCT; Alkaline earth metal oxide such as zinc oxide, magnesium oxide; Other metal oxide such as aluminum oxide, silicon-dioxide, ferric oxide and manganese oxide; Metal hydroxides such as magnesium hydroxide and aluminium hydroxide; Metal borate such as hydration or non-hydrated zinc borate; And P contained compound.The example of P contained compound has zinc phosphate, ammonium phosphate, ammonium pyrophosphate, ammonium polyphosphate, ethylene diamine phosphate, piperazine phosphate, piperazine pyrophosphate, melamine phosphate, the di(2-ethylhexyl)phosphate melamine, melamine pyrophosphate, the Tripyrophosphoric acid melamine, the phosphoric acid melam, the tetra-sodium melam, the Tripyrophosphoric acid melam, the phosphoric acid melem, the tetra-sodium melem, the Tripyrophosphoric acid melem, phosphoguanidine, phosphoric acid dicyandiamide, the phosphoric acid ester of the more high-grade condensation product of Ureaphil and melamine and/or melem, the mixture of pyrophosphate and polyphosphate and these phosphoric acid ester.Also can use acid, salt, mixing hydrochlorate, ester, partial ester and the mixed ester of phosphoric acid ester.Also can use phosphine oxide, phosphine sulfide and phosphorinanes and phosphonic acid ester, phosphorous acid ester and phosphinate and their acid, salt, mixing hydrochlorate, ester, partial ester and mixed ester.The concentration of other flame retardance element of available can have big variation, but generally is not higher than the concentration of fire-retardant combination of the present invention.Preferred its amount is between 0-35% (weight), more preferably between 1-20% (weight).Preferred phosphoric acid ester, phosphinate and the phosphonic acid ester of using.The example of this compound is described in for example Encylcopedia of Chemical Technology of Kirk Othmer, the 10th volume, 396-419 page or leaf (1980).The example that people are familiar with has: the aluminium salt of the ester of TriMethylolPropane(TMP) and methyl-phosphorous acid, ethyl-methyl phospho acid and ethyl-methyl phospho acid.Here the chemical compound lot of mentioning also can promote the formation of carbon.Also can exist in other known compound such as the tetrafluoroethylene that exist in the fire-retardant combination.
Polymer composition also can contain other conventional additives such as thermo-stabilizer and ultra-violet stabilizer, releasing agent, softening agent, tenderizer, lubricant, dispersion agent, tinting material and/or pigment, and their consumption generally exceeds required character is not had a negative impact.
Can use the routine techniques of itself being familiar with to prepare polymer composition of the present invention, for example under drying conditions, in drum tumbler, mix all or part of component and then fusion in melt mixer such as Brabender mixing tank or single screw rod or Bitruder or kneader as people.The preferred Bitruder that uses.
The various components of polymer composition of the present invention can quantitatively be provided in the extruding machine trunnion together.They also can quantitatively provide at the different sites of extruding machine.Some components such as colorant, stablizer, fire-retardant combination, there are synergistic compound and/or other flame retardance element for example to join in the polymkeric substance with the form of master batch with fire-retardant combination.
Polymer composition of the present invention can use technology well known to those skilled in the art such as injection molding to be processed into semifinished or finished goods.
The present invention will further illustrate by the following examples.Comparative Examples A
Melamine (from the gas phase process product of DSM) quantitatively is fed to corotation with 3 kilograms/hour speed changes Bitruder (Werder ﹠amp; Pfleiderer, model ZSK 30/33) in.Barrel zone temperature is set in 330 ℃, and screw speed is 40rpm.The residence time of the component of weight feed extruding machine is 115 seconds.The solid mixture that comes out from extruding machine is for white and the composition below having: the more high-grade condensation product of 88% (weight) melamine, 6% (weight) melam, 2% (weight) melem and 4% (weight) melamine and/or melem.Volatile matter content is 1.6% (weight).Measure the composition of fire-retardant combination by high pressure lipuid chromatography (HPLC) (HPLC).The value that obtains has the relative error smaller or equal to 5%.
Embodiment 1
Melamine (from the gas phase process product of DSM) quantitatively is fed to corotation with 1 kilogram/hour speed changes Bitruder (Werder ﹠amp; Pfleiderer, model ZSK 30/33) in.Barrel zone temperature is set in 400 ℃, and screw speed is 40rpm.The residence time of the component of weight feed extruding machine is about 95 seconds.The solid mixture that comes out from extruding machine for white to light gray and the composition below having: the more high-grade condensation product of 8% (weight) melamine, 0.5% (weight) melam, 73% (weight) melem and 18.5% (weight) melamine and/or melem.Volatile matter content is 0.4% (weight).Measure the composition of fire-retardant combination by high pressure lipuid chromatography (HPLC) (HPLC).
Embodiment 2
Melamine (from the gas phase process product of DSM) quantitatively is fed to corotation with 2 kilograms/hour speed changes Bitruder (Werder ﹠amp; Pfleiderer, model ZSK 30/33) in.Barrel zone temperature is set in 450 ℃, and screw speed is 40rpm.The residence time of the component of weight feed extruding machine is about 100 seconds.The solid mixture that comes out from extruding machine for white to light gray and the composition below having: the more high-grade condensation product of 1.3% (weight) melamine, 0.1% (weight) melam, 64% (weight) melem and 23.7% (weight) melamine and/or melem.Volatile matter content is 0.1% (weight).Measure the composition of fire-retardant combination by high pressure lipuid chromatography (HPLC) (HPLC).
Embodiment 3
Melamine (from the gas phase process product of DSM) quantitatively is fed to corotation with 3 kilograms/hour speed changes Bitruder (Werder ﹠amp; Pfleiderer, model ZSK 30/33) in.Barrel zone temperature is set in 450 ℃, and screw speed is 40rpm.The residence time of the component of weight feed extruding machine is 80 seconds.The solid mixture that comes out from extruding machine for white to light gray and the composition below having: the more high-grade condensation product of 1% (weight) melamine, 0.1% (weight) melam, 86% (weight) melem and 12.9% (weight) melamine and/or melem.Volatile matter content is 0.2% (weight).Measure the composition of fire-retardant combination by high pressure lipuid chromatography (HPLC) (HPLC).
Embodiment 4
1008 gram (8 moles) melamines are imported in the autoclave with about 2000ml volume.Speed operation agitator with about 30rpm.Allow reactor reach temperature required then.Temperature of reaction is 500 ℃.The pressure of the ammonia that reaction in the autoclave is gathered the time by control valve is maintained at about 2Mpa.Reaction times is 60 minutes.Then autoclave is cooled off.The pressure that when cooling, keeps autoclave.When being reduced to below 200 ℃, temperature discharges ammonia pressure at once.The solid mixture that comes out from autoclave for white to light gray and the composition below having: the more high-grade condensation product of 0.4% (weight) melamine, 0.5% (weight) melam, 91% (weight) melem and 8% (weight) melamine and/or melem.Volatile matter content is 0.1% (weight).Measure the composition of fire-retardant combination by high pressure lipuid chromatography (HPLC) (HPLC).
Embodiment 5
Change Bitruder (Werder ﹠amp toward corotation; Pfleiderer, model ZSK 30/33) adding: the powdered product of 45 parts of polybutylene terephthalates, 30 parts of glass fibre, 15 parts of embodiment 2 and 10 parts of Antiblaze 1045 are (available from Albright ﹠amp; The cyclic phosphonate ester of Wilson).Barrel zone temperature is set to 250 ℃, and screw speed is 200rpm.From the sample of the compound 1.6mm thickness that obtains and be used for test.Combustionproperty according to UL 94 is V-0.Young's modulus is 10.1GPa, and extension at break is 2.0% (ISO 527/1).
Embodiment 6
Change Bitruder (Werder ﹠amp toward corotation; Pfleiderer, model ZSK 30/33) adding: the powdered product of 45 parts of polybutylene terephthalates, 30 parts of glass fibre, 15 parts of embodiment 3 and 10 parts of Antiblaze 1045 are (available from Albright ﹠amp; The cyclic phosphonate ester of Wilson).Barrel zone temperature is set to 250 ℃, and screw speed is 200rpm.From the sample of the compound 1.6mm thickness that obtains and be used for test.Combustionproperty according to UL 94 is V-0.Young's modulus is 10.0GPa, and extension at break is 2.0% (ISO 527/1).
Embodiment 7
Change Bitruder (Werder ﹠amp toward corotation; Pfleiderer, model ZSK 30/33) adding: the powdered product of 45 parts of polybutylene terephthalates, 30 parts of glass fibre, 15 parts of embodiment 4 and 10 parts of Antiblaze 1045 are (available from Albright ﹠amp; The cyclic phosphonate ester of Wilson).Barrel zone temperature is set to 250 ℃, and screw speed is 200rpm.From the sample of the compound 1.6mm thickness that obtains and be used for test.Combustionproperty according to UL 94 is V-0.Young's modulus is 10.2GPa, and extension at break is 2.1% (ISO 527/1).
Embodiment 8
Change Bitruder (Werder ﹠amp toward corotation; Pfleiderer, model ZSK 30/33) adding: the powdered product of 45 parts of polyamide 6s, 20 parts of glass fibre, 30 parts of embodiment 4 and 5 parts of Antiblaze 1045 are (available from Albright ﹠amp; The cyclic phosphonate ester of Wilson).Barrel zone temperature is set to 250 ℃, and screw speed is 200rpm.From the sample of the compound 1.6mm thickness that obtains and be used for test.Combustionproperty according to UL 94 is V-0.Young's modulus is 11.2GPa, and extension at break is 2.0% (ISO 527/1).
Embodiment 9
Change Bitruder (Werder ﹠amp toward corotation; Pfleiderer, model ZSK 25/38) add: the powdered product of 80 parts of polymeric amide 4,6 and 20 parts of embodiment 3.Barrel zone temperature is set to 300-315 ℃, and screw speed is 270rpm.From the sample of the compound 1.6mm thickness that obtains and be used for test.Combustionproperty according to UL 94 is V-0.Young's modulus is 3.6GPa, and extension at break is 25% (ISO 527/1).
Embodiment 10
Change Bitruder (Werder ﹠amp toward corotation; Pfleiderer, model ZSK 25/38) add: the powdered product of 90 parts of polymeric amide 4,6 and 10 parts of embodiment 3.Barrel zone temperature is set to 300-315 ℃, and screw speed is 270rpm.From the sample of the compound 1.6mm thickness that obtains and be used for test.Combustionproperty according to UL 94 is V-0.Young's modulus is 2.3GPa, and extension at break is 30% (ISO 527/1).
Embodiment 11
Change Bitruder (Werder ﹠amp toward corotation; Pfleiderer, model ZSK 30/33) add: 80 parts of polyamide 6s, the powdered product of 6 and 20 parts of embodiment 3.Barrel zone temperature is set to 270-280 ℃, and screw speed is 200rpm.From the sample of the compound 1.6mm thickness that obtains and be used for test.Combustionproperty according to UL 94 is V-0.
Embodiment 12
Change Bitruder (Werder ﹠amp toward corotation; Pfleiderer, model ZSK 30/33) add: the powdered product of 80 parts of acrylonitrile-butadiene-styrene (ABS)s (the Ronfalin of DSM contains 20 parts of rubber) and 20 parts of embodiment 3.Barrel zone temperature is set to 180-210 ℃, and screw speed is 200rpm.From the sample of the compound 1.6mm thickness that obtains and be used for test.Combustionproperty according to UL 94 is V-0.
Embodiment 13
98.0% melamine, 0.81% urea, the 0.03%CO that will obtain according to the method for US 4565867
2, 0.05% cyanurodiamide related impurities (as cyanurodiamide, melon, cyanuric acid and uridomelamine) and 0.07% organic solid (melem, melam and other non-oxygen compound) mixture quantitatively be fed to corotation with 8 kilograms/hour speed and change Bitruder (Werder ﹠amp; Pfleiderer, model ZSK 30/33) in.Barrel zone temperature is set in 450 ℃, and screw speed is 40rpm.The residence time of the component of weight feed extruding machine is 110 seconds.The solid mixture that comes out from extruding machine for white to light gray and the composition below having: the more high-grade condensation product of 7% (weight) melamine, 2% (weight) melam, 76% (weight) melem, 14% (weight) melamine and/or melem and the unknown lingering section of about 1% (weight).Volatile matter content is 0.2% (weight).Measure the composition of fire-retardant combination by high pressure lipuid chromatography (HPLC) (HPLC).
Embodiment 14
Change Bitruder (Werder ﹠amp toward corotation; Pfleiderer, model ZSK 30/33) adding: the powdered product of 45 parts of polybutylene terephthalates, 30 parts of glass fibre, 15 parts of embodiment 13 and 10 parts of Antiblaze 1045 are (available from Albright ﹠amp; The cyclic phosphonate ester of Wilson).Barrel zone temperature is set to 250 ℃, and screw speed is 200rpm.From the sample of the compound 1.6mm thickness that obtains and be used for test.Combustionproperty according to UL 94 is V-0.Young's modulus is 10.0GPa, and extension at break is 2.4% (ISO 527/1).
Embodiment 15
The melamine of the purity 99.92% that will obtain according to the method for US 3210352 quantitatively is fed to corotation commentaries on classics Bitruder (Werder ﹠amp with 8 kilograms/hour speed; Pfleiderer, model ZSK 30/33) in.Barrel zone temperature is set in 450 ℃, and screw speed is 40rpm.The residence time of the component of weight feed extruding machine is 110 seconds.The solid mixture that comes out from extruding machine for white to light gray and the composition below having: the more high-grade condensation product of 6% (weight) melamine, 1% (weight) melam, 77% (weight) melem, 16% (weight) melamine and/or melem.Volatile matter content is 0.3% (weight).Measure the composition of fire-retardant combination by high pressure lipuid chromatography (HPLC) (HPLC).
Embodiment 16
Change Bitruder (Werder ﹠amp toward corotation; Pfleiderer, model ZSK 30/33) adding: the powdered product of 45 parts of polybutylene terephthalates, 30 parts of glass fibre, 15 parts of embodiment 15 and 10 parts of Antiblaze 1045 are (available from Albright ﹠amp; The cyclic phosphonate ester of Wilson).Barrel zone temperature is set to 250 ℃, and screw speed is 200rpm.From the sample of the compound 1.6mm thickness that obtains and be used for test.Combustionproperty according to UL 94 is V-0.Young's modulus is 10.5MPa, and extension at break is 2.2% (ISO 527/1).
Embodiment 17
98.7% melamine, 1.0% urea, the 0.06%CO that will before quench step post crystallization step, obtain according to the method for US 3210352
2, 0.1% cyanurodiamide related compound (as cyanurodiamide, melon, cyanuric acid), 0.12% organic solid (melem, melam and other compound) and the residual organic catalyst of 0.02% (200ppm) mixture quantitatively be fed to corotation with 8 kilograms/hour speed and change Bitruder (Werder ﹠amp; Pfleiderer, model ZSK30/33) in.Barrel zone temperature is set in 450 ℃, and screw speed is 40rpm.The residence time of the component of weight feed extruding machine is 110 seconds.The solid mixture that comes out from extruding machine for white to light gray and the composition below having: the more high-grade condensation product of 6% (weight) melamine, 1% (weight) melam, 74% (weight) melem, 20% (weight) melamine and/or melem.Volatile matter content is 0.3% (weight).Measure the composition of fire-retardant combination by high pressure lipuid chromatography (HPLC) (HPLC).
Embodiment 18
Change Bitruder (Werder ﹠amp toward corotation; Pfleiderer, model ZSK 30/33) adding: the powdered product of 45 parts of polybutylene terephthalates, 30 parts of glass fibre, 15 parts of embodiment 17 and 10 parts of Antiblaze 1045 are (available from Albright ﹠amp; The cyclic phosphonate ester of Wilson).Barrel zone temperature is set to 250 ℃, and screw speed is 200rpm.From the sample of the compound 1.6mm thickness that obtains and be used for test.Combustionproperty according to UL 94 is V-0.Young's modulus is 10.2GPa, and extension at break is 2.0% (ISO 527/1).
Embodiment 19
Melamine (from the gas phase process product of DSM) quantitatively is fed to corotation with 1 kilogram/hour speed changes Bitruder (Werder ﹠amp; Pfleiderer, model ZSK 30/33) in.Barrel zone temperature is set in 400 ℃, and screw speed is 40rpm.The residence time of the component of weight feed extruding machine is 95 seconds.To grind from the solid mixture that extruding machine comes out.Powdered product is washed the ratio of 3 liters of about water of 90 ℃ with about 200 grams.After 15 minutes by removing by filter hot slurry.Handle residue again 3 times with same step.To in vacuum drying oven, under 120 ℃, be dried to moisture content through the product of washing at last and be lower than 1% (weight).The product of Huo Deing is white and has following composition like this: the more high-grade condensation product of 1% (weight) melamine, 2% (weight) melam, 77% (weight) melem and 20% (weight) melamine and/or melem.Volatile matter content is lower than 0.3% (weight).Measure the composition of fire-retardant combination by high pressure lipuid chromatography (HPLC) (HPLC).
Claims (12)
1. fire-retardant combination comprises:
The melem of 10-90% (weight),
The melam of 0.01-30% (weight),
The melamine of 0.01-15% (weight),
The summation that the more senior condensation product of 0.1-65% (weight) melamine and/or melem, the concentration of volatile constituent are lower than 3% (weight) and each component is 100% (weight).
2. the summation that method for preparing fire-retardant combination, the concentration that is characterised in that the more senior condensation product of melamine, 0.1-65% (weight) melamine and/or melem of melam, 0.01-15% (weight) of the melem that comprises 10-90% (weight), 0.01-30% (weight) and volatile constituent are lower than 3% (weight) and each component is that the fire-retardant combination of 100% (weight) prepared by the time of raw material more than 0.1 second that contains melamine in 350-800 ℃ temperature and 1KPa heating under the pressure of 50MPa.
3. according to the method for claim 2, be characterised in that the described melamine raw material that contains heats in autoclave or extruding machine.
4. according to the method for claim 3, be characterised in that the described melamine raw material that contains heats in extruding machine, the residence time in extruding machine is 0.1 second to 60 minutes.
5. according to each method of claim 2-4, be characterised in that fire-retardant combination washed with water subsequently to make a part of melamine and the dissolving of other water soluble ingredient and from fire-retardant combination, remove.
6. according to each method of claim 2-5, be characterised in that the melamine of the more high-grade condensation product that is doped with melam and/or melem and/or melamine and/or melem is used as initial feed.
7. according to each method of claim 2-5, be characterised in that used raw material is the melamine that is prepared before the initial product of melamine device or the crystallization in gas-phase apparatus.
8. according to each method of claim 2-5, be characterised in that the melamine that obtains by liquid phase method is used as raw material.
9. flame retardant compositions comprises following component:
A.65-95% (weight) contains the composition of polymkeric substance
B.5-35% (weight) is according to the fire-retardant combination of claim 1.
10. according to the flame retardant compositions of claim 8, be characterised in that described composition also comprises fortifying fibre.
11. use the article of producing according to the flame retardant compositions of claim 9 or 10.
12. based on the fire-retardant combination of specification sheets and embodiment, its preparation method with in the purposes of fire-retardant combination described in the polymer composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1011631A NL1011631C2 (en) | 1999-03-22 | 1999-03-22 | Flame-retardant composition and method for its preparation. |
| NL1011631 | 1999-03-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1351642A true CN1351642A (en) | 2002-05-29 |
| CN1192079C CN1192079C (en) | 2005-03-09 |
Family
ID=19768889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB00807657XA Expired - Fee Related CN1192079C (en) | 1999-03-22 | 2000-02-28 | Flame-retarding composition and process for the preparation thereof |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JP4303426B2 (en) |
| KR (1) | KR100632555B1 (en) |
| CN (1) | CN1192079C (en) |
| AT (1) | ATE229062T1 (en) |
| AU (1) | AU768261B2 (en) |
| BR (1) | BR0009207A (en) |
| CA (1) | CA2365173A1 (en) |
| DE (1) | DE60000923T2 (en) |
| ES (1) | ES2186632T3 (en) |
| NL (1) | NL1011631C2 (en) |
| RU (1) | RU2225876C2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457450C (en) * | 2003-02-24 | 2009-02-04 | 纳幕尔杜邦公司 | Flame retardant surface coverings |
| CN101395235B (en) * | 2006-02-10 | 2012-07-11 | 3M创新有限公司 | Flame resistant covercoat for flexible circuit |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006049519A1 (en) * | 2006-10-20 | 2008-04-24 | Lanxess Deutschland Gmbh | Flame retardant for curable molding materials comprises ethylenediamine phosphate, a halogen-free phosphorus compound and a halogen-free nitrogen compound |
| KR20090067663A (en) * | 2007-12-21 | 2009-06-25 | 루브리졸 어드밴스드 머티어리얼스, 인코포레이티드 | Halogen-free flame retardant thermoplastic polyurethanes |
| ES2440516T3 (en) * | 2008-08-15 | 2014-01-29 | Otis Elevator Company | Elevator system comprising a load bearing element with a nanometric flame retardant and corresponding method of manufacturing said load bearing element |
| DE102010035103A1 (en) * | 2010-08-23 | 2012-02-23 | Catena Additives Gmbh & Co. Kg | Flame retardant compositions containing triazine-intercalated metal phosphates |
| EP3071649B1 (en) * | 2013-11-21 | 2017-12-20 | DSM IP Assets B.V. | Flame-retardant polyamide composition |
| RU2556212C1 (en) * | 2014-07-07 | 2015-07-10 | Общество с ограниченной ответственностью "ТермоФасад" | Composition for obtaining of fireproof polyurethane foam |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD242941A (en) * | ||||
| DE1694254C3 (en) * | 1968-03-16 | 1984-06-28 | Bayer Ag, 5090 Leverkusen | Self-extinguishing fiber-reinforced polyamide molding compounds |
| DD143918A1 (en) * | 1979-07-17 | 1980-09-17 | Norbert Schubert | METHOD FOR PRODUCING MODIFIED POLYAMIDE MOLD |
| JPS5945352A (en) * | 1982-09-09 | 1984-03-14 | Nissan Chem Ind Ltd | Novel flame-retardant resin composition |
| JPS60144348A (en) * | 1984-09-11 | 1985-07-30 | Nissan Chem Ind Ltd | Flame-retardant resin composition |
-
1999
- 1999-03-22 NL NL1011631A patent/NL1011631C2/en not_active IP Right Cessation
-
2000
- 2000-02-28 CN CNB00807657XA patent/CN1192079C/en not_active Expired - Fee Related
- 2000-02-28 KR KR1020017011988A patent/KR100632555B1/en not_active IP Right Cessation
- 2000-02-28 RU RU2001128303/04A patent/RU2225876C2/en not_active IP Right Cessation
- 2000-02-28 ES ES00908106T patent/ES2186632T3/en not_active Expired - Lifetime
- 2000-02-28 JP JP2000606699A patent/JP4303426B2/en not_active Expired - Fee Related
- 2000-02-28 CA CA002365173A patent/CA2365173A1/en not_active Abandoned
- 2000-02-28 AT AT00908106T patent/ATE229062T1/en active
- 2000-02-28 DE DE60000923T patent/DE60000923T2/en not_active Expired - Lifetime
- 2000-02-28 BR BR0009207-0A patent/BR0009207A/en not_active IP Right Cessation
- 2000-02-28 AU AU29478/00A patent/AU768261B2/en not_active Ceased
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457450C (en) * | 2003-02-24 | 2009-02-04 | 纳幕尔杜邦公司 | Flame retardant surface coverings |
| CN101395235B (en) * | 2006-02-10 | 2012-07-11 | 3M创新有限公司 | Flame resistant covercoat for flexible circuit |
Also Published As
| Publication number | Publication date |
|---|---|
| NL1011631C2 (en) | 2000-09-27 |
| KR20020015684A (en) | 2002-02-28 |
| JP4303426B2 (en) | 2009-07-29 |
| JP2002540249A (en) | 2002-11-26 |
| BR0009207A (en) | 2001-12-26 |
| CN1192079C (en) | 2005-03-09 |
| AU768261B2 (en) | 2003-12-04 |
| RU2225876C2 (en) | 2004-03-20 |
| AU2947800A (en) | 2000-10-09 |
| CA2365173A1 (en) | 2000-09-28 |
| ATE229062T1 (en) | 2002-12-15 |
| DE60000923D1 (en) | 2003-01-16 |
| ES2186632T3 (en) | 2003-05-16 |
| DE60000923T2 (en) | 2003-09-04 |
| KR100632555B1 (en) | 2006-10-09 |
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