TW201114825A - Flame-protected polymer composition - Google Patents

Abstract

The invention relates to a flame-protected polymer composition made of a polyamide or a polybutylenterephthalate, comprising a selected phosphor compound as a flame protected agent, and to molded parts produced therefrom.

Description

201114825 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a composition of a flameproof polymer composed of a polydecylamine or a polybutylenterephthalate (Polybutylenterephthalat), which contains Once the selected phosphorus compound is used as a flame retardant, and the cast component made from the composition. [Prior Art] A flame-retardant composition, such as a polyamine-based structure, is used in the manufacture of molded articles in many fields of application due to various superior properties summarized therein. Especially for components in the power X and electronic X industries, it is important that the flame retardant polymer composition has superior flame retardant properties to ensure adequate flame resistance. In addition to these superior flame retardant properties, other physical properties, such as tensile modulus of elasticity, tear strength, and elongation at tear point, are equivalent to the corresponding values for each application. is important. In addition, these flame-retardant polymer compositions should be free of steroids for both toxicological reasons. Polymer compositions are known in the state of the art which contain a phosphorus-based, halogen-free flame retardant. For example, European Patent No. EP 67 862 B1 describes a polymer composition made of the selected polyamine and which contains a phosphorus compound which is selected as a flame retardant. In addition, several polymer compositions are disclosed in the European Patent Publication No. EP 1 012 244 A1, which all contain a phosphorus-free compound containing no sulphate, and in this case a selected phosphorus compound is also used. However, what has always appeared is that the flame-retardant polymer group, which is known in the foregoing, is still satisfactory in terms of its flame-retardant properties when it is processed into a cast component. Moreover, its disadvantages are physical properties such as tensile elastic modulus, which, in many instances, are insufficient even with good flame retardant properties. 201114825 [Description of the Invention] Based on the facts stated, it is therefore an object of the present invention to provide several novel flame-retardant polymer compositions in which various cast components made from such flame-retardant polymer compositions are The main properties of the combination of elongation at break, tear strength and elongation at tear point, and tensile modulus of elasticity should also be provided for the properties of the flame retardant. The object of the present invention is in terms of the polymer composition in accordance with the features of item 1 of the scope of the patent application, and in the case of the casting element, in accordance with the features of item 8 of the scope of the patent application. Their sub-items indicate their advantageous extension. According to the invention there is thus provided a flame-retardant polymer composition comprising from 2 to 10% by weight of polydecylamine (PA) or polybutylene terephthalate (ρΒτ) as a polymer, or as a compound of a flame retardant selected from the group consisting of: bl

B.2 b.3 4 201114825 b.4

B.5

And/or

The correct chemical names for these compounds are listed below. Bl : 10-Benzylmethyl 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10_oxide (10-Benzyl-9,10-dihydro-9-oxa-1 〇-phosphaphenanthren- 10-oxi d) or 6-phenylmethyl-6H-dibenzo[c,e][l,2]oxyscale heterocyclohexane-6-oxide (6-phenyl-methyl-6H-dibenz[ c,e][l,2]oxaphosphorin-6-oxid) b.2 : 1,2-di-(6-oxo-6H-dibenzo[c,e][ 1,2]oxyphosphorane Hexane·6_yl) 1,2· ethylene glycol (1,2-1^-(6-〇说〇-611-(1心112[(^][1,2](^?11(^ 11〇1^-6- yl)-l,2-ethandiol) b.3 5 201114825 1- [2_(6.oxo-book-dibenzo[c,e][i,2]oxyphosphorus heterocycle Hexane_6-yl)ethyl]_2_0 is more than argon-(l-[2-(6-oxido_6H-dibenz[c,e][l,2]〇xa.phosphorin-6-yl) ethyl]-2 - pyrrolidon) b.4 : 2- [2-(6-oxo-benzo-benzo[c,e][l,2]oxazepine-6-yl)ethyl p ratio^ ( 2-[2-(6-oxido-6H-dibenz[c,e] [ 1,2]oxaphosphorin-6-yl)ethyl] -pyridin) b.5 : 4-[2-(6-oxo-book -dibenzo[c,e][l,2]oxyphospholane_6_yl)ethyl]_0 ratio^(4-[2-(6-oxido-6H-dibenz[c,e]] [l,2]〇xaphosphorin-6-yl)ethyl] -pyridin) b.6 : 1 -(6-oxo-6H-dibenzo[c e] [ 1,2] oxaphospholane „6_yl)_2_carbamoyl-decylamine (l-(6-oxido-6H-dibenz[c,e][l,2]oxaphosphorin -6-yl)-2-carbamoyl-hydrazincarboxamid). Compounds such as b.3, b.4 and b.5 may also contain a small amount of corresponding stereoisomers linked by 2-ethyl groups instead of 2-ethyl groups. The present invention now shows a flame-retardant polymer composition comprising the above-mentioned selected phosphorus compound as a flame retardant, which still has superior properties in the UL_94 flammability test when it is processed into a cast component. In particular, the polymer compositions according to the invention may be emphasized in that the casting elements made from the compositions also have a flame reaction (GWFI) above the average and one over average when igniting the plastic. A value above the reaction (GWIT) and a very good oxygen limit index (L〇I). In addition, these components did not exhibit undesirable reactions in terms of other physical properties such as tear strength, elongation at tear point, and/or tensile modulus of elasticity. The more specific properties of these discovered polymer compositions are attributed to the use of the 201114825 content ratios named after bl, b.2, b.3, b.4, b.5 and/or b.6. Phosphorus compound. The component b) is used in an amount of from 9 to 20% by weight, preferably from 10 to 18% by weight, especially from 12 to 16% by weight, and from 12 to 14% by weight. The polymers contained in the polymer composition of the invention, especially the following polyamines, are highlighted as preferred ones: PA6, PA11, PA12, PA46, PA66, PA6H, PA618, PA6I/6T, and the like. Among the preferred polyamines are PA6, PA12, PA46, PA614, PA618 and PA6I / 6T with PA46 or with PA66 or with PA614 or with PA618. Extremely preferred are PA12, PA614, PA618 and PA6I/6T with PA46 or with PA66 or with PA614 or with PA618. The weight ratio of pA6I/6T to aliphatic hydrocarbon polyamine is 10 · 90 to 40 : 60 in a mixture of polyamine PA6I / 6T and aliphatic hydrocarbon polyamine pA46, PA66, PA614 or PA618. The preference is 15:85 to 30:70, especially the preference is 20:80 to 30:70, and the extreme preference is 25:75. For the awkward stock PAOl / 6T, the weight ratio of the unit 61 to the unit 计 is expressed as .μ to 100 : 〇, prefers 6G: 4G to 8G: 2G, especially the preference is 67:33. If a mixture containing p A 61 / 6 T is used as the main engraving, the polymer city of the present invention will be characterized by a ship-to-length ratio with a high height. t: 2: 1166 or PA46, the relative viscosity of polyamine (measured in toluene solution between 20 points) is (3) to 2.5, prefers 1.45 to 2.35, especially preference h5 () Until 2 25. Tong County ^ ^ Α μ6 PA6 ^ PA46 aspect viscous viscosity (under 2 〇〇 C at 1 2 5 ^: ; Ϊ f to 3.80 ' extreme preference 2.65 to 3.5 〇. In 10,000, phase _ ( ( 2 (as measured by TC. 5 parts by weight of benzene 7 201114825 expected/tetrachloroethane solution (60/40 g/g)) is 丨25 to 2.10, prefers 1.30 to 2.0, especially preference 1.35 to 1.9. Especially preferred is the type of polyamine which is referred to above as an amine group. The term "amino group as terminal group" means the amino group of the polyamine. The terminal group (NH2) is more than the base group. The concentration of the amine terminal group of the polyamine is 40 microgram equivalents/gram to 230 micrograms equivalent/gram, preferring 45 microgram equivalents/gram to 180 micrograms equivalent. / gram 'especially preferred 55 microgram equivalent / gram to 14 〇 microgram equivalent / gram, extreme preference 55 micrograms when bright / gram to 80 micrograms when bright / gram ❶ If the flame retardant polymer composition only consists of components a) and b When composed, the proportion of component b) is at least 9 weight percent and at most 20 weight percent. Furthermore, in terms of the polymer composition according to the present invention, another flame retardant or synergist (component) may be added in addition to the flame retardant as described above in an amount of from 〇 to 3 重量% by weight. c)). Preferred as component c) are nitrogen-containing compounds, nitrogen-containing and phosphorus-containing compounds, metal borates, metal carbonates, metal hydroxides, metal hydroxide oxides, metal nitrides, Metal oxides, metal phosphates, metal sulfides, metal stannates, metal ruthenium stannates, silicates, zeolites, basic zinc citrate and/or citric acid. It can be ascertained that, in addition to the flame retardant (component b) in the polymer composition, it additionally contains another flame retardant or synergist from 5 to 22% by weight. In the case of c)), a particularly advantageous property can be achieved in terms of flame suppression. This is a preferred alternative according to the invention, that is to say that the polymer composition contains, in addition to component b), another flame retardant. , referred to above as component c). The content of component c) is preferably in the range of from 8 to 20 weight percent, especially from 1 to π weight percent, and from 10 to 14 weight percent. Examples of component c) are triazine derivatives, melamine, 胍8 201114825 (Guanidin), anthraquinone derivatives, Biuret, Triuret, Tartrazin, Gan Glycoluril, Acetoguanamin, Butyroguanamin, Caprinoguanamin, Benzoguanamin, Cyanursaure melamine derivative, isocyanide Isocyanursaure melamine derivative, melamine cyanurate, melamine condensation product, melamine pyrophosphate, melamine condensation product pyrophosphate, dimelamine phosphatate, dimelamine phosphatate Dimelaminpyrophosphat, Melamine poly-phosphat, Dicyandiamid, Ammonium poly-phosphat, Ammonium hydrogen phosphat, Ammonium dihydrogen phosphat, Melamine condensation Product polyphosphate, melamine sulfate, allantoin, Aluminium, synthetic aluminum oxide (Aluminium hydroxi-oxid), natural ammonia emulsion (Aluminium metahydrochemistry), alumina, calcium borate, calcium carbonate, calcium carbonate Magnesium, calcium oxide, calcium sulfide, iron oxide, magnesium borate, magnesium carbonate, magnesium hydroxide, iron nitride, magnesium oxide, magnesium sulfide, manganese hydroxide, manganese oxide, titanium nitride, titanium dioxide, zinc borate, metaboric acid , zinc carbonate, zinc hydroxide, zinc nitride, phosphoric acid, sulfurized words 'zinc stannate, zinc oxystannate, alkaline zinc citrate, zinc oxide hydrate and combinations thereof. More preferred as component c) users have 胍 粦 粦 、, tris, gland, melamine cyanuric acid, melamine polyphosphate, dimelamine pyrophosphate, Melon polyphosphat, synthetic aluminum hydroxide oxide (Aluminiummeta_ Hydroxid) (Aluminium hydroxioxid), Aluminiummetahydrate (Natural Alumini surface hydr〇xi〇xid) ' Carbon 201114825 Calcium, Calcium Carbonate, Magnesium Carbonate, Magnesium Hydroxide, Zinc Borate 'Zinc carbonate, zinc stannate and/or zinc sulfide. Preferred is a flame-retardant polymer composition containing from 3 to 30 parts by weight of component c). If the flame-retardant polymer composition contains component c) in addition to components a) and b), then the ratio of component b) to component c) is between 2.3:1 and 1:1.5 'The preference is between 1.8:1 and 1:1.2. The preference is especially between h4:丄 and 1:1.2. The extreme preference is between 1.2:1 and 1:1.2. The polymer composition according to the invention, as known in the state of the art, may of course also contain additives in an amount of from 〇 to 10% by weight, more preferably from 〇丨 to 1% by weight, wherein the additives are preferred by inorganic Stabilizer, organic stabilizer, lubricant, pigment and marking substance, inorganic pigment, organic pigment, infrared absorber, antistatic agent, anti-caking agent, nucleating agent, crystallization accelerator, crystal retarder, Metal carboxylate, additive for lengthening chain length, conductive additive, carbon black, graphite, carbon nanotube, mold release agent, mold separating agent, optical brightener, additive for photochromic reaction, increase Plasticizer, foreign polymer, acid bismuth: a two-claw modifier, an adhesive, an anti-drip agent, a metallic pigment, a metal micro-chip, a metal-coated particle, and/or a mixture thereof ( Group ingredients d)). In terms of the polymer composition according to the invention, it is furthermore contemplated that the composition may contain, in addition to the content from 〇 to 65 weight percent, more preferably from 〇 to 50 weight percent, especially preference 3 to 5 重量 by weight, extremely preferred 6 to 45 weight percent of fibrous or granular filler. Examples of fibrous or reinforced fillers include glass fibers, carbon fibers, metal fibers, aromatic hydrocarbons, plant fibers, polymer fibers, filament fiber devices, and age-like materials. . The resistance of the polymer can be determined by the use of a filler plus - (iv) and / or an adhesion 201114825 agent. Among them, the preferred users are glass fiber and/or carbon fiber. The glass fiber, carbon fiber or polymer fiber has a cross section of a circle, an oval, an ellipse, an angle or a rectangle. In addition, fibers having a non-circular cross section ("flat fibers"), especially oval, elliptical, angular or rectangular fibers, may also be used. Among the flat fibers, especially preferred are flat glass fibers. The glass fibers, carbon fibers and/or polymer fibers may be incorporated into the polymer composition in the form of a seamless strand (roving) or in a cut form (short fiber). One: The diameter of the glass fibers used by k is in the range of 5 micrometers to 2 micrometers, more preferably in the range of 5 micrometers to 15 micrometers, and particularly preferably between 5 micrometers and 1 micrometer. Carbon fibers have diameters ranging from 3 microns to 12 microns, more preferably between 4 microns and 10 microns, and especially between 4 microns and 9 microns. If used as a glass fiber using a jointless fiber (roving) in a pultrusion process, the fibers have a diameter of from 10 μm to 2 μm, more preferably from 10 μm to 18 μm. Especially preferred is between 10 microns and 14 microns. Carbon fibers can also be used as jointless fibers in the pultrusion process. The invention also includes (4) granulated filling. It is suitable as a granular filler and has a granular filling. The following are selected as follows: I纟 and the group contains, stone, talc, mica, dolomite, broken acid salt, quartz, dioxide drink, Crushed stone, strontium carbonate, magnesium oxide, white, polished glass, slab scale, ground carbon fiber, ground or precipitated carbon ray, lime, feldspar, sulfuric acid lock, permanent magnetism Or a magnetizable metal or alloy, a glass sphere, a hollow glass sphere, a hollow spherical citrate filler, a synthetic flaky Wei salt, a natural flaky citric acid drum, or the like. These granular fillings are more preferred than those of the processor. ' Preferred for a flame retardant polymer composition with a) 25 to 85 weight percent polyamide, 201114825 b) 10 to 18 weight percent phosphorus compounds, c) 5 to 22 weight percent A flame retardant/or synergist, d) 0.1 to 1% by weight of an additive and e) 0.1 to 50% by weight of a filler, wherein the total result from a) to e) is 100 Weight percentage. The polymer composition according to the present invention can be prepared according to a substantially known method. f When the composition is prepared, the components are homogenized in a multi-functional machine, for example, in a single-screw or twin-screw extruder, or a screw-spinning machine. It is common practice to pre-mix the components a) to e), partially pre-mix or 10,000-forced feeds, eg when using a lateral feeder, if they are individually located at the same or different locations The metering feeder is fed into the compound machine. The step of homogenizing the polymer melt is carried out below the temperature of the barrel, which is based on the melting of the main particles, from 22 G to 32 G. Vacuum or gas removal can be applied before the nozzle. The lysate is then sent out of the machine in the form of a line, which is then cooled in a water bath and then pelletized. The particles are then dried under nitrogen or under vacuum at 80 ° C to 12 (TC is dried for 12 hours to 24 hours until the water content is below a significant percentage. When PBT is used as the primary particle, the water content of the product is dried to low 0.02 significant percentages. If the individual components are premixed with component a), this is a dry mixing process. For dry mixing preparation, the dried granules are mixed with other components in addition to the fibrous filler. The mixture was homogenized using a rolling mixer, R5hn roller mixer or a rolling dryer for 1 to 4 minutes. To avoid moisture absorption, the mixing step can be carried out under a dry protective gas. Fibrous fillers are always divided into _ weight and (four). Filler shots are added to the feeder and to the melt of the polymer. 12 201114825 The preferred component is component b) weighed separately via a broken scale and added to the feeder or melt of the polymer. If component c) is used, it is recommended to mix component b) and component c) first, then weigh the mixture and add it to the feeder or to the polymer melt. The components b) to e) may be used either directly or in the form of a masterbatch, wherein the masterbatch may contain more than one component of b) to e). The carrier material of the masterbatch is preferred to be associated with a polymer which is selected from the same polymer species, such as component a), especially with respect to component a) itself. The invention also relates to a cast component (Application No. 8) which is prepared from a flame resistant polymer composition as described above. The cast elements are also shown in the present invention, for example, having a wall thickness of 1.6 mm according to the ul_94 flammability test, satisfying the condition of the flammability classification v〇, which is preferred when the wall thickness is 0.8 mm. The flammability classification v〇 is achieved, especially if the wall thickness is 0.4 mm, the flammability classification v〇 has been reached. In addition, the cast elements exhibit superior properties in terms of suppression of combustion (GWFI), ignition reaction (GWIT), and oxygenation limit (LOI). For example, a cast component having a wall thickness of 1 mm has a GWIT of at least 80 (TC, preferring at least 85 〇. 〇, especially preferring at least 875 ° C and/or having a GWFI of at least _t, preferred At least for 5. (: 'Special preference is at least 9 thieves. The value of L〇I should be at least %, preferring at least 28', especially at least 3〇. The (4) polymer composition of the present invention is purely used as (4) tools. , households •= supplies, electrical equipment supplies, electronic equipment supplies, can be used in the nuclear electronic = supplies, telecommunications equipment supplies, entertainment electronics _ goods, computers, notebooks = or, read (for example or connectors, etc.) The material may be used in industries such as construction, skimming, furniture, energy, or machinery. [Embodiment] 13 201114825 Hereinafter, a plurality of synthetic examples by sorting phosphorus compounds and by the listed tables will be used. The invention is described. 1) Synthesis of a sample compound of bl

In practice, 1405 grams (6.5 moles) of 9,1 〇-dihydro _9_oxa phosphaphenanthene oxide (DOPO) was placed in a 4 liter reactor, and then added to the gram. (65 mole) of tributylamine. The mixture was placed at a jacket temperature of 140. Melting was carried out under nitrogen and nitrogen blowing. At this time, a mixture containing two phases was formed. 823 g (6.5 mol) of benzyl gas was added dropwise at 12 Torr and 13 〇〇c. To the mixture, it took 2 hours. Then the mixture was heated to 16 ° C, followed by stirring for 5 hours. At this point the reaction mixture became clear and transparent. Then the temperature of the outer cover was adjusted to 25 ° C, then carefully 丨 3 〇 〇 ml i methanol was added to the mixture. This clarified solution was dispersed in 3250 ml of deionized water at a product temperature of about 45 C. At this point, a mixture containing two phases was formed, which formed crystals after a few minutes. After standing at room temperature for 16 hours, the crystallization solution was filtered to remove the liquid, and the crystals were dried under a vacuum of 75 Torr and 5 mbar. The appearance of the yield was 1686 gram (accounting for the theoretical value) 84.8 %) white powder

Melting point: lll °C Purity: 98.0 area·% (gas chromatography) Water content: 〇.12% (KF) 201114825 Elemental analysis: theoretical value carbon = 74.5 % 'hydrogen = 4.94 % actual value carbon = 73.7 %, argon =5.83 %, chlorine = 0.052 % 2) Synthesis of compound reaction of phosphorus compound b.2

Reaction mixture 300.0 g (1.38 mol) 102.0 g (0.70 mol) 750.0 ml DOPO (^99.5 %) 40% glyoxal aqueous solution methanol pa, Mok actually operated 300.0 g DOPO and 450 ml methanol One i liter in the reactor. The reaction contents were heated to 55 ° C to 60 ° C. At 45. (: When D〇p〇 is dissolved, it becomes a clear and colorless solution. When the temperature of the mixture solution reaches 55〇CB, the solution of Ethylene is added to the mixture in a trickle for a minute. Then at 60 The mixture was stirred at ° C for 4 hours. After the reaction was continued for 3 minutes, D〇p〇_ 乙乙醒 began to form crystals. After further 60 minutes of reaction, 1 mL of methanol was added to the mixture. After continuing the reaction for 3 hours, 1 ml of the methyl group was added to the mixture. Finally, after reacting for 4 hours, the mixture was cooled to 40 ° C, and the mud liquid was poured into a beaker, and then _100 liters of methanol to dilute it and cool to room temperature. Place the slurry on a vacuum concentrator and roll it under a hearing of 100 to 200 mbar. Place it and dry it under the voyage and 20 mbar until the weight reaches the odds. In the middle ' 15 201114825 Yield: 330.7 grams (97.4% of the theoretical value) Appearance: The ratio of white powder to water insoluble matter: 91.2% ratio of water-soluble substances: 6. 6 % 3) Synthesis example of phosphorus compound b.3 Reaction

Reaction mixture 302.70 g (1.4000 m) 1.30 g (0.0070 m) 155.60 g (1.4000 m) 458.20 g (530 ml) Actual operation DOPO (^99.5%) p-benzoic acid monohydrate (^98 %) » Fluka 1 -Ethyl-2-0-pyrrolidyl (2 98 %), Fluka xylene isomer mixture (^97 %) > Fluka 302.7 grams of DOPO, 1.30 grams of p-toluene The acid monohydrate and 530 ml of xylene (isomer mixture) were placed in a one liter reactor. The reactor was then rendered inert and inactivated with nitrogen. The reaction contents were heated to 140. (:. Then, 155.60 g of 1-ethylmercapto-2-pyrrolidone was added dropwise to the mixture at a product temperature of 140 ° C for 90 minutes. Then continue to stir at 140 ° C 30 minutes. When the reaction continues, the product begins to crystallize. The 201114825 slurry is then cooled to room temperature and the crystallization reaction is completed. The slurry is filtered through a G4-sintered glass block and The residue of the filter was washed twice with 150 ml of xylene. Finally, the crystals were placed in a vacuum drying oven and dried at 80 ° C and 10 mbar for 8 hours until the weight became constant. : 353.2 grams (77.1% of theory) Appearance: Light yellow crystal

Melting point: 200 ° C to 215 ° C Purity: 99.6 area -% (gas chromatography) Free DOPO : 0.4 area -% (gas chromatography) Phosphorus content: 9.60 % (theoretical value 9.48%) 4) Phosphorus compound b .4 synthetic example reaction

Practical operation 432.3 grams (2.0 moles) of DOPO was placed in a 2 liter multi-necked round bottom bottle equipped with a reflux cooling unit and a dropping funnel. The round bottom bottle was then inerted to a non-activated state with nitrogen and the contents of the round bottom bottle were heated to 150 °C. Then, 210.3 g (2.0 mol) of 2-vinylpyridine was added dropwise to the mixture under a lapse of 60 minutes. The reaction mixture was then heated to 18 Torr. (:, and let it continue to react for 6 hours. The reaction mixture was cooled to 50. (:, and it was divided into several portions and added to 500 ml of acetone. The resulting crystalline paste liquid was then sintered with a pore size of 4 The glass frit was filtered and additionally washed with 400 ml of acetone, 17 201114825 and then placed in a vacuum oven for drying. The result was a pale yellow crystal of DOPO-2-ethenylpyridine. The yield is 42%. 5) Synthesis of phosphorus compound b.5

Practical operation This synthesis was carried out in accordance with the procedure of Example 4, using 4-vinylpyridine instead of 2-vinylpyridine. As a result, a pale yellow crystal of DOPO-4-vinylpyridine was obtained in a yield of 65%. 6) Synthesis example of phosphorus compound b.6 Reaction

Practical operation 21.6 grams (0.10 mole) of DOPO was placed in a 250 ml multi-necked round bottom bottle equipped with a reflux cooling unit. The round bottom bottle was then inerted to a non-activated state with nitrogen and the contents of the round bottom flask were heated to 14 (TC.) then 11.6 grams (0.10 mole) of azocarbamate was added with stirring ( A suspension solution consisting of Azodicarboxamid) and 70 ml of phenylmethyl ether (Anisol) was added to the mixture for 2 minutes. After the completion of the addition step, the reaction mixture was heated to reflux and maintained at reflux in 201114825. Heated for 6 hours. The joint anti-filament was cooled to room temperature, and the resulting crystals were aspirated by the sintered block of No. 4, followed by 8 dioxane ____ product, and It was placed in a vacuum = dry. The result was - D (10) · azo dimethyl, and t point was 230. (: and the yield was 57 %. Dan Zheng 7) Application examples are as described above. The 彳 method (10)% of the WEI machine is mixed with the components listed in Tables 1 to 6 to: several casting compositions.

PA12 : PA12A : PA6 : PA6A : PA66 : PA 66 A : PA 614 : PA 614 A : PA 46 : PA 6I/6T : PA6I/6TA , the dimples and raw materials listed in Tables 1 to 6 are as follows: ' Polyamide 12, RV2.2 polyamine 12, heart 2.15, clear 57 microgram equivalents / gram polyamine 6, RV2.8 polyamide 6, slave 2.8, _2 66 microgram equivalent / gram polyamide 66, RV2.9 Polychlorinated 66, RV2.9 'called 58 microgram equivalents per gram of polyamido 614, RV 1.97 polyamine 614, RV h94, NH2 61 microgram equivalents per gram of polyamido 46, RV3.1 polydecylamine 6I/6T, RV 1.54 Polyamide _T ' RV 1.52, NH2 55 μg equivalent / gram "A" in the name of polyamine refers to "(5) Shaoguan and - amine-based terminal amine; ^ Base U" RV: Relative viscosity in terms of PA6, PA66 or PA46, the relative viscosity is fried! 201114825 weight percent of 96% sulfuric acid solution was measured. The relative viscosity for PA 12 was measured at 0.5 ° C in a cresol solution at 20 °C. Abbreviation description ΡΑ6 Polyamine 6 consisting of ε-caprolactam 6. Polyamine u 12 consisting of π·aminoundecanoic acid 12 Heterocyclic tridecane-2-one or ω-amine 10 Polyamide 12 composed of alkanoic acid ΡΑ46 Polyamine 46 composed of butanediamine and adipic acid ΡΑ66 Polyamine 66 composed of hexamethylenediamine and adipic acid ΡΑ614 From hexamethylenediamine And polydecylamine consisting of tetradecanedioic acid 614 ΡΑ 618 consisting of hexamethylenediamine and octadecanedioic acid polyamine 618 ΡΑ 6Ι/6Τ from hexamethylenediamine, isophthalic acid and Copolyamide composed of phthalic acid 6Ι/6Τ Melamine cyanurate: MelapurMC25, manufacturer Ciba Melamine polyphosphate: Melapur200/70, manufacturer Ciba Glass fiber: Vetrotex EC10-4.5 Micron 99B, manufacturer Saint_Gobain Vetrotex Relative viscosity : ISO 307 Temperature 20 ° C Relative viscosity (RV) is determined according to the German industrial standard u 算 算 算 算 : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : Method for performing an amine-based terminal group, in the middle, and then Isopropanol was added. The content of the amine group terminal group is measured. 201114825 Tensile modulus: ISO 527, the speed of stretching is 1 mm / min ISO-stretch test rod, German industrial standard, IS 〇 / CD 3167, type A1, 170 X 20/10x4 mm

Temperature 23°C Tear strength and elongation at tear point: ISO 527, the rate of stretching is 5 mm/min for unreinforced material, and 5 mm/min for tensile-strength ISO-stretching Test Rod 'German Industrial Standard, IS〇/CD 3167, Type A1, 170 X 20/10x4 mm

Temperature 23 ° C Example of Preparation of Pound Composition The preparation of a polymer composition according to the present invention will be described hereinafter in accordance with several compositions used in Example 43. The constrained composition was prepared in a ZSK 25 twin-screw extruder manufactured by Werner and Pfleiderer. The dried polyamide particles pA614 A (17.25 kg) and PA 6I/6T (5.75 kg) were mixed and then uniformly mixed in a rolling mixer for 25 minutes. The dry mixture is weighed through a scale and then added to the feeder. Then, 6 〇 kg of the anti-burning agent b 2 and 6 公斤 kg of the melamine polyphosphate are mixed and added to the feeder via a separate scale. The Μ 之 之 之 — — 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 . The temperature of the first shell < temperature is adjusted to the thief, and the temperature of the remaining housing is adjusted to 26 〇 C. The speed used was 200 rpm and the flow rate was 1 〇 kg/hr, and the gas was shouted before the nozzle. The resulting strands are placed in a human water bath and cooled, 21 201114825 and cut into 'the obtained pellets and then dried at 8 (TC and vacuum for 24 hours to a water content of less than 0.1 wt%. All made from this pellet) The standard test samples were produced by an injection molding machine manufactured by Arburg, Model Allrounder 320-210-750 Hydronica. The cylinder temperature used to prepare these standard test samples was 265. (: to 28〇t: The curve of the upward trend. The casting temperature used for the VO-standard test rod is 60 °C, and the temperature used for casting all other standard test samples is 80 °C. The standard test sample used in the test is used in a dry state. For this purpose, the standard test sample is placed in a dry environment after casting, that is, it is placed on the silicone and stored at room temperature. At least 48 hours. Standard test samples used for flammability testing are stored in accordance with the provisions of the German Industrial Standards. From Tables 1 to 6, not only the composition of the polymers according to the present invention, but also Physical properties such as tensile modulus, tear strength and elongation at tear point, as well as UL-94 flammability test, GWIT, GWFI and LOI. UL-94 flammability test in accordance with ISO 1210 In the vertical flammability test V0, the automatic extinguishing must occur after an average of less than 5 seconds. The possible drop may not ignite the cotton, and the remaining spark must be extinguished after 30 seconds. The flame reaction of the GWFI (glow wire flammability index, IEC 60695-2-12) is carried out in accordance with the relevant standard operating regulations. The GWFI is measured on the test board and is a measure of the surface of the plastic product. A measure of the fire-breathing response exhibited by, for example, a glow wire or an overheated resistor. The test object is squeezed by a heated glow wire for 1 second for up to 3 seconds. The depth to which the glow wire is pressed is limited to 7 mm. Fire resistance test 22 201114825 refers to the burning of the test object in less than 30 seconds after removal of the glow wire and If the paper placed under the test object is not ignited, the GWFI value is provided by the manufacturer for the flame retardant material and is listed on the yellow card data sheet. Glow wire can ignite the temperature (GWIT ' glow Wire ignition temperature, IEC 60695-2-13) is measured on a test panel and is a measure of how a plastic article can be ignited by, for example, a glow wire or an overheated resistor. When determining the temperature of the ignition, the subject itself may not be ignited during the entire test period. Ignition is defined as the phenomenon of migration for more than 5 seconds. This temperature is then quoted as GWIT, which is 25 higher than the highest temperature at which ignition has not yet occurred. Hey. The Oxygen Limit Index (LOI) is measured according to ISO 4589-2. As seen from Tables 1 to 6, the scaled members made of the flame resistant polymer composition according to the present invention showed superior properties in the UL-94 flammability test. For example, the examples cited in the tables show that the flammability classification v is achieved when the sample thickness is 1.6 mm, even when the sample thickness is 〇 8 mm. The result is more noteworthy because the simultaneous tear strength, elongation at tear point, and tensile modulus of elasticity also have excellent properties. Even GWIT and GWFI are listed in the superior nature of these comparative examples. The vo-tests for the cast compositions of Examples 24 '25 and 26 were also tested for test bars having a thickness of 〇·4 $ meters. The results are v〇, which are now presented as test bars with thicknesses of 1.6 mm and 0.8 mm. " For the example listed in Table 6 for the mixture containing PA 6I/6T as the main particle (Example 40 to Example 50), it is especially necessary to emphasize the elongation of the tear point at which the height is achieved. . 23 201114825

Example\〇幽77.2 10.8 CN 1330 § 240 Ο 〇>> 930 800 960 960 〇〇 (N ΙΛ 77.2 1 10.8 (N 1250 JT) 200 Ο 〇>> 930 800 960 960 00 CN Tf 79.2 1 10.8 〇1200 210 Ο 〇>> 900 775 960 960 Comparative Example 81.2 幽 10.8 00 1190 220 <N CN >> 900 750 960 960 fS 83.2 1 10.8 〇1170 230 <N CN >> 900 750 1 1 960 960 88.6 1 inch VO 1080 250 <N (N >> 875 750 1 1 960 960 (N unit weight percent weight percent weight percent weight percent MPa MPa 1.6 mm 0.8 mm 1 mm 3 mm 1 1 1 Millimeter 3 mm 1 group composition PA 12 PA 12 A melamine cyanuric acid test tensile elastic modulus tear strength tear point elongation UL-94 GWIT GWFI L0I 201114825

Example m 9800 120 Ο ο >> 900 875 960 960 <N 〇VO <N (N 1 3300 卜 in ο ο >> 850 825 960 960 Comparative example 〇\ ο 〇10100 125 〇\ ΗΒ 775 775 775 775 800 00 ο 10540 140 〇<N C5 CQ Κ X 750 775 750 775 v〇<N 1> g ο 〇1 3540 (Ν (Ν >> 775 750 775 800 unit weight percentage by weight Weight percent Weight percent MPa MPa 1.6 mm 0.8 mm 1 mm 3 mm 1 mm 3 mm 1 Group composition PA6 Melamine polyscalate j6 Glass fiber test Tensile elastic modulus Tear strength Tear point elongation UL-94 GWIT GWFI L0I 201114825

Example CN CN 10550 110 Ο ο >> 825 850 1 1 960 960 CN ΓΛ GC 10500 in ο ο >> 825 825 960 960 〇〇 11700 in (N r-* Ο (Ν >> 825 825 850 900 VO CN CN 1 3950 l〇卜Ο ο >> 850 850 1 ! 960 960 Ρ: Os 〇1 4100 i〇VO G\ ο ο >> 775 775 1 1 800 825 〇\ CN m 卜11110 i〇tH ΗΒ ΗΒ 800 800 I 1 900 960 Comparative Example 2 〇〇 (N 10190 m — CQ > ffi 775 825 875 960 2 v 〇 10480 115 ΗΒ 775 775 825 i I 750 960 Unit weight percent by weight Weight percent Weight percent MPa MPa 1.6 mm 0.8 mm 1 mm 3 mm 1 mm 3 mm 1 Group composition PA 66 Melamine polyphosphate X) Glass fiber test tensile elastic modulus tear strength tear point elongation UL-94 GWIT 1 1 GWFI L0I 201114825

Example 1 I 1 1 CN CN Ο 10900 inch · ο ο , >> 1 900 900 〇\ ΓΛ <s 1 1 jn 1 1 m Τ"Η (Ν ο m 10000 (Ν — ο ο >> ' 930 960 v〇m 00 η 1 1 1 1 <Ν 1 3800 Ο ο ο >> ' 930 960 v〇cn 1 sun g 1 1 Ο Ο 1 3900 οο (Ν ο ό >> 1 900 930 inch CO v〇fS sun 79.2 1 1 10.8 I ο 1 1850 180 ο ο ο >>> 900 960 VO m tn fS 79.2 1 1 1 10.8 I ο 1 1800 inch (Ν ο ο ο >>> 900 960 v〇fS 80.4 1 1 1 Os 1 ο 1 1750 inch (Ν ο ο ο >>> 1 sun fS Ο Ό \ 1 1 1 1 1 ο 1 1410 ο inch ο m ο ο , >> ' 875 960 v〇(N n fS 1 1 1 1 00 00 10400 120 ο iri (Ν — >> 1 850 850 沄 mn 1 1 1 1 00 00 10200 115 in in (Ν — >> ' 800 825 o fS (Ν ΟΝ 1 1 1 1 1 00 晒 1350 Ο in v〇 (Ν CN >> ' 825 900 inches (N unit weight percent weight percent weight percent weight percent weight percent weight percent weight percent Weight percentage MPa MPa 1.6 millimeters 0.8 mm 0.4 mm 1 mm 1 mm 1 group composition PA 12 PA 12 A PA 6 A PA 66 A melamine cyanuric acid melamine polyphosphate (Ν glass fiber test tensile elastic modulus tear strength tear point elongation UL-94 GWIT GWFI LOI 201114825

Example 〇 1 1 1 1 CN CN ο m 10800 〇1-H Ο ο >> 900 900 875 960 mm 90 1 幽 JTJ 1 幽 m CN ο m 9950 〇CO o <N ο ο >> 875 875 960 960 P; 1 1 1 1 CN CN 1 3750 yn m 〇ο ο >> 800 800 850 960 \〇(N Π 幽 77.2 1 1 10.8 1 CN 1 1200 oo <N ο ο > &gt 900 775 960 960 卜 (N ΙΛ Π 77.2 1 1 1 10.8 1 1 1160 o inch oo CN ο ο >> 900 775 960 960 78.2 1 1 1 10.8 1 1 1140 o inch o CN ο ο >> 900 750 960 960 Comparative Example 1 1 1 1 〇Ο Ο m 10890 o (N —(Ν >> 800 825 775 930 rs 1 1 § 1 1 Ο ο 1 3680 o 卜 (Ν CN >> 750 725 800 900 (N ι·Η 79.2 1 1 1 10.8 I ο 1 1100 inch l〇(N (Ν <Ν >> 875 725 960 960 in CN unit weight percent weight percent weight percent weight percent weight percent weight percent Weight percent Weight percent MPa MPa Ο 00 —〇1 mm 3 mm 1 mm 3 mm Group I composition PA 12 PA 12 A PA 6 PA 66 Melamine cyanurate melamine Polyphosphate cn χ> Glass fiber test tensile elastic modulus tear strength tear point elongation UL-94 L________ι GWIT GWFI LOI 201114825 Example Sun 1 1 34.5 11.5 1 CN 1 1 <N ο CO 11200 110 00 CN ο ο >> 1 1 19.5 1 1 (N 1 1 CN Ο to 15450 120 Ο (N ο ο >> 00 34.5 1 1 1 11.5 1 rs 1 t CN ο m 11100 S (N ο ο >>19.5 1 1 1 1 (N 1 CN 1 17150 120 r> ο ο >> 1 1 1 34.5 11.5 1 (N 1 <N sun 11250 110 Os ri ο ο >> ΙΛ 1 drying 19.5 1 V〇1 CN 1 (N 1 15500 125 卜CN ο ο >> 1 1 34.5 1 1 11.5 (N 1 (N 1 9800 115 CN ο ο >> 1 1 34.5 1 1 CN 1 (N 1 9800 o Tf- ο ο >> 1 34.5 1 1 11.5 1 CN 1 (N 1 9500 in rn ο ο >> 1 34.5 Sun 1 1 <NI 1 9400 100 〇cn ο ο >> Ο 34.5 1 1 1 11.5 1 (N rH CN Τ"Η 1 1 11050 105 <N ο ο >> Unit Weight Percent Weight Percent Weight Percent Weight Percent Weight Percent Weight Percent Weight Percent Weight Specific weight percentage Weight percent Weight percentage MPa MPa 1.6 mm 0.8 mm Composition ΡΑ 66 ΡΑ614 ΡΑ 614 A PA46 PA 61 / 6T PA 61 / 6T A Melamine polyphosphate (N Μ glass fiber test tensile modulus tear strength tear Crack elongation UL-94

Claims (1)

201114825 VII. Patent application scope: 1. A flame-retardant polymer composition containing at least one phosphorus compound as a flame retardant, characterized in that it contains a) 20 to 91 weight percent polyamine (PA) or polybutylene terephthalate (PBT) as a polymer, b) one of 9 to 20 weight percent of a phosphorus compound as a flame retardant selected from the group consisting of The group contains: bl b.2 b.3 b.4 30 201114825 b.5 And / or b.6 c) 0 to 30 weight percent of another flame retardant and/or synergist, d) 0 to 10 weight percent of another additive and e) 0 to 65 weight percent - fibrous or granular The result of the addition of a) to e) is equal to 1% by weight. 2. A flame-retardant polymer composition according to claim 1 of the patent application, characterized in that PA (composition a) is composed of PA 6, PA 11, PA 12, Pa 46, PA66, PA614, PA618, PA6I/ A mixture of 6T and its equivalent is selected. 3. A flame-retardant polymer composition according to at least one of items 1 to 2 of the patent application, characterized in that it contains 3 to 30 parts by weight of component c). 4. A flame-retardant polymer composition according to one of the first to third aspects of the patent application, characterized in that component c) is a nitrogen-containing compound, a nitrogen-containing and scaly compound, a metal borate Metal carbonates, metal hydroxides, metal hydroxide oxides, metal nitrides, metal oxides, metal phosphates, metal sulfides, metal stannates, metal hydroxide stannates, Citrate, 31 201114825 Zeolite, alkaline zinc citrate and/or citric acid were selected. 5. A flame-retardant polymer composition according to at least one of claims 1 to 4, characterized in that the additive (composition d)) is an inorganic stabilizer, an organic stabilizer, and a lubricant Agents, pigments and marking substances, inorganic pigments, organic pigments, infrared absorbers, antistatic agents, anti-caking agents, nucleating agents, crystallization accelerators, crystal retarders, metal carboxylates, lengthening of chain length Additives, conductive additives, carbon black, graphite, carbon nanotubes, mold release agents, mold separating agents, optical brighteners, additives for photoreactive discoloration, plasticizers, foreign polymers, bismuth A crashworthy modifier, an adhesive, an anti-drip agent, a metallic pigment, a metal microchip, a metal coated particle, and/or a mixture of the same is selected. 6. A flame-retardant polymer composition according to at least one of claims 1 to 5, characterized in that the user is a fibrous or reinforced filler, as a component e, including glass fibers , carbon fiber, metal fiber, aromatic hydrocarbon polyamide fiber, vegetable fiber, polymer fiber, filament fiber, mineral fiber, synthetic flaky citrate, natural flaky citrate and/or mixtures thereof Or a particulate filler, which is selected from the group consisting of ore, talc, mica, dolomite, silicate, quartz, titanium dioxide, ash stone, ridge soil, broken Acid, magnesium carbonate, magnesium hydroxide, white, ground glass, glass flakes, ground carbon fiber, ground or precipitated calcium carbonate, lime, feldspar, barium sulfate, permanent magnetic or magnetizable metal or alloy , glass spheres, hollow glass spheres, hollow spherical citrate fillers, synthetic flaky citrates, natural flaky citrates and/or mixtures thereof. 7. Anti-combustion polymerization 32 201114825 composition according to the scope of the application of the scope of the patent application, which is characterized in that it contains. a) 25 to 85 weight percent polyamine, b 10 to 18 weight percent of the phosphorus compound, c) 5 to 22 weight percent of at least one other flame retardant/or synergist, d) 0.1 to 10 weight percent of one of the additives and e) 0.1 to 50 One of the weight percentage fillers, wherein the total of the results from a) to e) is 1% by weight. 8. A casting element which can be prepared from a flameproof polymer composition according to at least one of items 1 to 7 of the patent application. 9. A casting element according to item 8 of the scope of the patent application, characterized in that a reinforced component having a wall thickness of 1.6 mm satisfies the condition of the flammability class V0 in the UL-94 flammability test. 10. A casting element according to one of the items 8 to 9 of the patent application, characterized in that the casting element having a wall thickness of 1 mm has a GWIT (IEC 60695-2-13) of at least 800 ° C and / or GWFI (IEC 60695-2-12) is at least 800 〇C. 11. A fire-resistant polymer composition using one of items 1 to 7 of the patent application garden as a power tool, household electrical appliance, electrical equipment, electronic equipment, portable electric or electronic equipment , telecommunications equipment supplies, entertainment electronic equipment supplies, computers, notebook computer enclosures or components of materials, or used in construction, automotive, furniture, energy or machinery industries. 33 201114825 IV. Designated representative map: (1) The representative representative of the case is: (). (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: B.l 2