TW201527424A - Flame retardant thermoplastic polymer compositions - Google Patents

Abstract

The invention provides a flame retardant thermoplastic polymer composition. The composition contains a thermoplastic organic polymer and at least one flame retardant agent. The flame retardant agent is an amino-functional silicone resin.

Description

Flame retardant thermoplastic polymer composition

The present invention relates to a flame retardant for a thermoplastic organic polymer composition and a flame retardant thermoplastic polymer composition containing the same. The invention is particularly applicable to polyamines, but can also be used in other thermoplastic polymers such as polyesters.

The present invention provides flame retardant thermoplastic polymer compositions. The composition contains a thermoplastic organic polymer and at least one flame retardant. The flame retardant is an amine functional polyoxyl resin.

The composition is typically a mixture of at least two chemically distinct compounds. Thermoplastic organic polymer compositions comprise a combination of a thermoplastic organic polymer and typically other ingredients (sometimes referred to as additives). Thermoplastic organic polymers typically form a polymer matrix. Other ingredients or additives may contain, for example, a flame retardant, a filler, a fortifier, a mineral powder, and the like.

A flame retardant is a compound capable of providing flame retardant properties. Generally, flame retardants provide flame retardant properties when added to compositions containing thermoplastic organic polymers. Flame retardant properties are believed to be obtained when the flame retardant-containing composition exhibits increased resistance to combustion or other flame-induced decomposition as compared to flame retardant-free compositions. Compositions containing a flame retardant are more resistant to flame than the same composition without flame retardant. The flame retardant composition can comprise a thermoplastic polymer that typically forms a matrix and one or more flame retardants.

The polyoxyalkylene or polyoxynene contains a ruthenium-containing compound having a repeating Si-O-Si bond. The decane is a ruthenium-containing compound which does not contain a repeating Si-O-Si bond. Polymers contain compounds which typically form repeating units of one or more chains. The organic polymer is a polymer containing a repeating C-C bond. organic A polymer is sometimes defined as a polymer in which at least 50% of the atoms in the polymer backbone are carbon atoms. Thermoplastic polymers are polymers having thermoplastic properties. Thermoplastic polymers allow the plastic to deform when heated.

Polyoxymethylene is typically based on materials containing polymer chains that repeat Si-O-Si bonds. The polyoxygen oxide may include monofunctional (M), difunctional (D), trifunctional (T) and/or tetrafunctional decane (Q) units. The Si atom of the M unit is bonded to one O atom. The Si atom of the D unit is bonded to 2 O atoms. The Si atom of the T unit is bonded to 3 O atoms. The Si atom of the Q unit is bonded to 4 O atoms.

The polyoxyxene resin contains at least one T unit and/or at least one Q unit. Preferably, the polyoxynoxy resin contains two or more T units and/or Q units.

The M unit usually has the formula R ₃ SiO _1/2 . The D unit typically has the formula R ₂ SiO _2/2 . The T unit typically has the formula RSiO _3/2 . The Q unit usually has the formula SiO _4/2 . Each R is linked to a substituent (also referred to as a group) of a deuterium atom. Where the unit contains more than one R, R may be the same or may differ on one deuterium atom. In addition, R can be different on different germanium atoms. R is usually an organic substituent, i.e., a substituent containing at least one C atom, preferably a plurality of C atoms forming a CC bond.

Unless otherwise indicated, the weight percentages mentioned in the following description are based on the weight of the total composition (ie, the composition containing the polymer and all other ingredients). The thermoplastic organic polymer can be formed from one or more polymers.

In a preferred embodiment of the invention, one of the polymers forming the thermoplastic organic polymer is polyamine. Preferably, at least 50% by weight, based on the total weight of all of the thermoplastic organic polymers present in the composition, is formed from polyamine. Preferably, the thermoplastic organic polymer is formed substantially from polyamine. Amino-polysiloxane resins have been found to be particularly suitable for providing flame retardant properties to polyamidoamines.

In other preferred embodiments, the thermoplastic organic polymer contains a polyester. In these preferred embodiments, based on the total weight of the thermoplastic organic polymer present in the composition Preferably at least 50% by weight is formed from polyester. More preferably, the thermoplastic organic polymer is substantially formed of a polyester.

It is believed in the art that an amine polyoxyxylene resin is incorporated into the thermoplastic matrix in the absence of reaction between the amine functional group of the additive and the substrate. Preferably, the thermoplastic matrix is free of reactive unsaturation that would otherwise potentially react with the amine functional groups of the flame retardant. It is believed in the art that the amine functional groups of the flame retardant are only susceptible to reaction in the event that the composition is exposed to a flame.

Reactive unsaturated systems are unsaturated in response to non-reactive unsaturation. For example, the unsaturation contained in an aryl group such as a phenyl group has extremely low reactivity due to its aromatic character. Therefore, their unsaturation is considered to be non-reactive unsaturated. The polymer matrix used in the present invention is preferably free of a mixture of reactive unsaturated polymers, copolymers or polymers. If present, the unsaturation of the polymer, copolymer or mixture of polymers is preferably only non-reactive.

Preferably, the thermoplastic polymer is free of polymers containing reactive unsaturation. Preferably, the thermoplastic polymer is free of ABS (acrylonitrile butadiene styrene), SBS (poly(styrene-butadiene-styrene)) and/or diene elastomer. Preferably, the thermoplastic polymer is free of polyphenylene esters. Preferably, the thermoplastic polymer is free of EPDM (ethylene propylene diene rubber).

The thermoplastic polymer can be substantially free of unsaturated saturated polymers. The thermoplastic polymer can be PE (polyester), PA (polyamide), polyolefin (such as PP (polypropylene)) or PE (polyethylene), PC (polycarbonate), PS (polystyrene), PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PMMA (poly(methyl methacrylate)), POM (polyoxymethylene), PEEK (polyether ether ketone), PES (polyether oxime), PPO (poly(phenylene ether)).

The thermoplastic polymer can be a mixture or copolymer of polymers.

Thermoplastic polyamides are widely used in many applications in which polyamides are formed by, for example, injection molding, blow molding, or extrusion. For example, thermoplastic polyamide compositions are commonly used in the casing of electrical equipment or wires. In this application, the thermoplastic polyamide composition is required to have a certain A degree of fire resistance, but polyamine does not have inherent flame retardancy. The flame retardant polyamide composition is made to include a flame retardant containing a halogen such as brominated polystyrene, polybrominated diphenyl or polybrominated diphenyl oxide. Such halogen-containing flame retardants may be harmful to health, and a flame retardant thermoplastic polyamide composition containing no halogen-containing flame retardant is required in the industry.

CN-102604377-A describes flame retardant thermoplastic polyamide compositions comprising from 30% by weight to 90% by weight of thermoplastic polyamide resin, from 5% by weight to 40% by weight of bromine-containing flame retardant, 0.5% by weight -15% by weight of an auxiliary flame retardant and 0-50% by weight of a reinforcing material. The auxiliary flame retardant includes zinc borate and an organic polyoxyl resin in a weight ratio of 9:1 to 1:1.

JP-2004-115582-A describes the preparation of a flame-retardant polyamide composition by kneading 80% by weight to 99.9% by weight of a polyamide resin and 0.1% by weight to 20% by weight of liquid polyfluorene. JP-2004-115651-A describes a flame-retardant polyamine composition comprising a polyamine resin containing an aromatic unit and a metal borate compound. JP-2003-192923-A describes a resistance comprising 20% by weight to 94.9% by weight of a thermoplastic resin, 0.1% by weight to 20% by weight of a vinyl-containing polyoxonium compound and 5% by weight to 60% by weight of a strengthening agent. A flammable thermoplastic resin composition.

It has been found in accordance with the present invention that certain polyoxyxides are particularly effective as flame retardants in halogen-free polyamine compositions and other thermoplastic organic polymer compositions. The industry believes that amine-based polyoxynitrides containing only M and D units do not provide a flame retardant effect. At least one T and/or at least one Q unit is required. Linear amine polyoxyxides are not suitable for use in the present invention.

The halogen-free flame-retardant thermoplastic organic polymer composition of the present invention comprises a thermoplastic organic polymer, and is characterized in that the composition contains an amino-functional polyoxyalkylene resin as a flame retardant.

According to an aspect of the invention, the flame retardant for the thermoplastic organic polymer composition is characterized in that the flame retardant comprises from 5% by weight to 90% by weight based on the total weight of all of the flame retardants of 100%. Preferably from 50% to 90% by weight of the amine functional polyoxyn tree Fat, 5% to 30% by weight of an auxiliary flame retardant selected from the group consisting of borate, melamine compound and phosphinate, and 0 to 45% by weight of mineral powder.

The invention also encompasses the use of a flame retardant comprising an amine functional polyoxyxylene resin for improving the flame retardancy of a thermoplastic organic polymer composition.

The amine groups present in the polyoxyxylene resin are typically present as at least one R substituent which is linked to a hydrazine atom as explained above. R is preferably an alkyl, aryl or aralkyl substituent substituted with an amine group. For example, an R-based aminoalkyl substituent.

Of the amine functional silicon siloxane unit group may include poly silicone selected from: wherein R ₃ SiO _1/2 M units of the formula R ₂ SiO _2/2 or R ₂ SiO _1/2 OZ of D units a T unit of the formula RSiO _3/2 , RSiO _2/2 OZ or RSiO _1/2 (OZ) ₂ and a formula of SiO _4/2 , SiO _3/2 OZ, SiO _2/2 (OZ) ₂ or SiO _1/2 (OZ) A Q unit of ₃ , wherein each R represents an organic group bonded to hydrazine or an amine group bonded to hydrazine, and Z represents hydrogen or an alkyl group. The amine group of the polyoxyxylene resin is usually present as an organic group R, and R may be an alkyl group, an aryl group or an aralkyl group substituted with an amine group, such as an aminoalkyl group. At least some of the siloxane units of the polyoxygenated resin are T units or Q units. Therefore, the amino functional polyoxyxene resin has the formula M _x D _y T _z Q _w , wherein x, y, z and w are each expressed in mol% and can be 0-100% (premise that z+w is not equal to 0) ), preferably at least 1%.

The amino group substituted with an amine group may have, for example, the formula R'-(N(R")-A') _q -N(R")-A-, wherein A and A' each independently have from 1 to 10 a carbon atom and optionally an ether-linked linear or branched alkyl, aryl or aralkyl group; q = 0-4; R' is hydrogen or an alkyl group having from 1 to 10 carbon atoms; A hydroxyalkyl, aryl or aralkyl group; and each R" is independently hydrogen or an alkyl, hydroxyalkyl, aryl or aralkyl group having from 1 to 10 carbon atoms. When A and/or A' When the alkyl group is extended, the alkylene group may have, for example, 1 to 6 carbon atoms. When R' and/or R" is an alkyl group, the alkyl group may have, for example, 1 to 8 carbon atoms, usually 1 to 4 One carbon atom. For example, an amino group-substituted organic group may contain a primary aminoalkyl group, wherein R' and R" are both hydrogen; q = 0 or 1; and A and A' (if present) each contain 2 to 4 carbons Examples of preferred aminoalkyl groups include: -(CH ₂ ) ₃ NH ₂ , -(CH ₂ ) ₄ NH ₂ , -(CH ₂ ) ₃ NH(CH ₂ ) ₂ NH ₂ , -CH ₂ CH ( CH ₃ )CH ₂ NH(CH ₂ ) ₂ NH ₂ , -(CH ₂ ) ₃ NHCH ₂ CH ₂ NH(CH ₂ ) ₂ NH ₂ , -CH ₂ CH(CH ₃ )CH ₂ NH(CH ₂ ) ₃ NH ₂ , -CH ₂ NH ₂ , -(CH ₂ ) ₃ NH(CH ₂ ) ₄ NH ₂ and -(CH ₂ ) ₃ O(CH ₂ ) ₂ NH ₂ . Many of these groups contain primary and secondary Both amine groups. The amine group substituted with an amine group may alternatively contain only a secondary amine group, such as -(CH ₂ ) ₃ -NH-(C ₆ H ₅ ) or -(CH ₂ ) ₃ NH (CH ₃ ); or a tertiary amine group such as -(CH ₂ ) ₃ -N-(CH ₃ ) ₂ . Examples of preferred aminoaryl groups include aminophenyl groups such as 4-aminophenyl groups. Examples of preferred amino aralkyl groups include aminobenzyl groups such as -CH ₂ C ₆ H ₄ -NH ₂ and -CH(C ₆ H ₅ )NH ₂ . The amino group substituted with an amine group may be present in M. , D and / or T oxane units.

The amino functional polyoxyl resin preferably has an amine equivalent weight of from 200 g to 2000 g/amine nitrogen, more preferably from 300 g to 1000 g/amine nitrogen.

The organic group R other than the amino group-substituted organic group in the amino functional polyoxyalkylene resin may be, for example, an alkyl group and/or an alkenyl group having 1 to 6 carbon atoms and/or have 6 to 10 An aryl or aralkyl group of a carbon atom. The alkyl group R bonded to hydrazine is preferably a methyl group, but may be, for example, an ethyl group. The alkenyl group is generally not present in the amino functional polyoxyl resin, but may be a vinyl group if present.

It has been found that an amino-functional polyoxyxylene resin containing an aryl group (e.g., a phenyl group) can be used as a more effective flame retardant for a polyamine composition than an amine group-free polyoxyl resin having no aryl group. . The amino-functional polyoxynoxy resin may include, for example, at least 50% by weight of an aryl group, more preferably at least 60% by weight of an aryl group based on the total weight of the organic group R in the amino-functional polyoxysiloxane resin, and may contain, for example, 70% by weight or 75% by weight, up to 80% by weight or more of an aryl group, preferably a phenyl group. Therefore, a preferred type of polyoxyxylene resin is an amino functional phenylmethyl polyoxyl resin.

The amino functional resin used as a flame retardant may contain a functional group other than an amino functional group. Preferably, the resin also contains an aryl functional group, such as a phenyl functional group. This means that the other functional groups are present in the resin and are not directly linked to the amine functional group. These aryl functional groups enhance compatibility with the polymer matrix and/or Tg and/or thermal resistance.

The amino functional polyoxyl resin contains T and/or Q units. It preferably comprises a combination of a T unit of the formula RSiO _3/2 with an M unit of the formula R ₃ SiO _1/2 and/or a D unit of the formula R ₂ SiO _2/2 . The organic group substituted with an amine group is usually present in the D unit. The D units may be a (meth)aminoalkyl oxane unit such as a (meth)aminopropyl fluorene unit NH ₂ (CH ₂ ) ₃ (CH ₃ )SiO _2/2 , (A) N-methylaminopropyl oxazane unit CH ₃ NH(CH ₂ ) ₃ (CH ₃ )SiO _2/2 , (methyl) N-phenylaminopropyl decane unit C ₆ H ₅ NH(CH ₂ ) ₃ (CH ₃ )SiO _2/2 or (methyl)-N-benzylaminopropyl oxazane unit C ₆ H ₅ (CH ₂ )NH(CH ₂ ) ₃ (CH ₃ ) SiO _2/2 . The group substituted with an amine group may alternatively be present in the M unit. The M units may be (dimethyl)aminoalkyl oxime units (for example NH ₂ (CH ₂ ) ₃ (CH ₃ ) ₂ SiO _1/2 ) or aminoalkyl oxane T units NH ₂ (CH ₂ ) ₃ SiO _3/2 . The amine group bonded to the oxime may be present in the D unit (e.g., (meth)amino oxime unit (H ₃ C)(NH ₂ )SiO _2/2 ). The aryl group may be present in a D unit (eg, a diphenyloxane unit or a methylphenyloxane unit) and/or a T unit (eg, a phenyloxane T unit). The aralkyl group may be present in the D unit (e.g., methylbenzyl oxoxane unit) and/or T unit (e.g., benzyl oxoxane T unit). The alkyl group may be present in unit D (e.g., a (meth)aminoalkyl oxane unit as set forth above) or a (meth)amino aryl oxane or a (meth)aminobenzyl oxime In the alkane unit, and optionally in the methylphenyloxane unit and/or the dimethyloxane unit, and/or in the M unit (eg, trimethylmethoxy unit) and/or T Unit (for example, methyl oxane unit CH ₃ SiO _3/2 ).

The amino functional polyoxynoxy resin preferably contains less than 25% by weight of hydroxyl groups and/or alkoxy groups, for example from 0 to 12% by weight or from 0 to 8% by weight of the combined hydroxyl groups and/or alkoxy groups. Preferably, the amino functional polyoxyl resin does not contain residual alkoxy groups. Any hydroxy and/or alkoxy group may be present in the T unit (eg, methyl methoxy polyoxy unit CH ₃ (OCH ₃ ) SiO _2/2 , methyl hydroxy polyoxy unit CH ₃ (HO) SiO _{2 / 2} or a phenylhydroxy polyanthracene unit C ₆ H ₅ (HO)SiO _2/2 ) or a D unit (for example, dimethylmethoxy polyanthracene unit (CH ₃ ) ₂ (CH ₃ O)SiO _1/2 Or a Q unit (for example ROSiO _3/2 wherein R is alkyl or H).

The amino functional polyoxynoxy resin can be a liquid or solid resin. The liquid amine functional polyoxyxene resin may have a kinetic viscosity of, for example, from 200 PCT to 50,000 PCT at 25 °C. The solid resin may preferably be readily incorporated into the polymer matrix which is typically also in solid form prior to forming the composition.

The thermoplastic organic polymer composition in which the amine functional polyoxymethylene resin flame retardant is incorporated includes a thermoplastic organic polymer and, optionally, one or more fillers and/or enhancers. The thermoplastic organic polymer is typically the major component of the thermoplastic organic polymer composition, i.e., it comprises at least 50% by weight of the total thermoplastic organic polymer composition. The thermoplastic organic polymer is, for example, polyamine or alternatively selected as a polyester. Polyamines are generally indicated by the term nylon.

Suitable thermoplastic polyamines include, for example, polycaprolactam (Nylon-6), polyhexamethylene hexamethylenediamine (Nylon-6,6), polyfluorene hexamethylenediamine (Nylon-6, 10), polytetramethylene hexamethylenediamine (Nylon-4,6), poly(p-xylylenediamine), polyhexamethylene phthalimide, polyhexamethylene Polyisophthalimide, poly-decalin polyphosphate derived from vegetable oil 11: polyundecyl bridge indoleamine (for example, Rilsan (trademark) of Arkema), polydecyl 12 (poly 12 Endoamine, such as Vestamid L (trademark) of Evonik. Alternatively, the thermoplastic polyamine may contain an aromatic moiety such as poly(m-xylylene hexamethylenediamine (Nylon 6I) or polyhexamethylene-p-xylyleneamine (Nylon 6T); or may be completely Aromatic polyamines such as Kevlar (trademark) or Nomex (trademark) from Dupont, Teijinconex from Teijin, Twaron or Technora (trademark), Kermel (trademark) from Kermel or Sepctra from Honeywell. Thermoplastic polyamides can be copolymers, such as nylon-6,66 prepared from its own indoleamine, hexamethylenediamine and adipic acid or prepared from hexamethylenediamine, adipic acid and sebacic acid Nylon-66,610. The thermoplastic polyamine can be a blend of any of the above polymers to achieve a more balanced set of properties.

Examples of suitable polyesters include polyethylene terephthalate and polybutylene terephthalate, as well as blends and copolymers thereof.

The amine functional polyoxymethylene resin flame retardant may be from 10% by weight to 50% by weight, preferably from 15% by weight to 50% by weight, for example 20% by weight, based on the weight of the thermoplastic organic polymer of the amino functional polyoxyl resin. Up to 40% by weight is incorporated in, for example, a thermoplastic organic polymer composition.

Examples of reinforcing agents which can be used in the thermoplastic organic polymer composition include fibrous compounds such as glass fibers, carbon fibers, metal fibers, natural fibers or ceramic fibers. The glass fibers can be in the form of, for example, continuous glass fibers, glass fibers cut to a constant fiber length, ground glass fibers, or non-woven or woven glass flame retardant fibers. The fibrous reinforcing agent may be present, for example, from 0 to 150% by weight based on the weight of the thermoplastic organic polymer. For example, the glass fibers may be present in the polyamide composition in an amount of from 10% to 150% by weight, preferably from 15% to 100% by weight, especially from 15% to 50% or 60% by weight, based on the weight of the thermoplastic organic polymer. . For example, the glass fibers may be present in an amount of from 0 to 60% by weight of the composition based on the weight of the organic polymer and the glass fibers.

Examples of fillers that can be used in the thermoplastic organic polymer composition include talc, ceria, calcium carbonate, mica, kaolin, titanium oxide, carbon black, metals, ceramic powders, borosilicates and/or clays (e.g. gray). The filler may be present, for example, based on 0 or 5 wt% to 50 wt% or 95 wt% of the weight of the thermoplastic organic polymer.

The amino functional polyoxyxylene resin can be used only as a flame retardant in thermoplastic organic polymer compositions, but is most effectively combined with an auxiliary flame retardant which can be selected, for example, from borate, melamine compounds and phosphinates. use. The amino functional polyoxyxylene resin is preferably present in a major proportion by weight of the total flame retardant in the thermoplastic organic polymer composition. The amino functional resin preferably comprises at least 50% by weight of the total weight of all flame retardants present in the composition.

Examples of suitable flame retardant borate are, for example, U.S. Borax, "Zinc Borate 500" Zinc borate sold. Zinc borate can be used, for example, based on 1% by weight to 20% by weight of the thermoplastic organic polymer.

An example of a melamine compound, a melamine hydrogen bonding compound, and a cyanuric acid suitable melamine compound, and is commercially available, for example, as "Melapur MC 25" from BASF. The melamine cyanurate can be used, for example, based on 1% by weight to 20% by weight of the thermoplastic organic polymer. Other examples of melamine compounds are melamine phosphate, such as melamine polyphosphate.

An example of a suitable phosphinate is the metal phosphinate sold by Clariant as "Exolit PO-1230". The metal phosphinate can be used, for example, based on 1% to 50% by weight, for example 1% to 20% by weight, based on the thermoplastic organic polymer.

Accordingly, the present invention comprises a halogen-free flame retardant for a thermoplastic organic polymer composition, characterized in that the flame retardant comprises from 50% by weight to 90% by weight of an amino functional polyoxyxylene resin, 5% by weight Up to 30% by weight of an auxiliary flame retardant selected from the group consisting of borate, melamine compound and phosphinate, and 0 to 45% by weight of mineral powder, based on the total weight of all flame retardants. The mineral powder can be, for example, talc. The flame retardant may contain an intumescent additive such as ammonium polyphosphate. No halogen-containing compound is added.

The flame retardant is therefore halogen-free, i.e. it contains less than 1% by weight of halogen and preferably has no measurable halogen content. Similarly, the thermoplastic organic polymer composition is halogen free, meaning that it contains less than 1% by weight of halogen. In a preferred embodiment, the composition is free of phosphorus, but in other embodiments the phosphorus compound may be present for a particular purpose, such as melamine phosphate or metal phosphinate as an auxiliary flame retardant or as an expansion additive. Ammonium polyphosphate.

The thermoplastic organic polymer composition can be formed by molding, for example by injection molding, extrusion or blow molding, to form a variety of products, such as sleeves, containers, profiles or fibers. The amine functional polyoxynoxy resin or the flame retardant comprising the amino functional polyoxyl resin can be conveniently combined with the thermoplastic organic polymer combination by extrusion, for example, in a twin screw extruder. In. If the amino-functional polyoxynene resin is a liquid, the twin-screw extruder can be equipped with a liquid injection line for polyoxyxides and a co-additive for feeding thermoplastic organic polymers and any powder form (eg Side feeder for auxiliary flame retardants or mineral powders). The thermoplastic organic polymer and co-additive can be physically mixed prior to introduction into the side feeder. The thermoplastic organic polymer can be conveniently pre-mixed with any fibrous reinforcing agent (such as glass fibers) and then mixed with other ingredients. If the amino functional polyoxyxene resin is a solid, all of the components of the thermoplastic organic polymer composition can be physically mixed prior to introduction into the extruder. The amine functional polyoxyxylene resin or the amino functional group can be polymerized in an internal mixer such as a Brabender Plastograph (trademark) mixer or a Banbury mixer equipped with a roller blade or on a roll mill The flame retardant of the oxyresin is alternatively incorporated into the thermoplastic organic polymer composition. When the injection molded article is formed from the thermoplastic organic polymer composition, the amine functional polyoxyxene resin or the flame retardant comprising the amine functional polyoxyl resin can be bonded to the thermoplastic by extrusion as explained above. In the organic polymer composition, the extrudate can be granulated and then molded in an injection molding machine.

Polyamine compositions, in particular based on nylon-6 or nylon-6,6 are widely used in electrical and electronic products and wire bushings, and are required to be flame retarded due to the risk of fire due to electrical failure. Sex. The primary benchmark for the compositions of such sleeves is the UL-94 test of Underwriters Laboratories, Inc., especially for vertical burn testing. In this test, a total of 5 samples each having a length of 125 mm and a width of 13 mm and a thickness of 0.7 mm or 1.5 mm or 3.0 mm were tested according to the thickness. Each sample was mounted with a long axis perpendicular and supported so that its lower end was 10 mm above the Bunsen burner. A 20 mm high blue flame was applied to the center of the lower edge of the sample for 10 seconds and removed. If the combustion stops within 30 seconds, the flame is applied for another 10 seconds. If the sample is dropped, the particles are allowed to fall onto the layer of dry absorbent surgical cotton placed 300 mm below.

The requirement for the UL94 rating of V-0 is that the flaming combustion of the sample after application of the test flame must not exceed 10 s. The total flaming time of the five flames applied shall not exceed 50 s. second The burning and afterglow time after the application of the secondary flame shall not exceed 30 s. The flaming or afterglow of the sample burning shall not reach the retaining clip and shall not drip the flaming particles, which will ignite the dry absorbent surgical cotton located 300 mm below. The requirement for the UL94 rating of V-1 is that the flaming combustion of the sample after application of the test flame shall not exceed 30 s. The total flaming time of the five flames applied shall not exceed 250 s. The burning and afterglow time after the second flame application shall not exceed 60 s. The flaming or afterglow of the sample burning shall not reach the retaining clip and shall not drip the flaming particles, which will ignite the dry absorbent surgical cotton located 300 mm below. For samples having a thickness of 1.5 mm, the halogen-free and phosphorus-free flame retardant polyamine composition of the present invention is capable of achieving a UL94 rating of V-1.

The invention is illustrated by the following examples in which the parts and percentages are by weight.

Examples 1 to 18

Preparation of polyamine compositions from the following materials in the ratios shown in Table 1 below

PA-6 nylon-6

GF glass fiber

ASR1 amino-functional polyoxyalkylene resin comprising NH ₂ (CH ₂ ) ₃ (CH ₃ )SiO _2/2 D unit, diphenyl siloxane O unit, phenyl oxane T unit and trimethyl a decyloxy M unit having an alkoxy group content of less than 0.5%, an amine hydrogen equivalent weight of 500 g/mole amine nitrogen, a phenyl content of 64.6%, and a viscosity of 3750 PCT at 25 ° C

ASR2 amino-functional polyoxyxylene resin comprising NH ₂ (CH ₂ ) ₃ (CH ₃ )SiO _2/2 D unit, phenyloxane T unit, diphenyloxane D unit, trimethyl a decyloxy M unit and a dimethylmethoxyoxy D unit having an alkoxy group content of 4%, an amine hydrogen equivalent of 890 g/moleamine nitrogen, a phenyl content of 70.0%, and a 5,000 PCT at 25 ° C Viscosity

ASR3 amino-functional polyoxyalkylene resin comprising NH ₂ (CH ₂ ) ₃ (CH ₃ )SiO _2/2 D unit, phenyloxane T unit and trimethyldecyloxy M unit, which has 2000 ° drag at 25 ° C

Talc Powder Talc from Imifabi for sale with HTP Ultra 5 talc

ZB US Borax Zinc Borate 500

MC MC 25 melamine cyanurate

All compositions were prepared by Albis Plastics. A masterbatch containing 70% PA-6 and 30% glass fiber sold under Altech ® PA6 A 2030/109 GF30. The Altech polyamine masterbatch was dried in a desiccant hot blast dryer at 100 ° C for 6 hours. The dried polyamine is physically mixed with the solid additives zinc borate, talc and melamine cyanide (if used). Feeding the solid additive mixed with polyamine to a liquid injection The main inlet of the head of the Brabender co-rotating twin-screw extruder with a screw diameter of D 20 mm and L/D 40, and when the polymer produced grains, began to inject the amino-functional polyoxymethylene resin. The amine functional polyoxyxylene resin was heated at 68 ° C to reduce its viscosity and pumped to the injection head in the extruder by a metal line maintained at 62 ° C. The total throughput of the extruder was 1.6 kg/h. The extruder temperature profile is from 260 ° C to 245 ° C to 240 ° C to 240 ° C to 240 ° C from the tank to the die portion. The screw speed was 180 rpm.

The extruded flame retardant polyamine composition was cooled by a water bath and then granulated. The granulated material was injection molded into a rectangular rod having a size of 135 mm x 12.5 mm x 1.5 mm for UL-94 testing. The polymer particles are dried again prior to injection molding to avoid any degradation due to moisture present in the particles. The sample bars were tested according to the UL-94 vertical burn test as set forth above. The results are shown in Table 2 below.

It can be seen that all of the products of Examples 1 to 18 passed the UL-94 vertical burning test and the rating was V-1.

Comparison example C1

30 wt.% glass filled nylon-6 polyamide was extruded and injection molded into sample bars as described above. The sample rods did not pass the UL-94 vertical burn test, burned to the fixed clip and ignited the dry absorbent surgical cotton located 300 mm below.

Comparative example C2

30 wt.% glass-filled nylon-6 polyamine was blended with talc and extruded using methoxy-terminated dimethyl, methoxyphenyl siloxane sulfonium sesquioxane resin. To form a composition comprising 56% nylon-6, 24% glass fiber, 16% sesquioxanes resin and 4% talc. The composition was granulated and injection molded into a sample stick as described above. The sample rods did not pass the UL-94 vertical burn test, burned to the fixed clip and ignited the dry absorbent surgical cotton located 300 mm below.

A comparison of Comparative Example C2 with the examples of the present invention indicates that the presence of an amine group in the polyfluorene oxide resin is necessary for the effective flame retardancy of the polyamine.

Comparative example C3

30wt.% glass-filled nylon-6 polyamine is blended with talc, melamine cyanide and zinc borate and uses aminopropyltriethoxydecane and diphenylmethylphenylpolyoxyl The resin mixture was extruded to form 47.25% nylon-6, 20.25% glass fiber, 15% aminopropyltriethoxydecane, 7.5% diphenylmethylphenyl polyoxyl resin, 4% talc A composition of 5% melamine cyanurate and 1% zinc borate. The composition was granulated and injection molded into a sample stick as described above. These sample rods did not pass the UL-94 vertical burning test, burned to the fixed clamp and ignited the dry absorption at 300 mm below. Surgical cotton.

A comparison of Comparative Example C3 with an example of the present invention (e.g., Examples 9, 17, and 18) indicates that the presence of an amine group in the polyanthracene resin is necessary for the effective flame retardancy of the polydecylamine, and the amine polyfluorene oxide and the phenyl group. The mixture of polyoxyxylene resins cannot be effectively used as a flame retardant for polyamine.

Claims (19)

A halogen-free flame-retardant thermoplastic polymer composition comprising a thermoplastic organic polymer, characterized in that the composition contains an amino-functional polyoxyl resin as a flame retardant. The halogen-free flame-retardant thermoplastic polymer composition of claim 1, wherein the composition contains from 10% by weight to 50% by weight, based on the weight of the thermoplastic organic polymer, of the amino-functional polyoxyalkylene resin. A halogen-free flame-retardant thermoplastic polymer composition according to claim 1 or 2, wherein the amino-functional polyoxysiloxane resin contains an aryl group. The halogen-free flame-retardant thermoplastic polymer composition of claim 3, wherein the polyoxyalkylene resin is an amino-functional phenylmethyl polyoxyl resin. A halogen-free flame-retardant thermoplastic polymer composition according to claim 3 or 4, wherein at least 50% by weight of the organic group aryl group bonded to the ruthenium atom of the polyfluorene oxide resin. The halogen-free flame-retardant thermoplastic polymer composition according to any one of claims 1 to 5, wherein the amino-functional polyoxysiloxane resin contains a T unit. The halogen-free flame-retardant thermoplastic polymer composition according to any one of claims 1 to 6, wherein the amine functional polyoxymethylene resin has an amine equivalent of 300 g/moleamine nitrogen to 1000 g/m Auramine nitrogen. The halogen-free flame-retardant thermoplastic polymer composition according to any one of claims 1 to 7, wherein the amino-functional polyoxysiloxane resin is 20% by weight to 40% by weight based on the weight of the thermoplastic organic polymer. presence. The halogen-free flame-retardant thermoplastic polymer composition according to any one of claims 1 to 8, wherein the composition contains 10% by weight to 50% by weight of glass fibers based on the weight of the thermoplastic organic polymer. The halogen-free flame-retardant thermoplastic polymer composition according to any one of claims 1 to 9, wherein the amino-functional polyoxyl resin occupies all of the flame retardant present in the thermoplastic polymer composition. 50% to 100%. The halogen-free flame-retardant thermoplastic polymer composition according to any one of claims 1 to 10, wherein the thermoplastic organic polymer is polyamine. The halogen-free flame-retardant thermoplastic polymer composition according to any one of claims 1 to 10, wherein the thermoplastic organic polymer is a polyester. A halogen-free flame retardant for a thermoplastic organic polymer composition, characterized in that the flame retardant comprises from 5 to 90% by weight of an amino functional polyoxyl resin, from 5 to 30% by weight The auxiliary flame retardant selected from the group consisting of borate, melamine compound and phosphinate and 0 to 45% by weight of mineral powder are based on the weight of all flame retardants. The halogen-free flame retardant of claim 13, wherein the auxiliary flame retardant comprises zinc borate. A halogen-free flame retardant according to claim 13 or 14, wherein the auxiliary flame retardant comprises melamine cyanurate. The halogen-free flame retardant according to any one of claims 13 to 15, wherein the auxiliary flame retardant comprises melamine polyphosphate. The halogen-free flame retardant of any one of claims 13 to 16, wherein the auxiliary flame retardant comprises a metal phosphinate. A use of a flame retardant comprising an amine functional polyoxyxylene resin for improving the flame retardancy of a thermoplastic organic polymer composition. A method of improving the flame retardancy of a thermoplastic organic polymer composition, wherein an amine functional polyoxymethylene resin is incorporated into the thermoplastic organic polymer composition as a flame retardant.