CN109467747B - Synergistic flame retardant combinations for polymer compositions and uses thereof - Google Patents

Synergistic flame retardant combinations for polymer compositions and uses thereof Download PDF

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CN109467747B
CN109467747B CN201810143528.2A CN201810143528A CN109467747B CN 109467747 B CN109467747 B CN 109467747B CN 201810143528 A CN201810143528 A CN 201810143528A CN 109467747 B CN109467747 B CN 109467747B
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CN109467747A (en
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H·鲍尔
S·赫罗尔德
M·西肯
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Abstract

The invention relates to flame retardant combinations comprising, as component A, a phosphinic acid salt of formula (I)
Figure DDA0001578221210000011
Wherein R is1And R2Represents ethyl, M is Al, Fe, TiOpOr Zn, m represents 2 to 3, and p ═ 4-m)/2, as component B a compound selected from: al, Fe, TiO salts of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid and/or dihexylphosphinic acidpA salt or a Zn salt, and-as component C a phosphonate of the formula (II)
Figure DDA0001578221210000012
Wherein R is3Representing ethyl, Met being Al, Fe, TiOqOr Zn, n representing 2 to 3, and q ═ (4-n)/2, -melamine polyphosphate as component D having an average degree of condensation greater than or equal to 20, and-melamine cyanurate as component E. The polymer compositions can be used for producing fibers, films and moldings, in particular for applications in the electrical and electronic fields.

Description

Synergistic flame retardant combinations for polymer compositions and uses thereof
Technical Field
The present invention relates to a novel synergistic combination of flame retardants and polymer compositions comprising said combination and their use.
Background
Flammable plastics must generally be equipped with flame retardants in order to be able to meet the high flame retardancy requirements demanded by plastic processors and partly by legislators. Preferably, also for ecological reasons, non-halogenated flame retardant systems are used, which form only little or no smoke.
In these flame retardants, salts of phosphinic acids (phosphinates) have proven to be particularly effective for thermoplastic polymers (DE 2252258A and DE 2447727A).
Furthermore, synergistic combinations of phosphinic salts with specific nitrogen-containing compounds are known, which are more effective as flame retardants in a series of polymers than the phosphinic salts alone (WO-2002/28953a1 and also DE 19734437 a1 and DE 19737727 a 1).
From US 7,420,007B2 it is known that dialkylphosphinic salts which contain small amounts of selected telomers are suitable as flame retardants for polymers which undergo only very little degradation when the flame retardant is incorporated into a polymer matrix.
Flame retardants must often be incorporated in high doses to ensure adequate fire resistance of plastics according to international standards. Due to their chemical reactivity, which is required for flame-retardant action at high temperatures, flame retardants can impair the processing stability of plastics, especially at higher dosages. Which may lead to enhanced polymer degradation, crosslinking reactions, gas release or discoloration.
High temperature modified X-ray reflection of aluminum salts of phosphinic acids is known from WO 98/03515a 1. The phosphinate is prepared at high temperatures.
Polyamide moulding compounds are known from WO 2014/135256a1, which have significantly improved thermal stability, reduced migration tendency and good electrical and mechanical properties.
Polyamide molding materials with high glow wire resistance are known from DE 102005041966 a1, which contain nitrogen-containing synergists as flame retardants in addition to phosphinates.
However, to date, phosphinate-containing flame retardant combinations have been lacking, which impart all the desired properties to the polymer compositions, such as good electrical values and effective flame retardancy.
Disclosure of Invention
It was therefore an object of the present invention to provide phosphinate-containing flame retardant systems which impart simultaneously all the aforementioned properties, in particular good electrical values (GWFI, GWIT, CTI) and effective flame retardancy which is characterized by as short a time-to-flame (UL-94, time) as possible to the polymers provided with them.
The subject of the present invention is therefore a flame retardant combination comprising
Phosphinic acid salts of the formula (I) as component A
Figure BDA0001578221200000021
Wherein R is1And R2Represents an ethyl group, and represents a linear or branched alkyl group,
m is Al, Fe, TiOpOr a combination of Zn and a metal selected from the group consisting of,
m represents 2 to 3, preferably 2 or 3, and
p＝(4–m)/2，
-as component B a compound selected from: al, Fe, TiO salts of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid and/or dihexylphosphinic acidpA salt or a Zn salt, and
phosphonates of the formula (II) as component C
Figure BDA0001578221200000022
Wherein R is3Represents an ethyl group, and represents a linear or branched alkyl group,
met is Al, Fe, TiOqOr a combination of Zn and a metal selected from the group consisting of,
n represents 2 to 3, preferably 2 or 3, and
q＝(4–n)/2，
-as component D, a melamine polyphosphate having an average degree of condensation greater than or equal to 20, and
melamine cyanurate as component E.
In the flame retardants according to the invention, the proportion of component A is generally from 5 to 85% by weight, preferably from 10 to 60% by weight.
In the flame retardants according to the invention, the proportion of component B is generally from 0.01 to 10% by weight, preferably from 0.1 to 2.5% by weight.
In the flame retardants according to the invention, the proportion of component C is generally from 0.01 to 10% by weight, preferably from 0.1 to 2.5% by weight.
In the flame retardants according to the invention, the proportion of component D is generally from 5 to 50% by weight, preferably from 10 to 30% by weight.
In the flame retardants according to the invention, the proportion of component E is generally from 5 to 50% by weight, preferably from 10 to 30% by weight.
In this case, the percentage values of the fractions of components a to E are based on the total amount of the flame retardant combination.
Preferred are flame retardant combinations, wherein
The proportion of component A is from 5 to 85% by weight,
the proportion of component B is from 0.01 to 10% by weight,
the proportion of component C is from 0.01 to 10% by weight,
the proportion of component D is from 5 to 50% by weight, and
the proportion of component E is from 5 to 50% by weight,
wherein the percentage values are based on the total amount of components A to E.
Particularly preferred are flame retardant combinations, wherein
The proportion of component A is from 10 to 60% by weight,
the proportion of component B is from 0.1 to 2.5% by weight,
the proportion of component C is from 0.1 to 2.5% by weight,
the proportion of component D is from 10 to 30% by weight, and
the proportion of component E is from 10 to 30% by weight.
Preferred salts for use as component A are those in which M ism+Represents Zn2+、Fe3+Or especially Al3+Those of (a).
Preferred salts for component B are zinc salts, iron salts or, in particular, aluminum salts.
Preferred salts of component C are those in which Metn+Represents Zn2+、Fe3+Or especially Al3+Those of (a).
Very particular preference is given to flame retardant combinations in which M and Met denote Al, M and n are 3 and in which the compounds of component B are present as aluminum salts.
The salts of diethylphosphinic acid used according to the invention as component A are known flame retardants for polymer molding materials.
The salts of diethylphosphinic acid having the proportion of phosphinates and phosphonates used according to the invention as components B and C are likewise known flame retardants. The preparation of such a combination of substances is described, for example, in US 7,420,007B 2.
The salts of diethylphosphinic acid of component A used according to the invention may comprise small amounts of salts of component B and of component C, for example up to 10% by weight of component B, preferably from 0.01 to 6% by weight and in particular from 0.2 to 2.5% by weight, and up to 10% by weight of component C, preferably from 0.01 to 6% by weight and in particular from 0.2 to 2.5% by weight, based on the amount of components A, B and C.
The salts of ethylphosphonic acid used according to the invention as component C are likewise known as additives to the diethylphosphinate salts in flame retardants for polymer molding compounds, for example from WO2016/065971A 1.
The use of polyphosphate derivatives of melamine having a degree of condensation of greater than or equal to 20, which are used according to the invention as component D, as flame retardants is also known. Thus, DE 102005016195 a1 discloses stabilized flame retardants comprising 99 to 1% by weight of melamine polyphosphate and 1 to 99% by weight of additives having a reserve alkalinity. It is also disclosed in this document that the flame retardant can be combined with phosphinic acids and/or phosphinates.
Preferred flame retardant combinations according to the invention comprise melamine polyphosphate as component D, having an average degree of condensation of from 20 to 200, in particular from 40 to 150.
A further preferred flame retardant combination according to the invention comprises, as component D, melamine polyphosphate having a decomposition temperature of greater than or equal to 320 ℃, in particular greater than or equal to 360 ℃, and very particularly preferably greater than or equal to 400 ℃.
Preferably, as component D, melamine polyphosphate is used, which is known from WO 2006/027340a1 (corresponding to EP 1789475B 1) and WO 2000/002869a1 (corresponding to EP 1095030B 1).
Preference is given to using melamine polyphosphates having an average degree of condensation of between 20 and 200, in particular between 40 and 150, and a melamine content of from 1.1 to 2.0mol, in particular from 1.2 to 1.8mol, per mole of phosphorus atom.
Preference is likewise given to using melamine polyphosphates having an average degree of condensation (number average) of >20, a decomposition temperature of > 320 ℃, a molar ratio of 1,3, 5-triazine compound to phosphorus of less than 1.1, in particular from 0.8 to 1.0, and a 10% suspension in water having a pH of above 5, preferably from 5.1 to 6.9, at 25 ℃.
The melamine cyanurate used according to the invention as component E is likewise known as a synergist in combination with diethylphosphinate salts in flame retardants for polymer moulding compounds, for example from WO97/39053A 1.
In another preferred embodiment, components A, B, C, D and E are present in particulate form, wherein the average particle size (d) is50) Is 1 to 100 μm.
In another preferred embodiment, the above flame retardant combination comprises as a further component F an inorganic phosphonate.
The use of inorganic phosphonates or also salts of phosphorous acid (phosphites) as flame retardants to be used according to the invention as component F is known. Thus, WO 2012/045414a1 discloses flame retardant combinations which, in addition to the phosphinates, also contain salts of phosphorous acid (═ phosphites).
Preferably, the inorganic phosphonate (component F) corresponds to the general formula (IV) or (V)
[(HO)PO2]2- p/2Katp+(IV)
[(HO)2PO]- p Katp+(V)
Wherein Kat is a p-valent cation, in particular of an alkali metal, of an alkaline earth metal, an ammonium cation and/or a cation of Fe, Zn or, in particular, of Al, including the cations Al (OH) or Al (OH)2And p represents 1,2, 3 or 4.
Preferably, the inorganic phosphonate (component F) is aluminum phosphite [ Al (H)2PO3)3]Next time
Figure BDA0001578221200000051
Aluminum phosphite [ Al ]2(HPO3)3]Basic aluminum phosphites [ Al (OH) (H)2PO3)2*2aq]Aluminum phosphite tetrahydrate [ Al2(HPO3)3*4aq]Aluminum phosphonate, Al7(HPO3)9(OH)6(1, 6-hexanediamine)1.5*12H2O，Al2(HPO3)3*xAl2O3*nH2O wherein x is 2.27-1 and/or Al4H6P16O18。
The inorganic phosphonate (component F) is preferably also an aluminium phosphite salt of the formula (VI), (VII) and/or (VIII)
Al2(HPO3)3x(H2O)q(VI),
Wherein q represents a number of 0 to 4,
Al2.00Mz(HPO3)y(OH)v x(H2O)w(VII),
wherein M represents an alkali metal cation, z represents 0.01 to 1.5 and y represents 2.63 to 3.5 and v represents 0 to 2 and w represents 0 to 4;
Al2.00(HPO3)u(H2PO3)t x(H2O)s(VIII),
wherein u represents 2 to 2.99 and t represents 2 to 0.01 and s represents 0 to 4, and/or
Is aluminum phosphite [ Al (H)2PO3)3]Is given by
Figure BDA0001578221200000061
Aluminum phosphite [ Al ]2(HPO3)3]Basic aluminum phosphite [ Al (OH) (H)2PO3)2*2aq]Is aluminum phosphite tetrahydrate [ Al ]2(HPO3)3*4aq]Being aluminium phosphonate, being Al7(HPO3)9(OH)6(1, 6-hexanediamine)1.5*12H2O is Al2(HPO3)3*xAl2O3*nH2O wherein x is 2.27-1 and/or Al4H6P16O18。
Preferred inorganic phosphonates (component F) are salts which are insoluble or poorly soluble in water.
Particularly preferred inorganic phosphonates are aluminum, calcium and zinc salts.
Particularly preferably, component F is the reaction product of phosphorous acid and an aluminum compound.
Particularly preferred components F are aluminum phosphites having CAS numbers 15099-32-8, 119103-85-4, 220689-59-8, 56287-23-1, 156024-71-4, 71449-76-8 and 15099-32-8.
The preparation of the preferably used aluminum phosphite is carried out by reacting an aluminum source with a phosphorus source and optionally a template in a solvent at 20-200 ℃ during a time interval of up to 4 days. For this purpose, an aluminum source and a phosphorus source are mixed for 1 to 4 hours, heated under hydrothermal conditions or under reflux, filtered, washed and dried, for example at 110 ℃.
Preferred aluminium sources are aluminium isopropoxide, aluminium nitrate, aluminium chloride, aluminium hydroxide (e.g. pseudoboehmite).
Preferred phosphorus sources are phosphorous acid, aluminum (acidic) phosphite, alkali metal salts of phosphorous acid or alkaline earth metal salts of phosphorous acid.
Preferred alkali metal salts of phosphorous acid are disodium phosphite, disodium phosphite hydrate, trisodium phosphite, potassium hydrogenphosphite.
Preferred disodium phosphite hydrates are those from Bruggemann
Figure BDA0001578221200000062
H10。
Preferred templates are 1, 6-hexanediamine, guanidine carbonate or ammonia.
The preferred alkaline earth metal phosphite is calcium phosphite.
The preferred ratio of aluminium to phosphorus to solvent is in this case 1:1:3.7 to 1:2.2:100 mol. The ratio of the aluminum to the template is 1:0 to 1:17 mol. The reaction solution preferably has a pH of 3 to 9. The preferred solvent is water.
Particularly preferably, the same salts of phosphinic acid as phosphorous acid are used in the application, i.e. for example aluminum diethylphosphinate together with aluminum phosphite or zinc diethylphosphinate together with zinc phosphite.
In a preferred embodiment, the above-mentioned flame retardant combination comprises as component F a compound of the formula (III)
Figure BDA0001578221200000071
Wherein Me is Fe and TiOrZn or, in particular, Al,
o represents 2 to 3, preferably 2 or 3, and
r＝(4–o)/2。
the compounds of the formula (III) which are preferably used are those in which Meo+Represents Zn2+、Fe3+Or especially Al3+Those of (a).
Component F is preferably present in an amount of from 0.01 to 10% by weight, in particular in an amount of from 0.1 to 2.5% by weight, based on the total amount of components A to F.
The invention also relates to the use of the flame retardant combination according to the invention for flame-retardant finishing of thermoplastic and thermosetting polymers and to polymer compositions flame-retardant finished with the flame retardant combination.
The thermoplastic and/or thermosetting polymer (hereinafter component G) is hereinafter referred to as polymer composition comprising the flame retardant combination according to the invention and optionally fillers and reinforcing materials and/or other additives, as defined below.
The thermoplastic polymers in which the flame retardant combination according to the invention can be effectively used are amorphous thermoplastic polymers or partially crystalline thermoplastic polymers having a melting point of less than or equal to 290 ℃, preferably less than or equal to 280 ℃ and very particularly preferably less than or equal to 250 ℃. Polymers of this type are described in detail in the literature and are known to the person skilled in the art.
The melting point of the thermoplastic polymers used according to the invention is determined by means of Differential Scanning Calorimetry (DSC) at a heating rate of 10K/sec.
Among the thermoplastic polymers used according to the invention are for example
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybutene-1, polyisoprene or polybutadiene, and also polymers of cycloolefins, for example of cyclopentene or norbornene; in addition to polyethylene which may optionally be crosslinked; such as High Density Polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), Medium Density Polyethylene (MDPE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), branched low density polyethylene (VLDPE).
2. Mixtures of the aforementioned polymers, for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDP) and mixtures of different polyethylene types, for example LDPE/HDPE.
3. Copolymers of monoolefins and diolefins with each other or with another vinyl monomer, for example ethylene-propylene copolymers, Linear Low Density Polyethylene (LLDPE) and mixtures thereof with Low Density Polyethylene (LDPE), propylene-butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers and the like. Furthermore, ethylene-alkyl acrylate copolymers, ethylene-vinyl acetate copolymers and copolymers thereof with carbon monoxide, or ethylene-acrylic acid copolymers and salts thereof (ionomers), and terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene norbornene; furthermore, mixtures of these copolymers with one another and with the polymers mentioned at point 1, for example polypropylene/-ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers, LDPE/ethylene-acrylic acid copolymers, LLDPE/ethylene-vinyl acetate copolymers, LLDPE/ethylene-acrylic acid copolymers, and alternating or statistically structured polyalkylene/carbon monoxide copolymers and mixtures thereof with further polymers, for example polyamides.
4. Polystyrene, poly (p-methylstyrene), poly (. alpha. -methylstyrene).
5. Copolymers of styrene or alpha-methylstyrene with dienes or acrylic derivatives, such as styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and styrene-butadiene-alkyl methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methacrylate; high impact-resistant mixtures of styrene copolymers and another polymer, for example polyacrylates, diene polymers or ethylene-propylene-diene terpolymers; and block copolymers of styrene, such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene/butylene-styrene or styrene-ethylene/propylene-styrene.
6. Graft copolymers of styrene or alpha-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene copolymer or polybutadiene-acrylonitrile copolymer, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or imide on polybutadiene, styrene and imide on polybutadiene; styrene and alkyl acrylate or methacrylate on polybutadiene; styrene and acrylonitrile on ethylene-propylene-diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates; styrene and acrylonitrile on acrylate-butadiene copolymers and mixtures thereof with the polymers mentioned at point 5 are known, for example, as so-called ABS polymers, MBS polymers, ASA polymers or AES polymers.
7. Halogen-containing polymers, such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; and copolymers thereof, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.
8. Polymers derived from alpha, beta-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polymethyl methacrylates, polyacrylamides and polyacrylonitriles impact-modified with butyl acrylate.
9. Copolymers of the monomers mentioned at point 8 with one another or with further unsaturated monomers, for example acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.
10. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine; and copolymers thereof with the olefins mentioned at point 1.
11. Polyacetals such as polyoxymethylene and those polyoxymethylene which contain comonomers such as ethylene oxide; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
12. Polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides.
13. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12; block copolymers of the aforementioned polyamides with: a polyolefin, olefin copolymer, ionomer, or chemically bonded or grafted elastomer; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Furthermore, polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing ("RIM-polyamide systems").
14. Polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.
15. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1, 4-dimethylolcyclohexane terephthalate, and also block polyether esters derived from polyethers having hydroxyl end groups; furthermore, polyesters modified with polycarbonates or MBS.
16. Polycarbonates and polyester carbonates.
17. Polysulfones, polyether sulfones and polyether ketones.
18. Mixtures of the aforementioned polymers (polymer blends), for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6,6 and copolymers.
19. Thermoplastic elastomers (TPE), such as styrene-based block copolymers (styrene-butadiene-block copolymers, styrene-isoprene-styrene-block copolymers, styrene-ethylene-butylene-styrene-block copolymers), block copolymers based on thermoplastic polyester elastomers, ether-based and/or ester-based block copolymers consisting of alternating blocks from diisocyanates and short-chain diols and from diisocyanates and long-chain diols, polyetherimides, copolyamides and/or polyetheramides.
Preferred TPEs are elastomeric blends such as thermoplastic olefins comprising polypropylene block copolymers, polyethylene block copolymers; polypropylene-, ethylene-propylene-rubber, ethylene-octene copolymer, styrene-ethylene-butadiene-styrene, polyolefin-ethylene-propylene-diene, polyolefin-ethylene-vinyl acetate copolymer and/or polyolefin-polyarylene ether.
Preferred TPEs are thermoplastic vulcanizates, such as ethylene-propylene-diene-rubber granules in a polypropylene matrix.
Thermosetting polymers which can be effectively used in the flame retardant combination according to the invention are likewise described in detail in the literature and are known to the person skilled in the art.
Preferably, the thermosetting polymer is an unsaturated polyester resin (UP resin) derived from copolyesters of saturated and unsaturated dicarboxylic acids or their anhydrides with polyhydric alcohols and vinyl compounds as crosslinking agents. UP resins are cured by free radical polymerization initiators (e.g. peroxides) and accelerators.
Preferred unsaturated dicarboxylic acids and dicarboxylic acid derivatives for the preparation of UP resins are maleic anhydride and fumaric acid.
Preferred saturated dicarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid.
Preferred diols are 1, 2-propanediol, ethylene glycol, diethylene glycol and neopentyl glycol, ethoxylated or propoxylated bisphenol A.
The preferred vinyl compound for crosslinking is styrene.
Preferred curing agent systems are peroxides and metal coinitiators, for example hydroperoxides and cobalt octoate and/or benzoyl peroxide and aromatic amines and/or UV light and photosensitizers, for example benzoin ethers.
Preferred hydroperoxides are di-tert-butyl peroxide, tert-butyl peroctoate, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, tert-butyl permaleate, tert-butyl perisobutyrate, benzoyl peroxide, diacetyl peroxide, succinyl peroxide, p-chlorobenzoyl peroxide and dicyclohexyl peroxydicarbonate.
Preferred metal coinitiators are cobalt compounds, manganese compounds, iron compounds, vanadium compounds, nickel compounds or lead compounds.
Preferred aromatic amines are dimethylaniline, dimethyl-p-toluene, diethylaniline and phenyldiethanolamine.
Further preferred thermosetting polymers are epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for example from bisphenol a diglycidyl ether and bisphenol F diglycidyl ether, which are crosslinked by means of customary curing agents and/or accelerators.
Suitable glycidyl compounds are bisphenol-A-diglycidyl ester, bisphenol-F-diglycidyl ester, polyglycidyl esters of phenol-formaldehyde resins and cresol-formaldehyde resins, polyglycidyl esters of phthalic, isophthalic and terephthalic acids and trimellitic acid, N-glycidyl compounds of aromatic amines and heterocyclic nitrogen bases and diglycidyl compounds and polyglycidyl compounds of polyhydric aliphatic alcohols.
Suitable curing agents are aliphatic, cycloaliphatic, aromatic and heterocyclic amines or polyamines, such as ethylenediamine, diethylenetriamine, triethylenetetramine, propane-1, 3-diamine, hexamethylenediamine, aminoethylpiperazine, isophoronediamine, polyamidoamine, diaminodiphenylmethane, diaminodiphenylether, diaminodiphenylsulfone, aniline-formaldehyde resins, 2, 4-trimethylhexane-1, 6-diamine, m-xylylenediamine, bis (4-aminocyclohexyl) methane, 2-bis (4-aminocyclohexyl) propane, 3-aminomethyl-3, 5, 5-trimethylcyclohexylamine (isophoronediamine), polyamidoamines, dicyandiamide and dicyanodiamide, and also polyacids or anhydrides thereof, such as phthalic anhydride, and mixtures thereof, Maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride and phenols, for example phenol-novolac-resins, cresol-novolac-resins, dicyclopentadiene-phenol adduct-resins, phenol aralkyl-resins, cresol aralkyl-resins, naphthol aralkyl-resins, bisphenol modified phenol aralkyl-resins, phenol trimethylolmethane-resins, tetrahydroxyphenylethane-resins, naphthol-novolac-resins, naphthol-phenol-cocondensate-resins, naphthol-cresol-cocondensate-resins, bisphenol modified phenol-resins and aminotriazine modified phenol-resins. The curing agents may be used alone or in combination with each other.
Suitable catalysts or accelerators for crosslinking during the polymerization are tertiary amines, benzyldimethylamine, N-alkylpyridines, imidazole, 1-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, metal salts of organic acids, Lewis acids and ammine salts.
Preferably, the thermosetting polymers are those derived from aldehydes on the one hand and phenols, ureas or melamines on the other hand, such as phenol-formaldehyde resins, urea-formaldehyde resins and melamine-formaldehyde resins.
Also preferably, the thermosetting polymer is an acrylic resin derived from a substituted acrylate, for example from an epoxy acrylate, a urethane acrylate or a polyester acrylate.
Further preferred thermosetting polymers to be used are alkyd, polyester and acrylate resins, which are crosslinked with melamine, urea, isocyanate, isocyanurate, polyisocyanate or epoxide resins.
Further preferably used thermosetting polymers are polyurethanes or polyureas, which are obtained by reaction of polyisocyanates or ureas with polyols or polyamines.
Preferred polyols are ethylene glycol, 1, 2-propylene glycol, bisphenol a, trimethylolpropane, glycerol, pentaerythritol, sorbitol, sugars or alkylene oxide adducts of degraded starch. Polyester polyols can also be used. These can be obtained by polycondensation of polyhydric alcohols, such as ethylene glycol, diethylene glycol, propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, methylpentanediol, 1, 6-hexanediol, trimethylolpropane, glycerol, pentaerythritol, diglycerol, glucose and/or sorbitol, with dibasic acids, such as oxalic acid, malonic acid, succinic acid, tartaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid and/or terephthalic acid.
Suitable polyisocyanates are aromatic, cycloaliphatic or aliphatic polyisocyanates and mixtures thereof having not less than two isocyanate groups. Preferred are aromatic polyisocyanates such as toluene diisocyanate, methylene diphenyl diisocyanate, naphthalene diisocyanate, xylene diisocyanate, tri-4-isocyanatophenyl) methane and polymethylene polyphenylene diisocyanate; alicyclic polyisocyanates such as methylene diphenyl diisocyanate, toluene diisocyanate; aliphatic polyisocyanates and hexamethylene diisocyanate, isophorone diisocyanate, Demeryl diisocyanate (2-heptyl-3, 4-bis (9-isocyanatononyl) -1-pentyl-cyclohexane), 1-methylenebis (4-isocyanatocyclohexane-4)4' -diisocyanato-dicyclohexylmethane-isomer mixture, 1, 4-cyclohexyldiisocyanate,
Figure BDA0001578221200000131
Form (Bayer) and lysine diisocyanate and mixtures thereof.
Suitable polyisocyanates are also modified products, which are obtained by reaction of polyisocyanates with polyols, ureas, carbodiimides and/or biurets.
Preferably, the polymers used according to the invention as component G are thermoplastic polymers, particularly preferably blends or polymer blends of the polystyrene-HI, polyphenylene ether, polyamide, polyester, polycarbonate and ABS (acrylonitrile-butadiene-styrene) or PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) or PPE/HIPS (polyphenylene ether/polystyrene-HI) type. polystyrene-HI is a polystyrene with improved impact toughness.
Particularly preferred thermoplastic polymers for use are polyamides, polyesters and PPE/HIPS blends.
The flame retardant combination used according to the invention stabilizes the polymer (component G) very well against thermal degradation. This is indicated by the change in the specific viscosity of the thermoplastic polymer upon compounding and shaping of the polymer composition according to the invention. The thermal stress generated here causes partial degradation of the polymer chains, which leads to a reduction in the average molecular weight and thus reveals a reduction in the viscosity of the polymer solution.
A typical value for the specific viscosity of polybutylene terephthalate, measured as a 0.5% solution in phenol/dichlorobenzene (1:1) at 25 ℃ according to ISO 1628 using a capillary viscometer, is therefore, for example, about 130cm3(ii) in terms of/g. Typical values for the specific viscosity of the processed polybutylene terephthalate (as determined as given above) after compounding and shaping of the polybutylene terephthalate composition according to the invention are between 110 and 129cm3Varied within the range of/g.
Preferably, for the uses mentioned, the flame retardant components a to E or a to F are used in a total concentration of from 1 to 40% by weight, in particular from 3 to 30% by weight, based on the polymer composition.
In the polymer compositions according to the invention, the proportion of component G is generally from 25 to 95% by weight, preferably from 25 to 75% by weight.
In the polymer compositions according to the invention, the proportion of component A is generally from 1 to 35% by weight, preferably from 5 to 20% by weight.
In the polymer compositions according to the invention, the proportion of component B is generally from 0.01 to 3% by weight, preferably from 0.05 to 1.5% by weight.
In the polymer compositions according to the invention, the proportion of component C is generally from 0.001 to 1% by weight, preferably from 0.01 to 0.6% by weight.
In the polymer compositions according to the invention, the proportion of component D is generally from 1 to 25% by weight, preferably from 4 to 10% by weight.
In the polymer compositions according to the invention, the proportion of component E is generally from 1 to 25% by weight, preferably from 4 to 10% by weight.
In the polymer compositions according to the invention, the proportion of component F is generally from 0 to 10% by weight, preferably from 1 to 8% by weight.
In this case, the percentage values of the fractions of components A to G are based on the total amount of the polymer composition.
Preferred are flame retardant polymer compositions according to the invention having a relative tracking index, measured according to the international electrotechnical commission standard IEC-60112/3, of greater than or equal to 500 volts.
The likewise preferred flame retardant polymer compositions according to the invention achieve the evaluation of V0 according to UL-94, in particular for measurements on moldings having a thickness of from 3.2mm to 0.4 mm.
Further preferred flame retardant polymer compositions according to the invention have a glow wire flammability index according to IEC-60695-2-12 of greater than or equal to 960 ℃, especially measured on moldings having a thickness of from 0.75 to 3 mm.
The polyamides of component G are particularly preferably homopolyamides or copolyamides which are derived from (cyclo) aliphatic or aromatic dicarboxylic acids or their polyamide-forming derivatives, such as salts thereof, and from (cyclo) aliphatic diamines or from (cyclo) aliphatic aminocarboxylic acids or their polyamide-forming derivatives, such as salts thereof.
The polyamides used according to the invention as component A can be prepared in a variety of different ways and synthesized from a variety of structural units and, in the case of specific applications, can be provided as materials having a specifically tailored combination of properties, alone or in combination with processing aids, stabilizers or also polymeric alloy partners, preferably elastomers.
For the preparation of polyamides, numerous routes are known in which, depending on the desired end product, different monomeric building blocks are used, various chain regulators for adjusting the molecular weight sought or also monomers having reactive groups for the later intended aftertreatment.
Industrially relevant processes for preparing polyamides are mostly carried out by polycondensation in the melt. Within this range, hydrolytic polymerization of lactams is also understood as polycondensation.
Preferably, the polyamide to be used as component G is a partially crystalline aliphatic polyamide having a melting point of less than or equal to 290 ℃, preferably less than or equal to 280 ℃. They can be prepared from aliphatic diamines and aliphatic dicarboxylic acids and/or cycloaliphatic lactams having at least 5 ring members or the corresponding amino acids.
As reactants, aliphatic dicarboxylic acids are considered, preferably adipic acid, 2, 4-trimethyladipic acid and 2,4, 4-trimethyladipic acid, azelaic acid and/or sebacic acid, aliphatic diamines, preferably tetramethylenediamine, hexamethylenediamine, 1, 9-nonanediamine, 2, 4-trimethylhexamethylenediamine and 2,4, 4-trimethylhexamethylenediamine, the isomeric diaminodicyclohexylmethanes, diaminodicyclohexylpropanes, bis (aminomethyl) cyclohexanes, aminocarboxylic acids, preferably aminocaproic acid or the corresponding lactams. Including copolyamides composed of a plurality of the above monomers. Caprolactam is particularly preferred, and epsilon-caprolactam is very particularly preferred.
Preferably, the aliphatic homo-or copolyamides used according to the invention are polyamide 12, polyamide 4,6, polyamide 6, polyamides6,9, polyamide 6,10, polyamide 6,12, polyamide 6,66, polyamide 7, polyamide 8, polyamide 9, polyamide 10, polyamide 11 or polyamide 12. These are for example under the trade name DuPont
Figure BDA0001578221200000161
Trade name of BASF corporation
Figure BDA0001578221200000162
Of DSM company
Figure BDA0001578221200000163
K122, DuPont corporation
Figure BDA0001578221200000164
7301; from Bayer corporation
Figure BDA0001578221200000165
B29 and Ems Chemie
Figure BDA0001578221200000166
Are known.
Also particularly suitable are compounds based on PA6, PA6,6 and other aliphatic homo-or copolyamides in which there are 3 to 11 methylene groups for one polyamide group in the polymer chain.
Preferred are flame retardant polyamide compositions wherein as component G one or more polyamides selected from PA6, PA 4,6, PA 12 and/or PA6, 10 are used.
Particularly preferred are flame retardant polyamide compositions wherein polyamide 6,6 or a polymer mixture of polyamide 6,6 and polyamide 6 is used as component G.
Very particular preference is given to flame-retardant polyamide compositions in which component G consists at least 75% by weight of polyamide 6,6 and at most 25% by weight of polyamide 6.
Particularly preferred polyesters of component G are generally (cyclo) aliphatic or aromatic-aliphatic polyesters which are derived from (cyclo) aliphatic and/or aromatic dicarboxylic acids or polyester-forming derivatives thereof, such as dialkyl esters or anhydrides thereof, and from (cyclo) aliphatic and/or araliphatic diols or from (cyclo) aliphatic and/or aromatic hydroxycarboxylic acids or polyester-forming derivatives thereof, such as alkyl esters or anhydrides thereof. The term "(cyclo) aliphatic" includes cycloaliphatic and aliphatic compounds.
The thermoplastic polyesters of component G are preferably selected from polyalkylene esters of aromatic and/or aliphatic dicarboxylic acids or dialkyl esters thereof.
Component G which is preferably used is an aromatic-aliphatic thermoplastic polyester and preferably of the type obtained by reacting an aromatic dicarboxylic acid or a polyester-forming derivative thereof with an aliphatic C2-C10Diols, especially with C2-C4-a diol reaction derived thermoplastic polyester.
Component G which is preferably used according to the invention is polyalkylene terephthalate, and among these polyethylene terephthalate or polybutylene terephthalate are particularly preferred.
The polyalkylene terephthalates preferably contain at least 80 mol%, in particular at least 90 mol%, based on the dicarboxylic acid, of units derived from terephthalic acid.
The polyalkylene terephthalates preferably used according to the invention as component G may contain, in addition to terephthalic acid residues, up to 20 mol% of residues of other aromatic dicarboxylic acids having 8 to 14C atoms or of aliphatic dicarboxylic acids having 4 to 12C atoms, such as residues of phthalic acid, isophthalic acid, naphthalene-2, 6-dicarboxylic acid, 4' -diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid or azelaic acid, cyclohexanediacetic acid or cyclohexanedicarboxylic acid.
The polyalkylene terephthalates preferably used according to the invention as component G may be branched by incorporating relatively small amounts of 3-or 4-membered alcohols or 3-or 4-membered carboxylic acids, which are described, for example, in DE-A-1900270. Examples of preferred crosslinkers are trimesic acid, trimellitic acid, trimethylolethane and trimethylolpropane and pentaerythritol.
Particularly preferred components G are polyalkylene terephthalates which have been prepared solely from terephthalic acid and its reactive derivatives (e.g.its dialkyl esters) and ethylene glycol and/or propylene glycol-1, 3 and/or butanediol-1, 4 (polyethylene terephthalates and polypropylene terephthalates and polybutylene terephthalates) and mixtures of these polyalkylene terephthalates.
Preferred polybutylene terephthalates contain at least 80 mole%, preferably at least 90 mole%, based on the dicarboxylic acid, of terephthalic acid residues and at least 80 mole%, preferably at least 90 mole%, based on the diol component, of butanediol-1, 4 residues.
Furthermore, preferred polybutylene terephthalates may contain, in addition to butanediol-1, 4 residues, up to 20 mol% of further aliphatic diols having 2 to 12C atoms or cycloaliphatic diols having 6 to 21C atoms, such as the following residues: ethylene glycol; 1,3 parts of propylene glycol; 2-ethyl propanediol-1, 3; neopentyl glycol; pentanediol-1, 5; hexanediol-1, 6; cyclohexanedimethanol-1, 4; 2, 4-methylpentanediol-3-yl; 2-methylpentanediol-2, 4; 2,2, 4-trimethylpentanediol-1, 3; 2-ethylhexanediol-1, 3; 2, 2-diethylpropanediol-1, 3; hexanediol-2, 5; 1, 4-bis- (β -hydroxyethoxy) -benzene; 2, 2-bis- (4-hydroxycyclohexyl) -propane; 2, 4-dihydroxy-1, 1,3, 3-tetramethyl-cyclobutane; 2, 2-bis- (3-. beta. -hydroxyethoxyphenyl) -propane and 2, 2-bis- (4-hydroxypropoxyphenyl) -propane.
Polyalkylene terephthalates that are preferably used according to the invention as component G are also copolyesters which are prepared from at least two of the abovementioned acid components and/or from at least two of the abovementioned alcohol components and/or butanediol-1, 4.
The thermoplastic polyesters used according to the invention as component G can also be used in a mixture with other polyesters and/or further polymers.
The polymer composition according to the invention may also comprise further additives as component H. Preferred components H in the sense of the present invention are antioxidants, UV-stabilizers, gamma stabilizers, hydrolysis stabilizers, co-stabilizers for antioxidants, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact modifiers, dyes, pigments, fillers, reinforcing materials and/or further flame retardants which differ from components A, B, C, D, E and F.
In the polymer compositions according to the invention, the proportion of the one or more components H is generally up to 60% by weight, preferably between 10 and 50% by weight, based on the total amount of the polymer composition.
Particularly preferred are polymer compositions according to the invention which comprise fillers and/or especially reinforcing materials, preferably glass fibers. Mixtures of two or more different fillers and/or reinforcing materials may also be used.
Preferred fillers are mineral particulate fillers based on talc, mica, silicates, quartz, titanium dioxide, wollastonite, kaolin, amorphous silica, nanoscale minerals, particularly preferably montmorillonite or nano-boehmite, magnesium carbonate, chalk, feldspar, glass beads and/or barium sulfate. Particularly preferred are mineral particulate fillers based on talc, wollastonite and/or kaolin.
Particularly preferably, acicular mineral fillers are also used. Acicular mineral fillers are understood according to the invention as mineral fillers having a very pronounced acicular character. Acicular wollastonite is preferred. Preferably, the mineral has an aspect ratio of from 2:1 to 35:1, particularly preferably from 3:1 to 19:1, especially preferably from 4:1 to 12: 1. The mean particle size of the acicular mineral fillers used according to the invention as component B is preferably less than 20 μm, particularly preferably less than 15 μm, particularly preferably less than 10 μm, determined using a CILAS particle sizer.
The reinforcing material preferably used according to the invention can be carbon fibers and/or glass fibers.
In a preferred embodiment, the fillers and/or reinforcing materials can be surface-modified, preferably with an adhesion promoter or an adhesion promoter system, particularly preferably based on silanes. In particular, in the case of glass fibers, it is possible to use polymer dispersions, film formers, branching agents (Verzweiger) and/or glass fiber processing aids in addition to silanes.
The glass fibers preferably used according to the invention can be short glass fibers and/or long glass fibers. Chopped fibers may be used as the short glass fibers or the long glass fibers. Short glass fibers may also be used in the form of milled glass fibers. Furthermore, the glass fibers can additionally be used in the form of continuous fibers, for example in the form of rovings, monofilaments, filament yarns or twines, or in the form of a woven web, for example as a glass fabric, as a glass fabric or as a glass mat.
Typical fiber lengths of the short glass fibers before introduction into the polyamide matrix range from 0.05 to 10mm, preferably from 0.1 to 5 mm. After introduction into the polyamide matrix, the length of the glass fibers becomes smaller. Typical fiber lengths of the short glass fibers after incorporation in the polyamide matrix range from 0.01 to 2mm, preferably from 0.02 to 1 mm.
The diameter of the individual fibers can fluctuate within wide ranges. Typical diameters of the individual fibers range from 5 to 20 μm.
The glass fibers may have any cross-sectional shape, such as circular, elliptical, polygonal (n-eckig) or irregular cross-sections. Glass fibers having a cross-section that is either mono-lobal or multi-lobal may be used.
The glass fibers may be used as continuous fibers or as cut or milled glass fibers.
The glass fibers themselves are independent of their cross-sectional area and their length, and can in this case be selected, for example, from E-glass fibers, A-glass fibers, C-glass fibers, D-glass fibers, M-glass fibers, S-glass fibers, R-glass fibers and/or ECR-glass fibers, with E-glass fibers, R-glass fibers, S-glass fibers and ECR-glass fibers being particularly preferred. The glass fibers are preferably provided with a sizing material, which preferably comprises polyurethane as film former and aminosilane as adhesion promoter.
E-glass fibers having the following chemical composition are particularly preferably used: SiO 22 50-56％；Al2O312-16％；CaO 16-25％；MgO≤6％；B2O3 6-13％；F≤0.7％；Na2O0.3-2％；K2O 0.2-0.5％；Fe2O3 0.3％。
The R-glass fibers used with particular preference have the following chemical composition：SiO2 50-65％；Al2O320-30％；CaO 6-16％；MgO 5-20％；Na2O 0.3-0.5％；K2O 0.05-0.2％；Fe2O3 0.2-0.4％；TiO2 0.1-0.3％。
The ECR glass fibers used with particular preference have the following chemical composition: SiO 2257.5-58.5％；Al2O3 17.5-19.0％；CaO 11.5-13.0％；MgO 9.5-11.5。
In the polymer compositions according to the invention, the proportion of fillers and/or reinforcing materials is generally from 1 to 45% by weight, preferably from 20 to 40% by weight.
The further additives H are known per se as additives for polymer compositions and can be used individually or in the form of mixtures or in the form of masterbatches.
The foregoing component A, B, C, D, E, G and optional F and/or H can be processed in various combinations into flame retardant polymer compositions according to the present invention. It is thus possible to mix the components into the polymer melt already at the beginning of the polycondensation or at the end thereof or during the subsequent compounding process. Furthermore, there are processes in which the individual components are added only later. This is especially practiced where pigment masterbatches or additive masterbatches are used. Furthermore, there is the possibility of drum processing the pulverulent components, in particular, onto polymer pellets which may be hot by the drying process.
It is also possible to combine two or more components of the polymer composition according to the invention by mixing before introduction into the polymer matrix. In this case, conventional mixing equipment can be used, in which the components are mixed in a suitable mixer, for example at from 0 to 300 ℃ for from 0.01 to 10 hours.
Pellets may also be prepared from two or more components of the polymer composition according to the invention, which may subsequently be introduced into the polymer matrix.
To this end, two or more components of the polymer composition according to the invention can be processed into pellets with granulation auxiliaries and/or binders in suitable mixers or pan granulators.
The first-produced crude product can be dried in a suitable dryer or tempered to form other particle structures.
The polymer composition according to the invention or two or more components thereof may in one embodiment be prepared by roll compaction.
The polymer composition according to the invention or two or more components thereof may in one embodiment be prepared therefrom: the ingredients are mixed, strand extruded, pelletized (or optionally crushed and classified) and dried (and optionally coated).
The polymer composition according to the invention or two or more components thereof may in one embodiment be prepared by spray granulation.
The flame-retardant polymer molding compositions according to the invention are preferably present in the form of pellets, for example as extrudates or as compounds. The pellets are preferably cylindrical, spherical, pillow-shaped, cubic, oblong, prismatic in shape with a circular, oval or irregular base.
Typical aspect ratios of the pellets are from 1 to 50 to 1, preferably from 1 to 5 to 1.
The pellets preferably have a diameter of from 0.5 to 15mm, particularly preferably from 2 to 3mm, and a length of from 0.5 to 15mm, particularly preferably from 2 to 5 mm.
When using a polymer or a precursor thereof processed into a thermosetting polymer composition, different preparation methods may be used.
The process for preparing a flame-retardant thermoset material is characterized in that a thermoset resin is mixed with a flame retardant combination according to the invention comprising component A, B, C, D, E as defined above and optionally F and optionally with further flame retardants, synergists, stabilizers, additives and fillers or reinforcing materials, and the resulting mixture is wet-pressed (cold-pressed) at elevated pressure, for example at a pressure of 3 to 10 bar and at moderate temperature, for example at a temperature of 20 to 60 ℃.
Another process for preparing a flame-retardant thermoset material is characterized in that a thermoset material is mixed with a flame retardant combination according to the invention comprising component A, B, C, D, E as defined above and optionally F and optionally with further flame retardants, synergists, stabilizers, additives and fillers or reinforcing materials and the resulting mixture is wet-pressed (hot-pressed) at elevated pressure, for example at a pressure of 3 to 10 bar and at elevated temperature, for example at a temperature of 80 to 150 ℃.
The subject of the invention is also moldings produced from the abovementioned flame-retardant polymer compositions comprising components A, B, C, D, E and G and optionally components F and/or H.
The moulded article according to the invention can be of any form. Examples of these are fibers, films or moldings which can be obtained from the flame-retardant polymer molding compositions according to the invention by any shaping process, in particular by injection molding or extrusion.
The preparation of the flame-retardant polymer-molded product according to the present invention may be carried out by any molding method. Examples of this are injection molding, pressing, foam injection molding, internal gas pressure injection molding, blow molding, film casting, calendering, laminating or coating with flame-retardant polyamide molding compounds at higher temperatures.
The molded part is preferably an injection molded part or an extruded part.
The flame-retardant polymer compositions according to the invention are suitable for the production of fibers, films and moldings, in particular for applications in the electrical and electronic fields.
The present invention preferably relates to the use of the flame retardant polymer composition according to the invention in or for the following items: connectors, energized components in power distributors (FI protection), circuit boards, potting material, power plugs, safety switches, lamp housings, LED housings, capacitor housings, coil form and fans, protection contacts, plugs, in/on circuit boards, housings for plugs, cables, flexible printed circuit boards, charger connection lines for mobile phones, engine covers or textile coatings.
The invention likewise preferably relates to the use of the flame-retardant polymer compositions according to the invention for producing moldings in the form of parts for the electrical/electronic sector, in particular for parts of printed circuit boards, housings, films, wires, switches, distributors, relays, resistors, capacitors, coils, lamps, diodes, LEDs, transistors, connectors, regulators, memories and sensors, in the form of large-area parts, in particular housing parts for switch cabinets and in the form of parts of complex design having a critical geometry.
The wall thickness of the moldings according to the invention may typically be up to 10 mm. Particularly suitable are moldings having a wall thickness of less than 1.5mm, more preferably less than 1mm and particularly preferably less than 0.5 mm.
Detailed Description
The following examples illustrate the invention without limiting it.
1. The components used
Flame retardant FM 1 (component a):
aluminium salt of diethylphosphinic acid, preparation analogous to example 1 of DE 19607635A 1
Flame retardant FM 2 (components a and B):
aluminium salt of diethylphosphinic acid, which contains 0.9 mol% of aluminium ethylbutylphosphinate, was prepared analogously to DE 102014001222A 1, example 1
Flame retardant FM 3 (components A, B and C):
aluminium salt of diethylphosphinic acid, containing 0.9 mol% of ethylbutylphosphinic acid aluminium and 0.5 mol% of ethylphosphinic acid aluminium, prepared according to example 3 of US 7,420,007B2
Flame retardant FM 4 (components A, B and C):
aluminium salt of diethylphosphinic acid, containing 2.7 mol% of ethylbutylphosphinic acid aluminium and 0.8 mol% of ethylphosphinic acid aluminium, prepared according to example 4 of US 7,420,007B2
Flame retardant FM 5 (components A, B and C):
aluminium salt of diethylphosphinic acid, containing 0.5 mol% of ethylbutylphosphinic acid aluminium and 0.05 mol% of ethylphosphinic acid aluminium, prepared according to the method of US 7,420,007B2
Flame retardant FM 6 (components A, B and C):
aluminium salt of diethylphosphinic acid, containing 10 mol% of aluminium ethylbutylphosphinate and 5 mol% of aluminium ethylphosphinate, prepared according to the method of US 7,420,007B2
Flame retardant FM 7 (component F):
aluminium salts of phosphonic acids, prepared according to DE 102011120218A 1, example 1
Flame retardant FM 8 (component D):
melamine polyphosphate, prepared according to the examples of WO 2000/002869A1
Flame retardant FM 9 (not according to the invention):
melamine polyphosphate having an average degree of condensation of 18, prepared analogously to WO 2000/002869A1
Flame retardant FM 10 (component E):
the preparation method of the melamine cyanurate comprises the steps of melamine cyanurate,
Figure BDA0001578221200000231
MC(BASF)
commercial polymer (component G):
polyamide 6,6(PA 6, 6-GV; melting range: 255-:
Figure BDA0001578221200000232
A27(BASF)
polyamide 6 (melting range: 217 ℃ C.):
Figure BDA0001578221200000233
B29(Lanxess)
polyamide 6T/6,6 (melting range: 310-320 ℃):
Figure BDA0001578221200000234
HAT plus 1000(Evonik)
polybutylene terephthalate (PBT):
Figure BDA0001578221200000235
4500(BASF)
glass fibers (component H):
glass fiber PPG HP3610, 10 μm diameter, 4.5mm length (PPG company, NL)
2. Preparation, processing and testing of flame-retardant thermoplastic moulding materials
2.1 Polyamide moulding materials
The flame retardant components are mixed in the proportions given in the table and fed to PA6,6 at a temperature of from 260 to 310 ℃ or to PA6 at a temperature of from 250 to 275 ℃ or to PA 6T/6,6 at a temperature of from 310 to 330 ℃ via the side feed opening of a twin-screw extruder (model: Leistritz ZSE 27/44D). Glass fibers are added through the second side feed holes. The homogenized polymer strand was drawn off, cooled in a water bath and subsequently pelletized.
After sufficient drying, the moulding compositions were processed on an injection moulding machine (model: Arburg 320℃ Allrounder) at a batch temperature of 250 to 320 ℃ to give test pieces and tested for fire resistance by means of the UL-94 test (Underwriter Laboratories) and classified. In addition to the classification, the afterflame time is also given.
The relative tracking index of the moulded article is determined according to the international electrotechnical commission standard IEC-60112/3.
The glow wire flammability index (GWIT index) is determined according to the standard IEC-60695-2-12.
Unless otherwise stated, all tests of each series were performed under the same conditions (such as temperature program, screw geometry and injection molding parameters) for comparability.
2.2 polyester moulding Compounds
The procedure is carried out, for example, in the case of polyamide molding compounds. The incorporation of the flame retardant component into the polymer was carried out only in a twin-screw extruder at temperatures of 240 ℃ and 280 ℃.
The dried molding materials were processed to give test pieces on an injection molding machine at a material temperature of 260 to 280 ℃.
Examples 1-5 and comparative examples V1-V12, using PA6,6
The results of the tests with the PA6,6 molding compound are set forth in the examples cited in the table below. All amounts are given in% by weight and are based on the polyamide molding compound including the flame retardant and the reinforcing material.
Figure BDA0001578221200000251
The polyamide compositions according to the invention of examples 1 to 5 are moulding compositions which achieve a fire rating of UL-94V-0 at 0.4mm, with a CTI of 600 volts, a GWFI of 960 ℃ and a GWIT of 800 ℃ or 825 ℃. The addition of component F in example 5 leads to a further improvement in the flame retardancy exhibited by the shortened afterflame times and to an improvement in the GWIT value.
The omission of component E in comparative examples V1 to V5 leads to a reduction in the flame retardancy exhibited by the extended afterflame times. GWFI values correspond to the values for moldings comprising component E. The CTI values are reduced compared with moldings comprising component E.
The omission of components B and C in comparative examples V6 and V7, in addition to the extended after-flame time, also leads to reduced CTI values and GWIT values compared with examples 1 to 4.
The omission of component C in comparative examples V8 and V9, in addition to the extended after-flame time, also leads to equally reduced CTI and GWIT values compared with examples 1 to 4.
The replacement of component D in comparative example V10 by a component with a lower degree of condensation caused the polyamide strand to foam during production and no measurement could be made.
The omission of component D in comparative example V11 results in reduced GWIT and GWFI values in addition to the deterioration of the fire rating compared to example 2.
In comparative example V12, an improvement in the fire protection rating is achieved compared with example V11 by increasing the concentration of components A, B and C. However the polyamide composition still shows a lower fire rating and reduced GWIT and GWFI values compared to example 2.
Examples 6 to 10 and comparative examples V13 to V23, using PA6, 6/PA6
The results of the tests with the PA6/PA6,6 molding compound are set forth in the examples cited in the table below. All amounts are given in% by weight and are based on the polyamide molding compound including the flame retardant and the reinforcing material.
Figure BDA0001578221200000271
The polyamide compositions according to the invention of examples 7 to 10 are moulding compositions which achieve a fire rating of UL-94V-0 at 0.4mm, with a CTI of 600 volts, a GWFI of 960 ℃ and a GWIT of 800 ℃ or 825 ℃. The addition of component F in example 10 leads to a further improvement in the flame retardancy exhibited by the shortened afterflame times and to an improvement in the GWIT value.
The omission of component E in comparative examples V13 to V16 leads to a reduction in the flame retardancy exhibited by the extended afterflame times. GWFI values correspond to the values for moldings comprising component E. The CTI values are reduced compared with moldings comprising component E.
The omission of components B and C in comparative examples V17 and V18, in addition to the extended after-flame time, also leads to reduced CTI values and GWIT values in comparison with examples 7 to 10.
The omission of component C in comparative examples V19 and V20, in addition to the extended afterflame time, also leads to equally reduced CTI and GWIT values compared with examples 7 to 10.
The replacement of component D in comparative example V21 by a component with a lower degree of condensation caused the polyamide strand to foam during production and no measurement could be made.
The omission of component D in comparative example V22 results in reduced GWIT and GWFI values in addition to the deterioration of the fire rating compared to example 8.
In comparative example V23, an improvement in the fire protection rating is achieved compared with example V22 by increasing the concentration of components A, B and C. However the polyamide composition still shows a lower fire rating and reduced GWIT and GWFI values compared to example 8.
Examples 13 to 17 and comparative examples V14 to V35, using PBT
The results of the tests with PBT moulding compounds are listed in the examples cited in the table below. All amounts are given in% by weight and are based on the polyester molding compound including flame retardant and reinforcing material.
Figure BDA0001578221200000291
The polyester compositions according to the invention of examples 11 to 15 are moulding compositions which achieve a fire rating of UL-94V-0 at 0.4mm, with a CTI of 600 volts, a GWFI of 960 ℃ and a GWFI of 775 ℃ or 800 ℃. The addition of component F in example 15 results in a further improvement in the flame retardancy exhibited by the shortened afterflame times and in an improvement in the GWIT value.
The omission of component E in comparative examples V24 to V28 leads to a reduction in the flame retardancy exhibited by the extended afterflame times. GWFI values correspond to the values for moldings comprising component E. The CTI values are reduced compared with moldings comprising component E.
The omission of components B and C in comparative examples V29 and V30, in addition to the extended after-flame time, also leads to reduced CTI values and GWIT values in comparison with examples 11 to 14.
The omission of component C in comparative examples V31 and V32, in addition to the extended after-flame time, also leads to equally reduced CTI and GWIT values compared with examples 11 to 14.
The replacement of component D in comparative example V33 with a component having a lower degree of condensation resulted in polyester strands which were foamed on preparation and could not be measured.
The omission of component D in comparative example V34 results in reduced GWIT and GWFI values in addition to the deterioration of the fire rating compared to example 12.
In comparative example V35, an improvement in the fire protection rating is achieved compared with example V34 by increasing the concentration of components A, B and C. However, the polyester composition still showed lower fire rating and reduced GWIT and GWFI values compared to example 12.
Comparative examples V36-V41, using PA 6T/6,6
The results of the tests with the PA 6T/6,6 molding compound are set forth in the examples cited in the table below. All amounts are given in% by weight and are based on the polyamide molding compound including the flame retardant and the reinforcing material.
Table 4: PA 6T/6,6 GF 30 test results (n.b. ═ not determined)
Example numbering V36 V37 V38 V39 V40 V41
G: polyamide 6T/6,6 48 48 48 48 48 48
H: glass fiber HP3610 30 30 30 30 30 30
A+B+C：FM 1 12 - - - - -
A+B+C：FM 2 - 12 - - 10 -
A+B+C：FM 3 - - 12 - - -
A+B+C：FM 4 - - - 12 - -
A：FM 5 - - - - - 12
A+B：FM 6 - - - - - -
F：FM 7 - - - - 2 -
D：FM 8 5 10 5 10 5 10
E：FM 10 5 - 5 - 5 -
UL 940.4 mm/time [ sec ]] n.b. n.b. n.b. n.b. n.b. n.b.
GWFI[℃] n.b. n.b. n.b. n.b. n.b. n.b.
GWIT[℃] n.b. n.b. n.b. n.b. n.b. n.b.
Colour(s) n.b. n.b. n.b. n.b. n.b. n.b.
CTI [ volt ]] n.b. n.b. n.b. n.b. n.b. n.b.
No test pieces could be produced from the PA molding compounds of comparative examples V36 to V41, since the PA molding compounds proved to be impossible to process. The polyamide strands foamed during the production and no test pieces suitable for the measurement could be produced.

Claims (30)

1. A flame retardant combination comprising
Phosphinic acid salts of the formula (I) as component A
Figure FDA0002940025030000011
Wherein R is1And R2Represents an ethyl group, and represents a linear or branched alkyl group,
m is Al, and M is a nitrogen atom,
m represents 2 to 3, and
-as component B a compound selected from: al salts of ethylbutylphosphinic acid, of dibutylphosphinic acid, of ethylhexylphosphinic acid, of butylhexylphosphinic acid and/or of dihexylphosphinic acid,
phosphonates of the formula (II) as component C
Figure FDA0002940025030000012
Wherein R is3Represents an ethyl group, and represents a linear or branched alkyl group,
the Met is Al and the content of the alloy is,
n represents 2 to 3, and
-as component D, a melamine polyphosphate having an average degree of condensation greater than or equal to 20, and
melamine cyanurate as component E.
2. The flame retardant combination of claim 1, wherein M and Met represent Al, M and n are 3, and component B is an aluminum salt.
3. The flame retardant combination according to claim 1 or 2,
the proportion of component A is from 5 to 85% by weight,
the proportion of component B is from 0.01 to 10% by weight,
the proportion of component C is from 0.01 to 10% by weight,
the proportion of component D is from 5 to 50% by weight, and
the proportion of component E is from 5 to 50% by weight,
wherein the percentage values are based on the total amount of components A to E.
4. The flame retardant combination of claim 3,
the proportion of component A is from 10 to 60% by weight,
the proportion of component B is from 0.1 to 2.5% by weight,
the proportion of component C is from 0.1 to 2.5% by weight,
the proportion of component D is from 10 to 30% by weight, and
the proportion of component E is from 10 to 30% by weight.
5. The flame retardant combination of claim 1 or 2, wherein components A, B, C and D are present in particulate form, wherein the average particle size D of these components50Is 1 to 100 μm.
6. The flame retardant combination according to claim 1 or 2, characterized in that the average degree of condensation of the melamine polyphosphate is from 20 to 200.
7. The flame retardant combination according to claim 1 or 2, characterized in that the melamine polyphosphate has a decomposition temperature of greater than or equal to 320 ℃.
8. The flame retardant combination according to claim 1 or 2, characterized in that the combination comprises an inorganic phosphonate as further component F.
9. The flame retardant combination of claim 8, wherein the inorganic phosphonate is a compound of formula (III)
Figure FDA0002940025030000031
Wherein Me is Fe and TiOrZn, or Al, in the presence of a metal,
o represents 2 to 3, and
r ═ 4-o)/2, where
The compounds of the formula (III) are present in an amount of from 0.01 to 10% by weight, based on the total amount of components A to F.
10. A combination according to claim 9, wherein o represents 2 or 3.
11. The flame retardant combination of claim 9, wherein the compound of formula (III) is present in an amount of 0.1 to 2.5 wt.%, based on the total amount of components a to F.
12. A polymer composition comprising a thermoplastic and/or thermoset polymer as component G and the flame retardant combination comprising components A, B, C, D and E according to any one of claims 1 to 7 or component A, B, C, D, E and optionally F according to any one of claims 8-11, wherein the thermoplastic polymer is an amorphous thermoplastic polymer or a partially crystalline thermoplastic polymer having a melting point of less than or equal to 290 ℃.
13. The polymer composition according to claim 12, characterized in that it has a relative tracking index, measured according to the international electrotechnical commission standard IEC-60112/3, of greater than or equal to 500 volts.
14. The polymer composition according to claim 12 or 13, wherein the composition achieves the evaluation V0 according to UL-94.
15. Polymer composition according to claim 14, characterized in that it is measured on moulded parts with a thickness of 3.2mm to 0.4 mm.
16. The polymer composition according to claim 12 or 13, wherein the composition has a glow wire flammability index according to IEC-60695-2-12 of greater than or equal to 960 ℃.
17. A polymer composition according to claim 16, characterized in that it is measured on a molded part with a thickness of 0.75-3 mm.
18. Polymer composition according to claim 12 or 13, characterized in that component G is a partially crystalline aliphatic polyamide having a melting point of less than or equal to 290 ℃.
19. Polymer composition according to claim 18, characterized in that component G is a partially crystalline aliphatic polyamide having a melting point of less than or equal to 280 ℃.
20. A polymer composition according to claim 19, wherein component G is selected from compounds based on PA6, PA6,6 and other aliphatic homo-or copolyamides having 3 to 11 methylene groups on the polyamide group in the polymer chain.
21. A polymer composition according to claim 20, wherein component G is selected from PA6, PA 4,6, PA 12 and PA6, 10.
22. A polymer composition according to claim 12 or 13, characterized in that component G is a polyalkylene terephthalate.
23. A polymer composition according to claim 22, wherein component G is polyethylene terephthalate or polybutylene terephthalate.
24. The polymer composition according to claim 12 or 13,
the proportion of component A is from 1 to 35% by weight,
the proportion of component B is from 0.01 to 3% by weight,
the proportion of component C is from 0.001 to 1% by weight,
the proportion of component D is from 1 to 25% by weight,
the proportion of component E is from 1 to 25% by weight,
the proportion of component F is from 0 to 10% by weight, and
the proportion of component G is from 25 to 95% by weight,
wherein the percentage values are based on the total amount of the polymer composition.
25. The polymer composition of claim 24,
the proportion of component A is from 5 to 20% by weight,
the proportion of component B is from 0.05 to 1.5% by weight,
the proportion of component C is from 0.01 to 0.6% by weight,
the proportion of component D is from 4 to 10% by weight,
the proportion of component E is from 4 to 10% by weight,
the proportion of component F is from 1 to 8% by weight, and
the proportion of component G is from 25 to 75% by weight.
26. The polymer composition according to claim 12 or 13, characterized in that the composition comprises as component H a further additive, wherein the further additive is selected from the group consisting of antioxidants, UV-stabilizers, gamma stabilizers, hydrolysis stabilizers, co-stabilizers of antioxidants, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact modifiers, dyes, pigments, fillers and/or further flame retardants different from components A, B, C, D, E and F.
27. A polymer composition according to claim 26, wherein the filler is a reinforcing material.
28. The polymer composition according to claim 12 or 13, characterized in that the composition comprises glass fibers.
29. Use of the polymer composition according to any of claims 12 to 28 for the preparation of fibers, films and moldings.
30. Use of the polymer composition according to claim 29 for applications in the electrical and electronic fields.
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