Patent Application
20240327612
Flame retardant thermoplastic polyurethane composition with improved mechanical properties
This invention is directed to a flame retardant thermoplastic polyurethane composition with improved mechanical properties.
Thermoplastic polyurethane compositions are well known and may be adapted for multiple requirements in different fields, e.g. cable applications where flame retardancy in combination with high flexibility is required see e.g. EP 3 110 882 A1 or EP 0 617 079 A2.
There is a broad range of applications, where classically very stiff polymers such as polyamide, are used. These applications are e.g. coverage in mobile devices such as e.g. cars, trains, plains, which are exposed to extreme temperature changes. In these devices the polymers very often in direct contact with metals and preferably should have comparable expansion to avoid dirt and water uptake between these two materials, to prevent inter alia the metal from corrosion. At the same time the coverage should fulfill additional requirements, such as flame retardance, damping and decoupling of vibration and should be able to bear high loads without cracking. The requirements are increasing in view of electromobility in very different applications.
Now therefore, there is a continuous need for the development of new materials which better and better fulfills all these requirements.
Surprisingly a thermoplastic polyurethane composition according to claim 1 fulfills these requirements.
A fist aspect of this invention and embodiment 1 is a composition comprising thermoplastic polyurethane, a flame retardant and a filler, wherein the thermoplastic polyurethane is the reaction product of a diisocyanate, a polyetherpolyol and a chain extender and the polyetherpolyol comprises a polytetrahydrofuran with a number average molecular weight of the polyetherpolyol between 1.3×103 g/Mol and 1.8×103 g/Mol, more preferred the number average molecular weight is 1.4×103 or 1.7×103 g/Mol.
The term composition indicates that the composition does not comprise the thermoplastic polyurethane only, but may comprise other polymers as well, same as additives and/or auxiliaries. In a preferred embodiment, the composition comprises the thermoplastic polyurethane as described below, without any further polymer.
The term “comprise” indicates that the respective component is used at least partly as respective compound. In preferred embodiments the term “comprise” has the meaning of “is”.
Preferably the thermoplastic polyurethane, is prepared by reacting a diisocyanate, with a polyetherpolyol, preferably having two hydroxyl groups reactive with isocyanate and, if desired, a chain extender preferably having a molecular weight of from 0.05×103 g/mol to 0.499×103 g/mol, if desired in the presence of a catalyst and/or an auxiliary and/or an additive.
The components diisocyanate, polyol, and chain extender are also addressed individually or together as structural components. The structural components including the catalyst and/or the auxiliary and/or the additive are also called input materials.
In order to adjust the hardness and melt index of the thermoplastic polyurethane (TPU), the molar ratios of the quantities of the structural components isocyanate, polyol and chain extender, and, if used, water, can be varied, whereby the hardness and melt viscosity increase with increasing content of chain extender, while the melt flow index decreases.
In a preferred embodiment 2 according to the precedent embodiment or one of its preferred embodiments, the Shore Hardness of the composition is 65 Shore D to 100 Shore D, preferably measured according to DIN ISO 7619-1: 2016, more preferably 65 Shore D to 85 Shore D. Preferably the thermoplastic polyurethane comprised in the composition has a Shore hardness of 75 Shore A to 85 Shore D, preferably measured according to DIN ISO 7619-1, 2016, preferably 95 Shore A to 75 Shore D, more preferably 60 Shore D to Shore 70 Shore D.
In order to prepare the thermoplastic polyurethane, the structural components diisocyanate, polyol, and chain extender are reacted, in preferred embodiments in the presence of a catalyst, and optionally auxiliaries and/or additives) in such quantities that the equivalent ratio of NCO groups of the diisocyanates to the sum of the hydroxyl groups of the polyol and the chain extender is 0.95:1 to 1.10:1, preferably 0.98:1 to 1.08:1 and in particular approximately 1.0:1 to 1.05:1.
In a preferred embodiment 3 comprising all features of one of the precedent embodiments or one of their preferred embodiments the thermoplastic polyurethane of the composition is a granulate and the thermoplastic polyurethane in this granulate preferably has a weight-average molecular weight between 0.03×106 g/mol and 0.15×106 g/mol, preferably between 0.04×106 g/mol and 0.12×106 g/mol, more preferably between 0.05×106 g/mol and 0.08×106 g/mol. In a preferred embodiment 4 according to one of the precedent embodiments or one of their preferred embodiments, the composition is in the form of a granulate and the thermoplastic polyurethane preferably has a weight-average molecular weight of between 0.03×101 g/mol and 0.12×106 g/mol, preferably between 0.04×106 g/mol and 0.12×106 g/mol, more preferably between 0.04×106 g/mol and 0.07×106 g/mol. The weight average molecular weight preferably is measured according to DIN 55672-2 2016-03.
The number average molecular weight Mn in the context of this invention is determined by gel permeation chromatography, preferably it is determined according to DIN 55672-1 2016-03.
Isocyanate
The diisocyanate preferably is selected from the group consisting of aliphatic, cycloaliphatic, araliphatic and aromatic isocyanates, or is a mixture thereof. The isocyanate more preferably is selected from the group consisting of tri-, tetra-, penta-, hexa-, hepta- and/or octamethylene diisocyanate, 2-methyl-pentamethylene 1,5-diisocyanate, 2-ethyl-butylene-1,4-diisocyanate, 1,5-pentamethylene diisocyanate (PDI), 1,4-butylene-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1,4-bis(isocyanatome-thyl)cyclohexane and/or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 2,4-paraphenylene diisocyanate (PPDI), 2,4-tetramethylene xylene diisocyanate (TMXDI), 4,4′-, 2,4′- and 2,2′-dicyclohexylmethane diisocyanate (H12 MDI), 1,6-hexamethylene diisocyanate (HDI),1,4-cyclohexane diisocyanate, 1-methyl-2,4- and/or −2,6-cyclohexane diisocyanate, 2,2′-, 2,4′- and/or 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), 2,4- and/or 2,6-tolu-ene diisocyanate (TDI), 3,3′-dimethyl-diphenyl diisocyanate, 1,2-diphenylethane diisocyanate and/or phenylene diisocyanate, or is a mixture thereof.
Aliphatic isocyanates are preferred when stability against electromagnetic waves e.g. light is of importance, whereas aromatic polyisocyanate is preferred when high mechanical strength of the thermoplastic polyurethane is required. A further advantage of aliphatic isocyanate is that it may be produced bio-based.
A very preferred aromatic isocyanate is 2,2′-, 2,4′- and/or 4,4′-diphenylmethane diisocyanate (MDI), especially preferred is 4,4′-diphenylmethane diisocyanate.
A very preferred aliphatic isocyanate is 1,5-pentamethylene diisocyanate. This has the additional advantage, that it can be produced bio based.
In a preferred embodiment 5 according to one of the precedent embodiments or one of its preferred embodiments the isocyanate is 2,2′-, 2,4′- and/or 4,4′-diphenylmethane diisocyanate (MDI), more preferred is 4,4′-diphenylmethane diisocyanate.
Polyol
The polyol has on statistical average at least 1.8 and at most 3.0 Zerewitinoff-active hydrogen atoms. This number is also referred to as the functionality of the polyol and indicates the quantity of the isocyanate-reactive groups of the molecule calculated theoretically down to one molecule from a quantity of substance. The functionality is preferred between 1.8 and 2.6, further preferred between 1.9 and 2.2 and especially preferred 2. Polyols are preferably those having a molecular weight between 0.500 g/mol and 8×103 g/mol, preferably between 0.7×103 g/mol and 6.0×103 g/mol, in particular between 0.8×103 g/mol and 4.0×103 g/mol.
The polyol preferably is essentially linear, more preferably linear, and is a single polyol or a mixture of different substances, in which case the mixture meets the above requirement. These long-chain compounds are used with a content of 1 mol % equivalent to 80 mol % equivalent, based on the isocyanate group content of the polyisocyanate. The polyol has the hydroxyl group as the reactive group with isocyanate The polyol is also referred to as polyhydroxy polyol.
In an embodiment 6 comprising all features of one of the precedent embodiments or one of their preferred embodiments the polyol is a diol.
In an embodiment 7 comprising all features of one of the precedent embodiments or one of their preferred embodiments the polyol is a polyether diol.
Preferred polyether polyols are polyether diols, further preferred those based on ethylene oxide, propylene oxide or butylene oxide, tetrahydrofuran, or a mixture thereof.
A preferred polyether polyol comprises beneath polytetramethylene ether glycol, PTMEG) respectively polytetrahydrofuran (PTHF), a polypropylene oxide glycol or a polybutylene oxide glycol, or a mixture thereof. Particularly preferred the polyether is polytetrahydrofuran (PTHF). PTHF is commercially available under the tradename PolyTHF®.
Polyetherpolyol has the advantage that it is more stable against.
According to the invention a chain extender is used in the synthesis of the thermoplastic polyurethane. The chain extender preferably is an aliphatic, araliphatic, aromatic and/or cycloaliphatic compound, or a mixture thereof, preferably with a molecular weight of 0.05×103 g/mol to 0.499×103 g/mol, preferably with 2 groups reactive with isocyanate, which are also referred to as functional groups. The chain extender is either a single chain extender or a mixture of at least two chain extenders.
The chain extender is preferably a difunctional compound, preferred examples being diamines or alkanediols having 2 to 10 carbon atoms in the alkylene radical, or a mixture thereof. In a preferred embodiment comprising all features of one of the precedent embodiments or one of their preferred embodiments, the chain extender is selected from the group consisting of 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentane-diol, 1,6-hexanediol, diethylene glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, okta-, nona- and/or deca alkylene glycole dipropylene glycol, 1,4-cyclohexanediol, 1,4-dimethanol cyclohexane, neopentylglycol and hydroquinone bis(beta-hydroxyethyl) ether (HQEE), or is a mixture thereof.
Preferably the chain extender is selected from the group consisting of 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol, di-, tri-, tetra-, penta-, hexa-, hepta-, okta-, nona- and/or deca alkylene glycole, preferably respective oligo- and/or polypropylene glycole, or is a mixture thereof.
In a preferred embodiment 8 comprising all features of one of the precedent embodiments or one of their preferred embodiments, the chain extender comprises, preferably is 1,3-propanediol, 1,4-butanediol or 1,6-hexanediol, or a mixture thereof.
A preferred mixture of chain extenders is 1,4-butanediol and either 1,6-hexandiol or 1,3-propanediol, wherein, the mol % of 1,4-butanediol preferably is between 80 mol-% and 98 mol-% referring to the whole amount of chain extender being 100 mol-%.
Another preferred mixture of chain extenders is 1,3-propanediol and either 1,6-hexandiol or 1,4-butanediol, wherein, the mol-% of 1,3-propaneiol preferably is between 80 mol-% and 98 mol-% referring to the whole amount of chain extender being 100 mol-%.
In one preferred embodiment 9 according to one of the precedent embodiments or one of their preferred embodiments the chain extender comprises, preferably is 1,4-budanediol.
Catalyst In one preferred embodiment 10 according to one of the precedent embodiments or one of their preferred embodiments the composition comprises a catalyst.
The catalyst in particular accelerates the reaction between the NCO groups of the isocyanate and the hydroxyl groups of the polyol, and the chain extender. Preferably the catalyst is selected from the group consisting of tertiary amine and organic metal compound, or is a mixture thereof.
A preferred tertiary amine is selected from the group consisting of triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N,N′-dimethyl-piperazine, 2-(dimethylaminoethoxy)ethanol, diazabicyclo[2.2.octane] or is a mixture thereof.
A preferred organic metal compound is selected from the group consisting of titanic ester, iron compound, tin compound, and bismuth salt, or is a mixture thereof. A preferred iron compound is iron(III) acetylacetonate. A preferred tin compound is selected from the group consisting of tin diacetate, tin dioctoate, tin dilaurate and dialkyl tin salts of aliphatic carboxylic acids, preferably tin dioctoate, or is a mixture thereof. A preferred titanic ester is tetrabutyl orthotitanate. In preferred bismuth salts, the bismuth is present in the oxidation states 2 or 3, in particular 3, with preference being given to salts of carboxylic acids, preferably carboxylic acids having from 6 to 14 carbon atoms, particularly preferably from 8 to 12 carbon atoms. A very preferred bismuth salt is bismuth(III) neodecanoate, bismuth 2-ethylhexanoate, or bismuth octanoate, or is a mixture thereof.
The catalyst is preferably used in an amount of from 0.0001 to 0.1 part by weight per 100 parts by weight of the polyol. Preference is given to using a tin catalyst, in particular tin dioctoate.
A very preferred catalyst is SDO (tin (II) 2-ethylhexanoate), preferably used in quantities of 0.35-0.4 parts per weight, referring to the composition.
In another preferred embodiment 11 according to one of the precedent embodiments or one of their preferred embodiments, the composition further comprises a polyamide or a co-polyamide.
A preferred polyamide or co-polyamide is derived from a diamine and a dicarboxylic acid or from an amino-carboxylic acids or from the corresponding lactams. Preferred polyamides have a melting point below 230° C. Examples for preferred polyamides are polyamide 5,10, polyamide 12, polyamide-11, Other preferred examples are amorph polyamides, preferably the amorph polyamides are the reaction product of 15 weight-% to 84 weight-% of at least one lactam, and 16 weight-% to 85 weight-% of a mixture of monomers (M) comprising the monomer (B) with 16 weight-% to 85 weight-% of a mixture (M) of monomer comprising the two monomers B1 and B2, wherein the monomer B1 is at least one dimeric acid with 32 to 40 carbon atoms (B1) and monomer B2 is at least one diamine 4 to 12 carbon atoms and the weight percentages of the components (A) and (B) are each based on the sum me of the weight percent-ages of the components (A) and (B).
The most preferred amorph polyamide is polyamide 6/6,36.
The lactam is either a single lactam or is a mixture of at least two lactams, preferred is one lactam. Preferred lactams have 4 to 12 carbon atoms, a very preferred lactam is epsilon-Caprolactam.
Other preferred copolymers are block copolymers of the abovementioned polyamides with poly-olefins, with olefin copolymers, with ionomers or with chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol, or are mixtures thereof. Other preferred examples are EPDM- or ABS-modified polyamides or co-polyamides; and also polyamides condensed during processing (“IM polyamide systems”).
In preferred embodiments 12 according to one pf the precedent embodiments or one of their preferred embodiments the weight ratio of the thermoplastic polyurethane and the polyamide respectively the co-polyamide in the composition is from 1 to 100 to 100 to 1, preferably 90 to 10, 80 to 20, 70 to 30 or 60 to 40, or any other ration in between.
In a preferred embodiment 13 according to one of the precedent embodiments or one of their preferred embodiments, an auxiliary or additive (e) is added to the structural components, meaning is comprised in the composition. Preferred examples include surface-active substances, fillers, flame retardants, nucleating agents, oxidation stabilizers, lubricating and demolding aids, dyes, antistatic agents, and pigments, if necessary, stabilizers, preferably against hydrolysis, light, heat or discoloration, inorganic and/or organic fillers, reinforcing agents, and/or plasticizers.
Stabilizers in the sense of this invention are additives which protect a plastic or a plastic composition against harmful environmental influences. Preferred examples are primary and secondary antioxidants, sterically hindered phenols, hindered amine light stabilizers, UV absorbers, hydrolysis inhibitors, quenchers, and flame retardants. Examples of commercial stabilizers are given in Plastics Additives Handbook, 5th Edition, H. Zweifel, ed., Hanser Publishers, Munich, 2001 ([1]), p.98-S136.
Preferably the UV absorber has a number average molecular weight greater than 0.3×103 g/Mol, in particular greater than 0.39×103 g/Mol. Furthermore, the preferred UV absorber has a molecular weight not exceeding 5×103 g/Mol.
The UV absorber is preferably selected from the group consisting of cinnamates, oxanilides, benzophenones, and benzotriazole, or is a mixture thereof, particularly suitable as UV absorbers is benzotriazole. Examples of particularly suitable UV-absorbers are Tinuvin® 213, Tinuvin® 234, Tinuvin® 312, Tinuvin® 571, Tinuvin® 384 and Eversorb® 82.
Preferably the UV absorbers is added in quantities of 0.01 wt. % to 5 wt. % based on the total weight of the composition, preferably 0.1 wt. % to 2.0 wt. %, in particular 0.2 wt. % to 0.5 wt. %.
Often a UV stabilization based on an antioxidant and a UV absorber as described above is not sufficient to guarantee a good stability of the composition against the harmful influence of UV rays. In this case, in addition to the antioxidant and/or the UV absorber, or as single stabilizer, a hindered-amine light stabilizer (HALS) is be added to the composition.
Examples of commercially available HALS stabilizers can be found in Plastics Additive Handbook, 5th edition, H. Zweifel, Hanser Publishers, Munich, 2001, pp. 123-136.
Particularly preferred hindered amine light stabilizers are bis-(1,2,2,6,6-penta, methylpiperidyl) sebacat (Tinuvin® 765, Ciba Spezialitatenchemie AG) and the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid (Tinuvin® 622). In particular, the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidines and succinic acid (Tinuvin® 622) is preferred, if the titanium content of the finished product is less than 150 ppm, preferably less than 50 ppm, in particular less than 10 ppm, based on the components used.
HALS compounds are preferably used in a concentration of from 0.01 wt. % to 5 wt. %, particularly preferably from 0.1 wt. % to 1 wt. %, in particular from 0.15 wt. % to 0.3 wt. %, based on the total weight of the composition.
A particularly preferred UV stabilization contains a mixture of a phenolic stabilizer, a benzotriazole and a HALS compound in the preferred amounts described above.
Further information on the above-mentioned auxiliaries and additives can be found in the technical literature, e.g. Plastics Additives Handbook, 5th edition, H. Zweifel, ed., Hanser Publishers, Munich, 2001.
e-Modulus
In a preferred embodiment 14 comprising all features of one of the precedent embodiments or one of their preferred embodiments, the e-modulus of the composition determined according to DIN EN ISO 527 is between 0.05×103 MPa and 15×103 MPa, preferably between 0.1×103 MPa and 10×103 MPa, preferably between 0.3×103 MPa and 8×10 3 MPa, more preferably between 1×103 and 5×103 MPa, even more preferably between 2×103 MPa and 3×103 MPa.
In a preferred embodiment 15 comprising all features of one of the precedent embodiments or on of their preferred embodiments, the Shore hardness of the composition is between 65 D and 100 D, more preferred between 65 D and 85 D. The Shore D hardness preferably is measured according to DIN ISO 7619-1, 2016.
The composition further comprises a filler. The chemical nature and the shape of the filler can vary within wide ranges if there is sufficient compatibility with the thermoplastic polyurethane. Preferred fillers are, for example, glass fibers, glass beads, glass microspheres, carbon fibers, aramid fibers, potassium titanate fibers, fibers of liquid-crystalline polymers, organic fibrous fillers or inorganic reinforcing materials. Preferred organic fibrous fillers are, for example, cellulose fibers, hemp fibers, sisal or kenaf. Preferred inorganic reinforcing materials are for example ceramic fillers, or mineral fillers. Preferred ceramic fillers are aluminum and boron nitride.
Preferred mineral fillers are asbestos, talc, wollastonite, microvit, silicate, chalk, calcined kaoline, mica and quartz flour, or a mixture thereof.
Fibrous fillers are preferred in the context of the present invention. The fibers preferably have a diameter of 3 μm to 30 μm, preferably 6 μm to 20 μm and especially preferably 8 μm to 15 μm. The fiber length in the compound preferably is 0.02 mm to 1 mm, preferably 0.18 mm to 0.5 mm and especially preferred 0.2 mm to 0.4 mm.
The fibrous fillers preferably are surface pretreated with a silane compound for better compatibility with the thermoplastic polyurethane.
Inorganic fibrous fillers are preferred. When inorganic fibrous fillers are used, a greater reinforcing effect is found as well as a higher heat resistance.
Particularly preferred inorganic fillers for the present invention are glass fibers, glass beads or glass microspheres.
In a further preferred embodiment 16 comprising all features of one pf the precedent embodiments, or one of their preferred embodiments, the filler comprises glass, preferably glass fiber, glass bead, or glass microspheres, more preferred glass fiber. The glass preferably is coated. If the glass is a fiber, the thickness of the fiber preferably is from 3 μm to 30 μm, especially 8 μm to 15 μm, and with a maximum of the fiber length distribution in the range of 0.03 mm to about 15 mm, especially 1 mm to 10 mm. By injection moulding the fibers get a preferred orientation in the composition, also referred to as flow direction.
The diameter of the glass beads can vary in wide ranges. Suitable and preferred are for example beads having an average diameter in the range of from 5 μm to 100 μm, preferably in the range of from 10 μm to 75 μm, more preferable in the range of from 20 μm to 50 μm, more preferred in a range of from 20 μm to 40 μm.
The diameter of the hollow glass microspheres can vary in wide ranges. Suitable are for example microspheres having an average diameter in the range of from 5 μm to 100 μm, preferably in the range of from 10 μm to 75 μm, more preferable in the range of from 20 μm to 50 μm, for example in a range of from 20 μm to 40 μm.
Thus, according to a further embodiment 17, the present invention also relates to a composition as disclosed above or one of their preferred embodiments, wherein the microspheres have an average diameter in the range of from 5 μm to 100 μm. The composition comprises one filler, or more fillers.
In a preferred embodiment 18 according to one of the precedent embodiments or one of their preferred embodiments, the proportion of the filler in the composition is in the range from 5 weight-% to 40 weight-% based on the total composition, preferably 10 weight-% to 30 weight-%, more preferably 10 weight-% to 20 weight-%, more preferred 12 weight-% to 18 weight-%. based on the weight of the total composition.
The composition of the present invention also comprises at least one flame retardant. In a preferred embodiment 19 comprising all features of one of the precedent embodiments or one of their preferred embodiments, the filler and the flame retardant comprise 10 weight-% to 60 weight % of the composition, being 100 weight-%, preferably 30 weight-% to 55 weight-%.
In a preferred embodiment 20 comprising all features of one of the precedent embodiments or one of their preferred embodiments, the composition comprises the flame retardant with 3 weight-% to 35 weight-%, preferably 20 weight-% to 35 weight-%, referring to the whole composition, being 100 weight-%, in one preferred embodiment 22 weight % to 28 weight-%.
In a preferred embodiment 21 according to one of the precedent embodiments or one of their preferred embodiments the flame retardant is halogen free.
In a further preferred embodiment 22 according to one of the precedent embodiments or one of their preferred embodiments, the flame retardant comprises nitrogen or phosphor.
A preferred kind of nitrogen containing flame retardant is a nitrogen based compound selected from the group consisting of benzoguanamine, tris(hydroxyethyl)isocyanurate, isocyanurate, allantoin, glycoluril, melamine, melamine cyanurate, melamine polyphosphate, dimelamine phosphate, melamine pyrophosphate, melamine borate, ammonium polyphosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate, condensation product of melamine selected from the group consisting of melem, melam, melon and higher condensed compounds and other reaction products of melamine with phosphoric acid, melamine derivatives, or a mixture thereof.
More preferably in an embodiment 23 according to one of the precedent embodiments or one of their preferred embodiments, the flame retardant is selected from the group consisting of melamine, melamine cyanurate, melamine polyphosphate, di-melamine phosphate, melamine pyrophosphate, melamine borate, ammonium polyphosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate, and melamine derivatives, or is a mixture thereof.
In another preferred embodiment 24 according to any of the precedent embodiments, or one of their preferred embodiments the composition comprises a flame retardant selected from the group consisting of melamine, melamine cyanurate, melamine borate, melamine polyphosphate and melamine derivatives, or a mixture thereof. In a very preferred embodiment, the flame retardant is melamine cyanurate. Melamine cyanurate is also referred to as 1,3,5-triazine-2,4,6(1H,3H,5H)-trione.
In a preferred embodiment 25 according to any of the precedent embodiments, or one of their preferred embodiments the composition comprises ammonium polyphosphate as a flame retardant. Preferred such flame retardants are ammonium orthophosphates, preferably NH4H2PO4, (NH4)2HPO4 or mixtures of these, are ammonium diphosphates, preferably NH4H3P2O7, (NH4)2H2P2O7, (NH4)3HP2O7, (NH4)4P2O7, or mixtures of these, ammonium polyphosphates, in particular but not exclusively those found in J. Am. Chem. Soc. 91, 62 (1969).
The ammonium phosphate component may or may not be coated. Suitable coated ammonium polyphosphates are for example described in U.S. Pat. Nos. 4,347,334, 4,467,056, 4,514,328, and 4,639,331.
In a preferred embodiment 26 according to any of the precedent embodiments, or one of their preferred embodiments, the flame retardant comprises an inorganic flame retardant, more preferably selected from the group consisting of magnesium oxide, magnesium hydroxide, silicon oxide, aluminum hydroxide and aluminum oxide, or a mixture thereof.
In a preferred embodiment 27 according to any of the precedent embodiments, or one of their preferred embodiments, the flame retardant comprises a phosphorus containing flame retardant. The phosphorus containing flame retardant preferably is liquid at 21° C.
Preference is given to derivatives of the phosphoric acid, derivatives of the phosphonic acid, or derivatives of the phosphinic acid, or a mixture of two or more of said derivatives.
It is preferable that the derivatives of the phosphoric acid, phosphonic acid, or phosphinic acid involve salts with an organic or an inorganic cation or involve organic esters. In one preferred embodiment, the organic ester involves an alkyl ester, and in another preferred embodiment it involves an aryl ester. It is particularly preferable that all the hydroxy groups of the corresponding phosphorus-containing acid have been esterified.
Organic phosphate esters are preferred, particularly the tri-esters of phosphoric acid, more preferred are the trialkyl phosphates. Other preferred embodiments are triaryl phosphates, especially preferred is tri-phenyl phosphate.
In another preferred embodiment, the phosphoric esters has the general formula (I)
where R denotes substituted alkyl, cycloalkyl, or phenyl groups, and n is a real number in the range of ≥1 to ≤15.
If R in the general formula (I) is an alkyl moiety, alkyl moieties that preferably are used are those having from 1 to 8 carbon atoms. The cyclohexyl moiety may be mentioned as a preferred example of the cycloalkyl groups. It is preferable to use phosphoric esters of the general formula (I) in which R denotes a phenyl or alkyl-substituted phenyl. Preferably, n is 1, or in the range of ≥3 to ≤6. Very preferred phosphoric esters of the general formula (1) are bis(diphenyl) 1,3-phenylenephosphate, bis(dixylenyl) 1,3-phenylenephosphate, and also the corresponding oligo-meric products, preferably with an average degree of oligomerization of n in the range of ≥3 to ≤6.
A very preferred phosphoric ester is resorcinol, more preferred resorcinol bis(diphenyl phosphate) (RDP). RDP preferably is present in oligomers.
In a preferred embodiment 28 according to one of the precedent embodiments or one of their preferred embodiments the phosphorus containing flame retardant comprises bisphenol A bis(diphenyl phosphate) (BDP) or diphenyl cresyl phosphate (DPC), or a mixture thereof. BPD usually takes the form of an oligomer.
The organic phosphates involve salts with an organic or inorganic cation or involve the esters of phosphonic acid. Preferred esters of phosphonic acid are the diesters of alkyl- or phenyl-phosphonic acids.
Other preferred phosphorus contain flame retardants are phosphinic esters having the general formula R1R2(P═O)OR3, wherein the moieties R3 is an organic group, and R1, R2 are organic groups or are hydrogen.
In one preferred embodiment the moieties R1, R2 and R3 are identical, in another preferred embodiment R1, R2 and R3 are different from each other.
R3 preferably is an aliphatic group, or an aromatic group, and preferably has from 1 to 20 carbon atoms, more preferably from 1 to 10. In a preferred embodiment the aliphatic group has from 1 to 3 carbon atoms, more preferably R3 is an ethyl radical or is a methyl radical.
The moieties R1, R2 preferably have from 1 to 20 carbon atoms, more preferably from 1 to 10, It is preferred, that at least one of the moieties R1, R2, or R3 is an aliphatic and it is more preferred that this aliphatic group has from 1 to 3 carbon atoms. It is more preferable that all of the moieties R1, R2 and R3 are aliphatic groups with the preferences as outlined above.
In one preferred embodiment R1 and R2 are ethyl radical, more preferably in this embodiment R3 is also an ethyl radical or is a methyl radical. In one preferred embodiment, R1, R2 and R3 are simultaneously either an ethyl radical or a methyl radical. In another preferred embodiment R1 and R2 are a hydrogen atom.
Preference is also given to metal (M+)phosphinate, which is the metal (M+) salt of phosphinic acid with the general formula M+ [R1R2(P═O)O]−. The groups R1 and R2 are either hydrogen, are aliphatic or aromatic, and preferably have from 1 to 20 carbon atoms, preferably from 1 to 10, more preferably from 1 to 3. It is preferable that at least one of the moieties is aliphatic, and it is more preferable that both moieties are aliphatic, and it is very particularly preferable that R1 and R2 are methyl radical or ethyl radical, most preferred ethyl radical.
In a preferred embodiment 29 according to one of the precedent embodiments or one of their preferred embodiments, the flame retardant comprises phosphinate.
In a preferred embodiment 30 according to one of the precedent embodiments or one of their preferred embodiments, the flame retardant comprises a phosphinate selected from the group consisting of aluminum phosphinate, calcium phosphinate, titanium phosphinate, zinc phosphinate, or is a mixture thereof. More preferred is aluminum phosphinate.
In other preferred embodiments the R1 or R2 group is a hydrogen atom. and the other group is an organic group with preference as given before. In yet another embodiment the R1 and R2 group is a hydrogen atom.
Preferred salts of phosphinic acids are aluminum, calcium, titanium, or zinc salts, or are mixtures thereof. More preferred is aluminum.
The more preferred metal phosphinate is selected from zinc diethyl phosphinate, aluminum diethyl phosphinate, aluminum phosphinate, calcium phosphinate, or is a mixture thereof. More preferred the metal phosphinate is aluminum diethyl phosphinate or is aluminum phosphinate, or a mixture thereof. Most preferred the metal phosphinate is aluminum diethyl phosphinate.
Preferably, the flame retardant is selected from derivatives of phosphinic acid, salts with organic or inorganic cation or organic esters. Organic esters are derivatives of phosphinic acid in which at least one oxygen atom directly bound to the phosphorus is esterified with an organic residue. In one preferred form the organic ester is an alkyl ester, in another preferred form an aryl ester. All hydroxy groups of phosphinic acid are particularly preferentially esterified.
Furthermore, piperazine pyrophosphate and polypiperazine pyrophosphate are used as flame retardant in preferred embodiments. The use of piperazine based flame retardants is in principle known from the state of the art, for example as disclosed in WO 2012/174712 A1.
The flame retardant is used in the form of single substance or in mixtures of several substances of either the same kind of flame retardants or different kind of flame retardants in the composition.
In a preferred embodiment 31 according to one of the precedent embodiments or one of their preferred embodiments, the flame retardant comprises a first phosphorus-containing flame retardant (F1) selected from the group consisting of melamine polyphosphate and a further phosphorus-containing flame retardant (F2) selected from the group consisting of derivatives of phosphinic acid as preference is given above, most preferred is aluminum phosphinate.
In a preferred embodiment 32 according to one of the precedent embodiments or one of their preferred embodiments, the flame retardant comprises melamine cyanurate [=(1,3,5-triazine-2,4,6(1H,3H,5H)-trione] and phosphoric acid ester, more preferred the phosphoric ester resorcinol bis(diphenylphosphate).
The melamine polyphosphate preferably has a phosphorus content between 7 weight % to 20 weight %, preferably in the range from 10 weight % to 17 weight %, more preferably in the range from 12 weight % to 14 weight %.
A further embodiment preferably employs a melamine polyphosphate which in aqueous solution has a pH in the range from 3 to 7, more preferably in the range from 3.5 to 6.5, particularly preferably in the range from 4 to 6, in each case determined according to ISO 976.
It is preferable when the flame retardant (F2) selected from derivatives of phosphinic acid with preferences as given above.
In a preferred embodiment 33 the water uptake of the composition according to one of the precedent embodiments or one of their preferred embodiments is less than 1% preferably measured according to DIN EN ISO 62, Method 1, and is less than 0.5% measured according to DIN EN ISO 62, Method 4.
In a preferred embodiment 34 according to one of the precedent embodiments or one of their preferred embodiments the composition has a glass temperature Tg of less than −30° C., preferably less than −40° C. and most preferably less than −50° C. The glass temperature Tg preferably is measured with dynamic mechanic analysis, with a torsion frequency of 1 Hz, loss modulus (Max G″) [° C.] (DIN 53 019 DIN EN 3219).
In a preferred embodiment 35 the composition according to one of the precedent embodiments, or one of their preferred embodiments passes the UL 94V vertical 2 mm test (ANSI, UL94, Tests for Flammability of Plastic Materials for Parts in Devices and Appliances” Sixth Edition, Dated Mar. 28, 2013. In a preferred embodiment the composition fulfills the UL 24 classification V0, V1, V2, more preferred the classification V0 or V1, and especially preferred the classification V0.
In a preferred embodiment 36 according to any of the precedent embodiments, or one of their preferred embodiments the shrinkage of the composition is less than 0,8%, preferably less than 0.6%, more preferably less than 0,4%, preferably determined according to ISO 294-4 CLTE (Coefficient of Linear Thermal Expansion) In a preferred embodiment 37 according to any of the precedent embodiments, or one of their preferred embodiments the CLTE (Coefficient of Linear Thermal Expansion) of the composition lengthwise to the direction of the fiber is less than 150 10−6 1/K, preferably less than 80 10−6 1/K, preferably determined according to ISO 11359-2. In further preferred embodiments 38 according to any of the precedent embodiments, or one of their preferred embodiments the CLTE of the composition, if applicable perpendicular to the fiber direction, is less than 150 10−6 1/K, preferably less than 80 10−6 1/K, preferably determined according to ISO 11359-2.
In a preferred embodiment 39 the composition according to one of the precedent embodiments or one of its preferred embodiments is in the form of a pellet or a powder. The pellet or powder in a preferred embodiment is a compact material. In another preferred embodiment the pellet or powder is expanded material, also referred to as foamed beads or foamed powder.
Another aspect of this invention and embodiment 40 is the use of the composition according to one of the precedent embodiments or one of their preferred embodiments for covering metal. The metal preferably is selected from the group consisting of aluminum, steel, iron, copper, lead, tin, zinc, or is an alloy thereof. In a preferred embodiment an alloy of lead and tin is a cover of the metal, preferably of the copper.
The advantage of covering these metals with the composition is their comparable expansion coefficient.
In a preferred embodiment 41 the metal is a device, preferably an electronic device. A preferred electronic device is an insulated conductor or an electronic connector, preferably a press-fit connector or a wire-to-board connector, or a busbar, more preferably a busbar.
Busbars are generally uninsulated, self-supporting and have sufficient distance from one another to ensure electrical insulation. The form of a busbar depends on its specific requirements such as installation space, number of plugs to be adapted voltage or flow of electricity. The material of the busbar conductive part of the busbar is metal, preferably selected from the group consisting of aluminum, steel, iron, copper, lead, tin, zinc, or is an alloy thereof. An alloy of lead and tin is a preferred cover of the metal, preferably of the copper.
In a preferred embodiment 42 the device according to embodiment 41 or one of its preferred embodiments fulfills the climate change test as outlined in detail in the Examples.
Another aspect and preferred embodiment 43 is the production of a device according to embodiment 41. In a preferred embodiment the electronic device is a busbar. In a preferred embodiment for producing this busbar the conductive part of the busbar is placed in a mould. In more preferred embodiments means for fixing the busbar are positioned together with the conductive part in the mould. In a next step the mould is filled with the composition, preferably by an injection moulding process, and after curing of the composition the device is demoulded. Preferable the granules of the composition are dried before being used for injection moulding, preferably for at least 3 hours, preferably at about 90° C.
Table 1 below shows the recipes of the thermoplastic polyurethanes (TPU) A to F in which the parts by weight (PW) of the individual starting materials are given. The polyols were placed in a container at 80° C. and mixed with the components according to the amounts given in table 1 under vigorous stirring in a reaction vessel. The isocyanate was added at last component. As soon as a reaction temperature of 110° C. was reached or the foam-level exceeded 80% of the reaction vessel volume. The reaction mixture was poured on a heating plate (120° C.) forming a slab. The slab was cured on the plate for 10 min, afterwards tempered at 80° C. for 15 h, crushed and extruded into granules.
The compositions 1-12 with mixtures of ingredients as indicated in tables 2 and 3 were produced in a ZE 40, which is a twin-screw extruder from Berstorff with a screw length of 35 D, di-vided into 10 barrel sections (compounding). Granules were obtained using an underwater pelletizing unit of Gala. The granules of the thermoplastic polyurethane used were dried at 90° C. for 3 hours before the compounding.
The mechanical properties of the thermoplastic polyurethanes (TPU)derived from recipes A to F and of the composition 1-12 were determined on injection molded test bodies. The TPU respectively compositions were dried at 90° C. for 3 hours before injection molding to test bodies and measured with the following specifications. The properties of the test bodies for the individual materials are summarized in tables 1, 2 and 3.
The thermoplastic polyurethanes, derived from the recipes D, E, and F achieved the desired stiffness of above 300 MPa,
Shrinkage is very high for all materials, none of the thermoplastic polyurethanes, derived from the recipes A to F achieved the required flame retardancy.
Compositions 4-6 had the required stiffness and flame resistance, and also passed the climate change test.
However, compositions 4-6 have a large shrinkage.
In addition to flame retardancy and low shrinkage, all formulations have a sufficiently high modulus of elasticity.
The climate change test is only passed by the formulations according to the invention with recipes comprising Poly THF mixtures with an average molecular weight of 1.4×103 g/mol and 1.7×103 g/mol
For producing the test busbars as outlined in more detail in the Figures, the thermoplastic polyurethane (TPU) respectively the compositions were dried at 90° C. for 3 hours. A standard injection molding machine was used. The molds were mounted on a rail system. A busbar made from copper having a coating made from lead/tin alloy was placed in the injection mold. The injection molding of the thermoplastic polyurethane respectively the composition took place with the following parameters:
| Number | Date | Country | Kind |
|---|---|---|---|
| 21189418.3 | Aug 2021 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/071044 | 7/27/2022 | WO |
