EP3679091A1 - Flammhemmende polyesterzusammensetzungen und deren verwendung - Google Patents
Flammhemmende polyesterzusammensetzungen und deren verwendungInfo
- Publication number
- EP3679091A1 EP3679091A1 EP18762080.2A EP18762080A EP3679091A1 EP 3679091 A1 EP3679091 A1 EP 3679091A1 EP 18762080 A EP18762080 A EP 18762080A EP 3679091 A1 EP3679091 A1 EP 3679091A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- polyester compositions
- compositions according
- flame retardant
- retardant polyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/5205—Salts of P-acids with N-bases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Definitions
- the present invention relates to flame-retardant polyester compositions and molded articles made therefrom.
- Flammable plastics generally have to be equipped with flame retardants in order to achieve the high flame retardance requirements demanded by plastics processors and in part by the legislation. Preference - also for ecological reasons - are non-halogenated
- dialkylphosphinates containing a small amount of selected telomers are suitable as flame retardants for polymers, the polymer only undergoing very little degradation upon incorporation of the flame retardant into the polymer matrix.
- Flame retardants must often be added in high dosages in order to ensure a sufficient flame retardancy of the plastic according to international standards. Due to their chemical reactivity, which for the
- Flame retardant especially at higher dosages, the processing stability of plastics. It can lead to increased polymer degradation, crosslinking reactions, outgassing or discoloration.
- thermoplastic polyester polycarbonate
- phosphinic acid salt phosphinic acid salt
- thermoplastic polyester thermoplastic polyester, phosphinic acid salt, phosphazene and
- reaction products of the melamine with phosphoric acid and / or condensed phosphoric acids or other nitrogen-containing flame retardants and optionally reinforcing agents and / or further additives are optionally reinforcing agents and / or further additives.
- Polyester compositions that achieve all the required properties at the same time, in particular good electrical values and effective
- polyester compositions based on phosphinate-containing flame retardant systems which have all the aforementioned properties at the same time and which in particular have good electrical values (CTI, GWFI) and effective flame retardancy, characterized by shortest possible afterburning times (UL94).
- the invention provides flame-retardant polyester compositions containing
- thermoplastic polyester as component A
- Phosphinic acid salt of the formula (I) as component C Phosphinic acid salt of the formula (I) as component C.
- Ri and R2 are ethyl
- M is Al, Fe, TiOp or Zn
- n 2 to 3, preferably 2 or 3
- R 3 is ethyl
- Met is Al, Fe, TiOq or Zn
- n 2 to 3, preferably 2 or 3
- Compositions contains the following reflexes:
- the X-ray spectra are taken with an X-ray powder diffractometer
- the sample is irradiated with Cu-K-alpha radiation and the step time is 1 second.
- Preferred polyester compositions according to the invention are those whose X-ray powder diffractogram contains the following reflections: in the angular range 2 ⁇ of 9.099 ° to 9.442 °, of 18.619 ° to 18.984 ° and of 26.268 ° to 26.679 °.
- the proportion of component A is usually 25 to 95% by weight, preferably 25 to 75% by weight.
- the proportion of component A is usually 25 to 95% by weight, preferably 25 to 75% by weight.
- Component B usually 1 to 45 wt .-%, preferably 20 to 40 wt .-%.
- the proportion of Component C is usually 1 to 35% by weight, preferably 5 to 20% by weight.
- the proportion of component D is usually 0.01 to 3% by weight, preferably 0.05 to
- the proportion of component E is usually 0.001 to 1% by weight, preferably 0.01 to
- the percentages for the proportions of components A to E are based on the total amount of the polyester composition.
- the proportion of component E is 0.001 to 1% by weight
- the proportion of component A is from 25 to 75% by weight
- the proportion of component B is from 20 to 40% by weight
- the proportion of component E is from 0.01 to 0.6% by weight
- Preferred salts of component C are those in which M m + Zn 2+ , Fe 3+ or in particular Al 3+ .
- Preferably used salts of component D are zinc, iron or
- Preferably used salts of component E are those in which Met n + Zn 2+ , Fe 3+ or in particular Al 3+ .
- the above-described flame retardant polyester compositions contain inorganic phosphonate as further component F. The use of the inventively used as component F.
- the inorganic phosphonate (component F) preferably corresponds to the general formulas (IV) or (V)
- Kat is a p-valent cation, in particular a cation of an alkali metal, 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) 2, and p is 1, 2, 3 or 4.
- the inorganic phosphonate (component F) is preferably also aluminum phosphites of the formulas (VI), (VII) and / or (VIII)
- Aluminum phosphite tetrahydrate [Al 2 (HPO 3) 3 * 4aq] to give aluminum phosphonate, Al 7 (HPO 3 ) 9 (OH) 6 (1,6-hexanediamine) i, 5 * 12H 2 O, by ⁇ 2 ( ⁇ 3 ) 3 * ⁇ 2 ⁇ 3 * ⁇ 2 ⁇ with x 2,27 - 1 and / or AUHePieOis.
- Preferred inorganic phosphonates are water-insoluble or sparingly soluble salts.
- Particularly preferred inorganic phosphonates are aluminum, calcium and zinc salts.
- component F is a
- Reaction product of phosphorous acid and an aluminum compound Reaction product of phosphorous acid and an aluminum compound.
- Particularly preferred components F are aluminum phosphites with the
- the preparation of the preferably used aluminum phosphites is carried out by reacting an aluminum source with a phosphorus source and optionally a template in a solvent at 20-200 ° C for a period of up to 4 days.
- the aluminum source and the phosphorus source are mixed for 1 to 4 hours, heated under hydrothermal conditions or at reflux, filtered off, washed and z. B. at 1 10 ° C dried.
- Preferred aluminum sources are aluminum isopropoxide, aluminum nitrate, aluminum chloride, aluminum hydroxide (eg pseudoboehmite).
- Preferred sources of phosphorus are phosphorous acid, (acidic)
- Preferred Alkaliphosphite are disodium phosphite, dinat umphosphithydrat, trisodium phosphite, Kaliumhydrogenphosphit Preferred Dinatriumphosphithydrat is Brüggolen ® H10 Fa. Brüggemann.
- Preferred templates are 1, 6-hexanediamine, guanidine carbonate or ammonia.
- Preferred alkaline earth metal phosphite is calcium phosphite.
- the preferred ratio of aluminum to phosphorus to solvent is 1: 1: 3.7 to 1: 2.2: 100 mol.
- the ratio of aluminum to template is 1: 0 to 1: 17 mol.
- the preferred pH of the reaction solution is 3 to 9.
- Preferred solvent is water.
- the same salt of phosphinic acid as the phosphorous acid is used in the application, so z.
- phosphinic acid aluminum diethylphosphinate together with aluminum phosphite or Zinkdiethylphosphinat together with zinc phosphite.
- the above-described flame retardant polyester compositions contain as component F
- Me is Fe, TiOr, Zn or in particular Al,
- o is 2 to 3, preferably 2 or 3
- Preferred compounds of the formula (III) are those in which Me is O 2 Zn 2+ , Fe 3+ or in particular Al 3+ .
- Component F is preferably in an amount of 0.005 to 10 wt .-%, in particular in an amount of 0.02 to 5 wt .-%, based on the
- the polyester composition according to the invention contains, as component H, a melamine polyphosphate having an average degree of condensation of from 2 to 200, preferably greater than or equal to 20.
- Polyphosphate derivatives of melamine with a degree of condensation greater than or equal to 20 as a flame retardant is known.
- DE 10 2005 016 195 A1 discloses a stabilized flame retardant containing 99 to 1% by weight.
- Phosphinic acid and / or a phosphinic acid salt can be combined.
- Preferred polyester compositions according to the invention contain as component H a melamine polyphosphate whose average
- Condensation degree 20 to 200 in particular from 40 to 150, is.
- the average is
- polyester compositions according to the invention comprise, as component H, a melamine polyphosphate having a decomposition temperature of greater than or equal to 320 ° C, in particular greater than or equal to 360 ° C and most preferably greater than or equal to 400 ° C.
- Melanin polyphosphates which are known from WO 2006/027340 A1 (corresponding to EP 1 789 475 B1) and WO 2000/002869 A1 (corresponding to EP 1 095 030 B1) are preferably used as components.
- Melanninpolyphosphate are preferably used, the average degree of condensation between 20 and 200, in particular between 40 and 150, and the melamine content of 1, 1 to 2.0 mol, in particular 1, 2 to 1, 8 mol per mole of phosphorus atom.
- Melanninpolyphosphate are also preferably used whose mean condensation ridge (number average) is> 20 whose decomposition temperature is greater than 320 ° C., whose molar ratio of 1,3,5-triazine compound to phosphorus is less than 1, 1, in particular 0.8 to 1, Is 0 and the pH of a 10% slurry in water at 25 ° C is 5 or higher, preferably 5.1 to 6.9.
- the proportion of component H is usually 0 and 25 wt .-%, preferably 1 to 25 wt .-%, in particular 2 to 10 wt .-%, based on the total amount of
- melamine polyphosphate as component H, the following are additionally present in the polyester compositions according to the invention
- Reflexes (as X-ray powder diffraction gram) measured: In the angular range 2 ⁇ from 14.765 ° to 15.076 °.
- the polyester composition according to the invention contains, as component I, melamine cyanurate.
- the melamine cyanurate used according to the invention as component I is known as a synergist in conjunction with diethyl phosphates in flame retardants for polymeric molding compositions, for example from WO 97/39053 A1).
- the proportion of component I is usually 0 and 25 wt .-%, preferably 1 to 25 wt .-%, in particular 4 to 10 wt .-%, based on the total amount of
- Polyester composition When using melamine cyanurate as component I are in the
- Polyester compositions having a Comparative Tracking Index measured according to the International Electrotechnical Commission Standard IEC-601 12/3, of greater than or equal to 500 volts. Also preferred flame-retardant according to the invention
- Polyester compositions achieve a rating of V0 to UL-94, especially measured on moldings of 3.2 mm to 0.4 mm thickness.
- Polyester compositions have a Glow Wire Flammability Index according to IEC-60695-2-12 of at least 960 ° C, in particular measured
- Polyester compositions have a glow-wire resistance, expressed by glow-wire-ignition temperature (GWIT) according to IEC-60695-2-13 of at least 775 ° C, in particular measured on molded parts of 0.75 - 3 mm thickness.
- GWIT glow-wire-ignition temperature
- the flame retardant combinations used according to the invention stabilize the polyester (component A) very well against thermal degradation. This is reflected in the change in the specific viscosity of the polyester
- Polyester compositions The thermal stress occurring there results in partial degradation of the polyester chains, which results in a reduction in the average molecular weight and, associated therewith, a reduction in the viscosity of a polyester solution.
- Capillary viscometers are 130 cm 3 / g. After compounding and shaping a polybutylene terephthalate composition according to the invention, typical values for the specific viscosity of the processed polybutylene terephthalate (determined as indicated above) range between 65 and 150 cm 3 / g, preferably between 100 and 129 cm 3 / g.
- polyester compositions according to the invention comprise as component A one or more thermoplastic polyesters.
- polyesters of component A are usually around
- (cyclo) aliphatic or aromatic-aliphatic polyesters derived from (cyclo) aliphatic and / or aromatic dicarboxylic acids or their polyester-forming derivatives, such as their dialkyl esters or anhydrides, and from (cyclo) aliphatic and / or araliphatic diols or from (cyclo) aliphatic and / or aromatic hydroxycarboxylic acids or their polyester-forming derivatives, such as their alkyl esters or anhydrides derived.
- (Cyclo) aliphatic includes cycloaliphatic and aliphatic compounds.
- thermoplastic polyesters of component A are preferably selected from the group of polyalkylene esters of aromatic and / or aliphatic dicarboxylic acids or their dialkyl esters.
- the thermoplastic polyesters used as component A can be prepared by known methods (Kunststoff-Handbuch, Vol. VIII, pages 695-710, Karl Hanser Verlag, Kunststoff 1973).
- Preferably used components A are aromatic-aliphatic
- thermoplastic polyesters and preferably thermoplastic polyesters derived by reacting aromatic dicarboxylic acids or their polyester-forming derivatives with aliphatic C 2 -C 10 -diols, in particular with C 2 -C 4 -diols.
- Polyalkylene enterephthalates and particularly preferably polyethylene terephthalates or polybutylene terephthalates.
- Polyalkylene terephthalates preferably contain at least 80 mol%, in particular 90 mol%, based on the dicarboxylic acid, units derived from terephthalic acid.
- polyalkylene terephthalates may contain up to 20 mol% of radicals of other aromatic dicarboxylic acids having 8 to 14 carbon atoms or radicals of aliphatic dicarboxylic acids having 4 to 12 carbon atoms, such as radicals of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid,
- Polyalkylene terephthalates can be prepared by incorporation of relatively small amounts of trihydric or trihydric alcohols or tribasic or tetrabasic carboxylic acids, as described, for example, in US Pat. As described in DE-A-19 00 270 are branched. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol. Particularly preferred components A are polyalkylene terephthalates which are prepared solely from terephthalic acid and its reactive derivatives (eg.,
- Dialkyl esters and ethylene glycol and / or propanediol-1, 3 and / or butanediol-1, 4 are prepared (polyethylene and Polytrimethylen- and
- Polybutylene terephthalate and mixtures of these polyalkylene terephthalates.
- Preferred polybutylene terephthalates contain at least 80 mol%
- the preferred polybutylene terephthalates may further contain, in addition to 1,4-butanediol radicals, up to 20 mol% of other aliphatic diols having 2 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms, e.g. B. residues of
- Polyalkylene terephthalates 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.
- thermoplastic component used as component A according to the invention is thermoplastic component used as component A according to the invention.
- Polyesters may also be used in admixture with other polyesters and / or other polymers.
- component B fillers and / or preferably reinforcing materials are used, preferably glass fibers. It can also be mixtures of two or several different fillers and / or reinforcing materials used.
- Preferred fillers are mineral particulate fillers based on talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin, amorphous silicas, nanoscale minerals, particularly preferably montmorillonites or nano-boehmites, magnesium carbonate, chalk, feldspar, glass beads and / or barium sulfate. Particular preference is given to mineral particulate fillers based on talc, wollastonite and / or kaolin.
- needle-shaped mineral fillers are also particularly preferably used. Under needle-shaped mineral fillers is understood according to the invention a mineral filler with pronounced needle-like character. Preferred are needle-shaped wollastonites.
- the mineral has a length to diameter ratio of 2: 1 to 35: 1, more preferably from 3: 1 to 19: 1, particularly preferably from 4: 1 to 12: 1.
- the average particle size of the acicular mineral fillers used according to the invention as component B is preferably less than 20 ⁇ m, more preferably less than 15 ⁇ m, particularly preferably less than 10 ⁇ m, determined using a CILAS granulometer.
- the components B preferably used according to the invention are reinforcing materials. This may, for example, to
- Reinforcement based on carbon fibers and / or glass fibers act.
- the filler and / or reinforcing material may in a preferred
- Be surface-modified embodiment preferably with a
- Adhesive or a primer system particularly preferably on
- Silane In particular when glass fibers are used, in addition to silanes, polymer dispersions, film formers, branching agents and / or
- Fiber processing aids are used.
- the glass fibers preferably used according to the invention as component B may be short glass fibers and / or long glass fibers. As short or long glass fibers, cut fibers can be used. Short glass fibers can also be used in the form of ground glass fibers.
- glass fibers can also be used in the form of continuous fibers, for example in the form of rovings, monofilaments,
- Filament yarns or twines or glass fibers can be used in the form of textile fabrics, for example as glass fabrics, as
- Glass braid or as a glass mat Glass braid or as a glass mat.
- Polyester matrix range from 0.05 to 10 mm, preferably from 0.1 to 5 mm. After incorporation into the polyester matrix, the length of the glass fibers has decreased. Typical fiber lengths for short glass fibers after the
- Incorporation into the polyester matrix ranges from 0.01 to 2 mm, preferably from 0.02 to 1 mm.
- the diameters of the individual fibers can vary within wide ranges. Typical diameters of the individual fibers range from 5 to 20 ⁇ m.
- the glass fibers can have any cross-sectional shapes, for example round, elliptical, n-cornered or irregular cross-sections. Glass fibers with mono- or multilobal cross-sections can be used.
- Glass fibers can be used as continuous fibers or as cut or ground glass fibers.
- the glass fibers themselves can be selected, for example, from the group of E-glass fibers, A-glass fibers, C-glass fibers, D-glass fibers, M-glass fibers, S-glass fibers,
- the glass fibers are preferably provided with a size, which preferably contains polyurethane as a film former and aminosilane as adhesion promoter.
- E glass fibers have the following chemical composition: S1O2 50-56%; AI2O3 12-16%; CaO 16-25%; MgO ⁇ 6%; B2O3 6-13%; F ⁇ 0.7%; Na 2 O 0.3-2%; K2O 0.2-0.5%; Fe 2 Os 0.3%.
- R glass fibers have the following chemical composition: S1O2 50-65%; AI2O3 20-30%; CaO 6-16%; MgO 5-20%; Na 2 O 0.3-0.5%; K2O 0.05-0.2%; Fe 2 Os 0.2-0.4%, T1O2 0.1-0.3%.
- ECR glass fibers have the following chemical composition: S1O2 57.5-58.5%; AI2O3 17.5-19.0%; CaO 11, 5-13.0%; MgO 9.5-1 1, 5.
- Component C may contain small amounts of salts of component D and salts of component E, for example up to 10 wt .-% of
- Component D preferably 0.01 to 6 wt .-%, and in particular 0.2 to 2.5 wt .-% thereof, and up to 10 wt .-% of component E, preferably 0.01 to 6 wt .-% , And in particular 0.2 to 2.5 wt .-% thereof based on the amount of components C, D and E.
- the salts of ethylphosphonic acid used according to the invention as component E are suitable as additives to diethyl phosphates in
- Flame retardants for polymeric molding compositions also known, for example from DE 102007041594 A1.
- components C, D, E and optionally F, H and / or I are in particulate form, wherein the average
- Particle size (dso) is 1 to 100 ⁇ .
- the polyester compositions according to the invention may contain as component G further additives.
- Preferred components I for the purposes of the present invention are antioxidants, UV stabilizers,
- Gamma ray stabilizers for antioxidants, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact modifiers, dyes, pigments and / or other flame retardants that differ from components C, D, E, F, H and I.
- phosphates such as melamine poly (metal phosphates).
- metal phosphates such as melamine poly (metal phosphates).
- Preferred metals for this purpose are the elements of FIG. 2.
- Main group the 3rd main group, the 2nd subgroup, the 4th subgroup and the subgroup Villa of the Periodic Table and cerium and / or lanthanum.
- Melamine poly (metal phosphates) are preferably melamine poly (zinc phosphates), melamine poly (magnesium phosphates) and / or melamine poly (calcium phosphates).
- melamine poly metal phosphates
- Hydrogen phosphato or pyrophosphato metallates with complex anions containing a have four- or réellebindiges metal atom as a coordination center with bidentate hydrogen phosphate or pyrophosphate ligands.
- melamine-intercalated aluminum, zinc or magnesium salts of condensed phosphates are also preferred.
- Bis-melamine-zinc diphosphate and / or bis-melamine alumotriphosphate Bis-melamine-zinc diphosphate and / or bis-melamine alumotriphosphate.
- Aluminum phosphates Preference is given to aluminum phosphates, aluminum monophosphates; Aluminum orthophosphates (AIPO4), aluminum hydrogen phosphate (Al2 (HPO4) 3) and / or aluminum dihydrogen phosphate
- calcium phosphate zinc phosphate, titanium phosphate and / or iron phosphate
- Calcium dihydrogen pyrophosphate magnesium pyrophosphate zinc pyrophosphate and / or aluminum pyrophosphate.
- the foregoing and other related and phosphates add about the types APP include Type II, AMPP, MPP, MPyP, PiPyP. PPaz, Safire ® 400, Safire ® 600, EDAP and others.
- DE-A-102007036465 and EP-A-31331 12 are expressly among the usable components I.
- the other additives are known per se as additives to polyester compositions and can be used alone or in admixture or in the form of masterbatches.
- the abovementioned components A, B, C, D, E and optionally F, G, H and / or I can be processed in a wide variety of combinations with the flameproofed polyester composition according to the invention. It is thus possible to mix the components into the polyester melt at the beginning or at the end of the polycondensation or in a subsequent compounding process. Furthermore, there are processing processes in which individual components are added later. This is especially practiced when using pigment or additive masterbatches. In addition, there is the possibility, in particular powdered components on by the
- Polyester compositions may be combined by mixing prior to incorporation into the polyester matrix.
- conventional mixing units can be used, in which the components in a suitable mixer, for. B. 0.01 to 10 hours at 0 to 300 ° C mixed.
- Polyester compositions can also be prepared granules, which can then be introduced into the polyester matrix.
- two or more components of the invention are also be prepared granules, which can then be introduced into the polyester matrix.
- Polyester composition with granulation and / or binder in a suitable mixer or a granulating are processed into granules.
- the initially formed crude product can be dried in a suitable dryer or tempered for further grain buildup.
- polyester composition of the present invention or two or more components thereof may be prepared by roll compaction in one embodiment.
- polyester composition according to the invention or two or more components thereof may in one embodiment be prepared by mixing, extruding, chopping (or breaking) the ingredients.
- polyester composition of the present invention or two or more components thereof may be prepared by spray granulation in one embodiment.
- the flame-retardant polymer molding composition according to the invention is preferably in granular form, for. B. as an extrudate or as a compound before.
- the granules preferably have a cylindrical shape with a circular, elliptical or irregular base, spherical shape, pillow shape, cube shape, cuboid shape, prism shape.
- Typical length to diameter ratio of the granules are 1 to 50 to 50 to 1, preferably 1 to 5 to 5 to 1.
- the granules preferably have a diameter of 0.5 to 15 mm, more preferably of 2 to 3 mm and preferably a length of 0.5 to 15 mm, particularly preferably 2 to 5 mm.
- the invention also relates to moldings produced from the flame-retardant polyester composition described above comprising the components A, B, C, D and E and optionally the components F and / or G.
- the molded parts according to the invention may be any desired formations. Examples of these are fibers, films or moldings, obtainable from the novel flame-retardant polyester molding compositions by any desired molding process, in particular by injection molding or extrusion.
- the preparation of the flame-retardant polyester moldings according to the invention can be carried out by any molding process. Examples include injection molding, pressing, foam injection, gas injection molding, blow molding,
- the molded parts are preferably injection-molded parts or extruded parts.
- the flame-retardant polyester compositions according to the invention are suitable for the production of fibers, films and moldings, in particular for applications in the electrical and electronics sector.
- the invention preferably relates to the use of the flame-retardant polyester compositions according to the invention in or for connectors, current-carrying parts in power distributors (Fl protection), circuit boards, potting compounds, power connectors, circuit breakers, lamp housings, LED housings,
- the invention likewise preferably relates to the use of the flame-retardant polyester compositions according to the invention for the preparation of
- the wall thickness of the shaped bodies according to the invention can typically be up to 10 mm. Particularly suitable are moldings with less than 1.5 mm wall thickness, more preferably less than 1 mm wall thickness and particularly preferably less than 0.5 mm wall thickness. The following examples illustrate the invention without limiting it.
- polyesters (component A):
- PBT Polybutylene terephthalate
- BASF Ultradur ® 4500
- PET Polyethylene terephthalate
- Leistritz ZSE 27 HP-44D Leistritz ZSE 27 HP-44D at temperatures of 240 to 280 ° C incorporated.
- the glass fibers were added via a side feeder.
- the homogenized polymer strand was stripped off, cooled in a water bath and then granulated.
- Injection molding machine type Arburg 320 C / KT processed to test specimens at melt temperatures of 260 to 280 ° C and tested for flame retardance and classified by the UL 94 test (Underwriter Laboratories).
- UL 94 test Underwriter Laboratories
- the Comparative Tracking Index of the molded parts was determined according to the International Electrotechnical Commission Standard IEC-601 12/3.
- the Glow Wire Flammability Index (GWFI Index) was standardized
- Polyamide compositions are measured using an X-ray powder diffractometer (XTert-MPD, Phillips). The sample was irradiated with Cu-K-alpha radiation and the step time was 1 second.
- XTert-MPD X-ray powder diffractometer
- polyester compositions according to the invention of Examples 1 to 5 are molding compositions which reach the fire classification UL 94 V-0 at 0.4 mm,
- Example 5 The addition of another component F in Example 5 leads to a further improvement of the flame retardancy expressed by a reduced afterburning time.
- Comparative Example C2 The omission of component D in Comparative Example C2 resulted in a reduced CTI value in addition to an extension of the fire protection time compared to Example 2.
- Comparative Example C3 was by increasing the concentration of
- polyester compositions according to the invention of Examples 6 to 10 are molding compositions which reach the fire classification UL 94 V-0 at 0.4 mm and at the same time have CTI 600 volts and GWFI 960 ° C.
- the addition of another component F in Example 10 leads to a further improvement of the flame retardancy expressed by a reduced afterburning time.
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102017215776.3A DE102017215776A1 (de) | 2017-09-07 | 2017-09-07 | Flammhemmende Polyesterzusammensetzungen und deren Verwendung |
PCT/EP2018/073230 WO2019048309A1 (de) | 2017-09-07 | 2018-08-29 | Flammhemmende polyesterzusammensetzungen und deren verwendung |
Publications (1)
Publication Number | Publication Date |
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EP3679091A1 true EP3679091A1 (de) | 2020-07-15 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP18762080.2A Withdrawn EP3679091A1 (de) | 2017-09-07 | 2018-08-29 | Flammhemmende polyesterzusammensetzungen und deren verwendung |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP3679091A1 (de) |
CN (1) | CN109467891B (de) |
DE (1) | DE102017215776A1 (de) |
TW (1) | TW201920408A (de) |
WO (1) | WO2019048309A1 (de) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102018220696A1 (de) | 2018-11-30 | 2020-06-04 | Clariant Plastics & Coatings Ltd | Flammschutzmittelmischungen, flammhemmende Polymerzusammensetzungen, damit ausgerüstete Kabel und deren Verwendung |
DE102019201824A1 (de) * | 2019-02-12 | 2020-08-13 | Clariant Plastics & Coatings Ltd | Flammschutzmittelmischungen, flammhemmende Polymerzusammensetzungen, damit ausgerüstete Kabel und deren Verwendung |
WO2023217401A1 (de) | 2022-05-12 | 2023-11-16 | Envalior Deutschland Gmbh | Kriechstromfeste polyesterzusammensetzungen |
CN115042497B (zh) * | 2022-08-16 | 2022-11-01 | 杭州和顺科技股份有限公司 | 一种双向拉伸阻燃聚酯薄膜及其制备方法 |
CN116265514B (zh) * | 2023-03-16 | 2023-11-24 | 江苏利思德新材料股份有限公司 | 一种颗粒型无卤阻燃剂及其制备方法与应用 |
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DE2252258A1 (de) | 1972-10-25 | 1974-05-09 | Hoechst Ag | Schwerentflammbare thermoplastische polyester |
DE2447727A1 (de) | 1974-10-07 | 1976-04-08 | Hoechst Ag | Schwerentflammbare polyamidformmassen |
DE19607635A1 (de) | 1996-02-29 | 1997-09-04 | Hoechst Ag | Schwerentflammbare Polyamidformmassen |
DE19614424A1 (de) | 1996-04-12 | 1997-10-16 | Hoechst Ag | Synergistische Flammschutzmittel-Kombination für Polymere |
DE19734437A1 (de) | 1997-08-08 | 1999-02-11 | Clariant Gmbh | Synergistische Flammschutzmittel-Kombination für Polymere |
DE19737727A1 (de) | 1997-08-29 | 1999-07-08 | Clariant Gmbh | Synergistische Flammschutzmittel-Kombination für Kunststoffe |
NL1009588C2 (nl) | 1998-07-08 | 2000-01-11 | Dsm Nv | Polyfosfaatzout van een 1,3,5-triazineverbinding met hoge condensatiegraad, een werkwijze voor de bereiding ervan en de toepassing als vlamdover in polymeersamenstellingen. |
NL1016340C2 (nl) | 2000-10-05 | 2002-04-08 | Dsm Nv | Halogeenvrije vlamvertragende samenstelling en vlamdovende polyamidesamenstelling. |
JP4951187B2 (ja) | 2002-12-26 | 2012-06-13 | ポリプラスチックス株式会社 | 難燃性樹脂組成物 |
DE10359814A1 (de) * | 2003-12-19 | 2005-07-28 | Clariant Gmbh | Dialkylphosphinsäure-Salze |
DE102004042833B4 (de) | 2004-09-04 | 2022-01-05 | Chemische Fabrik Budenheim Kg | Polyphosphatderivat einer 1,3,5-Triazonverbindung, Verfahren zu dessen Herstellung und dessen Verwendung |
DE102005016195A1 (de) | 2005-04-08 | 2006-10-12 | Clariant Produkte (Deutschland) Gmbh | Stabilisiertes Flammschutzmittel |
DE102007036465A1 (de) | 2007-08-01 | 2009-02-05 | Catena Additives Gmbh & Co. Kg | Phosphorhaltige Triazin-Verbindungen als Flammschutzmittel |
DE102007041594A1 (de) | 2007-09-01 | 2009-03-05 | Clariant International Limited | Flammwidrige Polyestercompounds |
US8674951B2 (en) | 2009-06-16 | 2014-03-18 | Intel Corporation | Contoured thumb touch sensor apparatus |
DE102010048025A1 (de) | 2010-10-09 | 2012-04-12 | Clariant International Ltd. | Flammschutzmittel- Stabilisator-Kombination für thermoplastische Polymere |
DE102010049968A1 (de) | 2010-10-28 | 2012-05-03 | Clariant International Ltd. | Flammwidrige Polyestercompounds |
DE102011120218A1 (de) | 2011-12-05 | 2013-06-06 | Clariant International Ltd. | Alkali-Aliminium-Mischphosphite, Verfahren zur ihrer Herstellung sowie deren Verwendung |
DE102014001222A1 (de) * | 2014-01-29 | 2015-07-30 | Clariant lnternational Ltd | Halogenfreie feste Flammschutzmittelmischung und ihre Verwendung |
PL3133112T3 (pl) | 2015-03-09 | 2022-05-02 | Lanxess Deutschland Gmbh | Termoplastyczne masy formierskie |
CN107828207B (zh) * | 2016-09-15 | 2020-12-25 | 科莱恩塑料和涂料有限公司 | 用于热塑性聚合物的阻燃剂-稳定剂组合 |
DE102017212099A1 (de) * | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Additivmischungen für Kunststoffe, lasermarkierbare Polymerzusammensetzungen enthaltend diese und deren Verwendung |
DE102017212100A1 (de) * | 2017-07-14 | 2019-01-17 | Clariant Plastics & Coatings Ltd | Additivmischungen für Kunststoffe, lasermarkierbare Polymerzusammensetzungen enthaltend diese und deren Verwendung |
-
2017
- 2017-09-07 DE DE102017215776.3A patent/DE102017215776A1/de not_active Withdrawn
-
2018
- 2018-02-12 CN CN201810143526.3A patent/CN109467891B/zh active Active
- 2018-08-27 TW TW107129746A patent/TW201920408A/zh unknown
- 2018-08-29 WO PCT/EP2018/073230 patent/WO2019048309A1/de active Search and Examination
- 2018-08-29 EP EP18762080.2A patent/EP3679091A1/de not_active Withdrawn
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Publication number | Publication date |
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TW201920408A (zh) | 2019-06-01 |
DE102017215776A1 (de) | 2019-03-07 |
CN109467891A (zh) | 2019-03-15 |
WO2019048309A1 (de) | 2019-03-14 |
CN109467891B (zh) | 2021-04-06 |
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