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
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0066—Flame-proofing or flame-retarding additives
• • 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
  • 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
  • C08K5/53—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
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/14—Glass
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/02—Flame or fire retardant/resistant

Definitions

• the disclosure is related to f!ame-retardant polymer compositions comprising a mixture of metal salts of phosphinic acid.
• Thermoplastic polymers such as polyester or po!yamide possess excellent mechanical properties, moldability, and chemical resistance and have therefore been used in automotive parts, electric/electronic components, and many other applications. In certain applications, it is desirable that these polymers also are flame-retardant, This can be achieved by the incorporation of various types of additives. Typically, halogenated organic compounds, such as brominated polystyrene, along with an antimony compound may be used. However, during the last twenty years or so, halogenated flame retardants have come under scrutiny due to environmental concerns.
• Phosphorus-containing products are one type of halogen-free flame retardants that have been used in the art.
• U.S. Patents are one type of halogen-free flame retardants that have been used in the art.
• U.S. Patents are one type of halogen-free flame retardants that have been used in the art.
• U.S. Patents are one type of halogen-free flame retardants that have been used in the art.
• the purpose of the present disclosure is to provide a polymer composition with improved flame-retardant properties.
• the flame-retardant polymer composition comprises (a) at least one polymer, (b) 10-30 wt% of a mixture of metal salts of phosphinic acid, and (c) 1 -20% of at least one nitrogen-containing compound, with the total wt% of all components comprised in the flame-retardant polymer composition totaling to 100 wt%,
• the mixture of metal salts of phosphinic acid consists essentially of a first metal salt of phosphinic acid having a Formula (!) and a second metal salt of phosphinic acid having a Formula ( ⁇ ) with a weight ratio of 3:1-1 :3,
• each of R 1 and R 2 is independently selected from the group consisting of linear Ci-Ce alkyl groups; each of R 3 and R 4 is independently selected from the group consisting of linear Ci-Ce alkyl groups; each of R 3 and R 4 is independently selected from the group consisting of linear Ci-Ce alkyl groups; each of R 3 and R 4 is independently selected from the group consisting of linear Ci-Ce alkyl groups; each of R 3 and R 4 is
• each of M and N is independently selected from the group consisting of magnesium ions, calcium ions, aluminum ions, zinc ions, antimony ions, tin ions, germanium ions, titanium ions, iron ions, zirconium, cerium ions, bismuth ions, strontium ions, manganese ions, lithium ions, sodium ions, potassium ions, and protonated nitrogen bases; and each of x and y is independently an integer from 1 to 4.
• the first metal salt of phosphinic acid is selected from aluminium
• methyiethylphosphinate and aluminium diethylphosphinate or the first metal salt of phosphinic acid is aluminium diethylphosphinate.
• the second metal salt of phosphinic acid is selected from the group consisting of aluminium isopropylisobutylphosphinate, aluminium
• the mixture of metal salts of phosphinic acid is present in the composition at a level of 10-25 wt% or 12-18 wt%, based on the total weight of the composition.
• the weight ratio between the first metal salt of phosphinic acid and the second metal salt of phosphinic acid is 2.5:1-1 :2.5.
• the at least one polymer is selected from the group consisting of polyamides, polyesters, polyolefins, polystyrenes, polyphenylene ethers, polycarbonates, acrylonitrile-butadiene-styrene terpolymers, and combinations or blends of two or more thereof, or the at least one polymer is selected from the group consisting of polyamides and polyesters, or the at least one polymer is selected from polyamides.
• the at least one polymer is present in the composition at a level of 20-89 wt%, or 30-80 wt%, or 30-70 wt%.
• the at least one nitrogen-containing compound is selected from the group consisting of melamine cyanurate; condensation products of meiamine; reaction products of phosphoric acid with melamine; reaction products of phosphoric acid with condensation products of meiamine; and combinations of two or more thereof, or the at least one nitrogen-containing compound is meiamine polyphosphate.
• the at least one nitrogen-containing compound is present in the composition at a level of 3-15 wt% or 5-12 wt%, based on the total weight of the composition.
• the composition further comprises up to 80 wt% or 5-50 wt% of reinforcing agents, based on the total weight of the composition.
• the reinforcing agents are selected from the group consisting of glass fibers, glass flakes, kaolin, clay, talc, woilastonite, calcium carbonate, silica, carbon fibers, potassium titanate, and combinations of two or more thereof, or the reinforcing agents are selected from glass fibers.
• the article is a molded article.
• the range includes any value that is within the two particular end points and any value that is equal to or about equal to any of the two end points.
• flame-retardant polymer compositions that comprise: (a) at least one polymer, (b) about 10-30 wt% of a mixture of meta salts of phosphinic acid, and (c) about 1-20 wt% of at least one nitrogen-containing compound, with the total wt% of all components comprised in the flame-retardant polymer composition totaling to 100 wt%.
• the mixture of metal salts of phosphinic acid consists essentially of a first metal salt of phosphinic acid having a Formula (I) and a second metal salt of phosphinic acid having a Formula (II) with a weight ratio of about 3:1 to about 1 :3,
• each of R 1 and R 2 is independently selected from the group consisting of linear d-Ce alkyl groups; each of R J and R 4 is independently selected from the group consisting of branched Cs-Ce alkyl groups: each of M and N is independently selected from the group consisting of magnesium ions, calcium ions, aluminum ions, zinc ions, antimony ions, tin ions, germanium ions, titanium ions, iron ions, zirconium, cerium ions, bismuth ions, strontium ions, manganese ions, lithium ions, sodium ions, potassium ions, and protonated nitrogen bases; and each of x and y is independently an integer from 1 to 4.
• the polymers used herein may be any suitable polymeric material.
• the polymers suitable herein may include, without limitation, po!yamides, polyesters, polyolefins (such as polypropylenes, poiyisobutylenes, or polyethylenes), polystyrenes (such as high-impact polystyrenes (HIPS)), polyphenylene ethers (PPE), polycarbonates (PC),
• ABS acrylonitrile-butadiene-styrene terpolymers
• PC/ABS blends PC/ABS blends
• PPE/HIPS blends and combinations of two or more thereof.
• the polymer used herein is selected from po!yamides and polyesters. In a further embodiment, the polymer used herein is selected from polyamides.
• suitable polyesters include, without limitation, polyethylene terephthalate (PET), polybutylene
• PBT polytnmethylene terephthalate
• PCT polycyclohexylene dimethylene terephthalate
• polyester elastomers such as
• polyesters used herein may also be obtained commercially from various vendors.
• suitable PET may be obtained commercially from E.L du Pont de Nemours and Company (U.S.A.) (hereafter "DuPont") under the trade name Rynite ⁇
• suitable PBT may be obtained commercially from DuPont under the trade name Crastin ®
• suitable PTT may be obtained commercially from DuPont under the trade name Sorona ®
• suitable PCT may be obtained commercially from Ticona, The Netherland under the trade name ThermxTM
• suitable copolyetheresters may be obtained commercially from DuPont under the trade name Hytrel ® .
• suitable polyamides include both aliphatic polyamides and aromatic polyamides.
• Polyamides are (a) condensation products of one or more dicarboxylic acids and one or more diamines, or (b) condensation products of one or more aminocarboxylic acids, or (c) ring opening polymerization products of one or more cyclic lactams.
• the aromatic polyamides used herein may be homopolymers, copolymers, terpolymers or higher polymers containing at least one aromatic monomer component.
• an aromatic polyamide may be obtained by using an aliphatic dicarboxylic acid and an aromatic diamine, or an aromatic dicarboxylic acid and an aliphatic diamine as starting materials and subjecting them to polycondensation.
• Suitable diamines used herein may be selected from aliphatic diamines, alicyclic diamines, and aromatic diamines.
• Exemplary diamines useful herein include, without limitation, tetramethylenediamine;
• Suitable dicarboxylic acids used herein may be selected from aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids.
• Exemplary dicarboxylic acids useful herein include, without limitation, adipic acid; sebacic acid; azelaic acid; dodecanedoic acid; terephthalic acid;
• isophthalic acid phthalic acid; g!utaric acid; pime!ic acid; suberic acid;
• Exemplary aliphatic poiyamides used herein include, without limitation, polyamide 6; polyamide 8,8; po!yamide 4,6; polyamide 6,10; polyamide 8,12; polyamide 5,6; polyamide 5,10; polyamide 5,12; polyamide 11 ; polyamide 12;
• poiyamide 6,15 poiyamide 6,16; poiyamide 6,13; and the like.
• Exemplary aromatic polyamides used herein include, without limitation, po!y(m-xy!ylene adipamide) (poiyamide MXD,6); poly(dodecamethylene terephthalamide) (poiyamide 12, T); po!y(hendecamethy!ene terephthalamide) (poiyamide 11 ,T); poly(decamethylene terephthalamide) (poiyamide 10,T); poly(nonamethylene terephthalamide) (poiyamide 9,1); poly(hexamethylene terephthalamide) (poiyamide 6,T); hexamethylene adipamide/hexamethylene terephthalamide copolyamide (poiyamide 6,176,6, i.e., poiyamide 6,T/6,6 having at least about 50 mol% of its repeating units derived from 6,T);
• hexamethylene terephtha!amide/hexamethylene adipamide copolyamide (poiyamide 8,6/6,T, i.e., poiyamide 6,6/6, T having at least about 50 mol% of its repeating units derived from 6,6); poly(hexamethy!ene
• terephtha!amide/hexamethylene isophthalamide (poiyamide 6,T/6,I, i.e., poiyamide 6,T/6,I having at least about 50 mol% of its repeating units derived from 6,T); hexamethylene terephthalamide/2-methylpentamethylene
• terephthalamide copolyamide (poiyamide 6,T/D,T); hexamethylene
• adipamide/hexamethylene terephthaiamide/hexamethylene isophthalamide copolyamide (poiyamide 6,6/6,176, i); poly(capro!actam-hexamethy!ene terephthalamide) (poiyamide 6/6, T); poly(hexamethy!ene
• isophthaiamide/hexamethylene terephthalamide) (poiyamide ⁇ , ⁇ / ⁇ , ⁇ , i.e., poiyamide 6,1/ ⁇ , ⁇ having at least about 50 mo!% of its repeating units derived from 6,1); poiy(hexamethyIene isophthalamide) (poiyamide 6,1);
• poly(metaxylyiene isophthalamide/ metaxylylene terephthalamide/ hexameihylene isophthalamide) polyamide MXD,l/MXD.T/6,i/6,T
• poly(metaxylylene isophthalamide/dodecamethylene isophthalamide) polyamide XD, 1/12,1)
• poly(meiaxylylene isophthalamide) polyamide MXD, I
• poly(hexamethyiene isophthalamide/dimethyldiaminodicyclohexylmethane isophthaiamide/dodecanamide) (polyamide 6,I/MACM,I/12);
• the at least one polymer may be present at a level of about 20-89 wt%, or about 30-80 wt%, or about 30-70 wt%.
• the weight ratio between the first metal salt of phosphinic acid of Formula (I) and the second metal salt of phosphinic acid of Formula (II) ranges from about 3:1 to about 1 :3 or preferably from about 2.5:1 to about 1 :2.5.
• the metal salt of phosphinic acid of Formula (I) used herein may be selected from those wherein, R 1 and R 2 are independently selected from methyl, ethyl, n-propyl, n-butyl and n-hexyl; M is selected from aluminium ions and zinc ions.
• the metal salt of phosphinic acid of Formula (I) used herein is selected from aluminium methylethylphosphinate and aluminium diethylphosphinate. More preferably, the metal salt of phosphinic acid of Formula (I) used herein is aluminium diethylphosphinate.
• the metal salt of phosphinic acid of Formula (I) is an aluminum diethylphosphinate having a Formula (Mi),
• the metal salt of phosphinic acid of Formula (!) used herein also may be obtained commercially from Clariant (Switzerland) under the trade name Exolit ® OP1230.
• the metal salt of phosphinic acid of Formula (II) used herein may be selected from those wherein, R 3 , R 4 are independently selected from isopropyl, isobutyl, tert-butyl, isopentyl, isohexyl, and the like; N is selected from aluminium ions and zinc ions.
• the metal salt of phosphinic acid of Formula (II) used herein is selected from aluminium isopropyiisobutylphosphinate, aluminium isopropy!tertbutylphosphinate and aluminium diisobutylphosphinate. More preferably, the metal salt of phosphinic acid of Formula (M) used herein is aluminium
• the metal salt of phosphinic acid of Formula ( ⁇ ) is an aluminum diisobutylphosphinate having a Formula (IV),
• the preparation methods may include, first, synthesizing a branched dialkylphosphinic acid in a free-radical addition reaction between an olefin or an alcohol and a hypophosphorous acid or salt in the presence of a catalyst (free-radical initiator), followed by reacting the branched dialkylphosphinic acid with a metal carbonate, a metal chloride, a metal hydroxide, or a metal oxide in an aqueous solution to form the metal salt of phosphinic acid of Formula (II) (see e.g., U.S. Patent Nos.
• aluminum diisobutylphosphinate with Formula (IV) may be prepared as those disclosed in U.S. Patent No. 7,807,737 and "Synthesis, characterization and thermal degradation kinetics of aluminum diisobutylphosphinate", Shao et al., Thermochimica Acta 547 (2012) 70-75, which are incorporated herein by reference. More specifically, the reaction scheme of aluminum diisobutylphosphinate with Formula (IV) may be as follow:
• the mixture of metal salts of phosphinic acid may be present at a level of about 10-30 wt% or about 10-25 wt%, or about 12-18 wt% .
• flame-retardant polymer compositions disclosed herein may include, without limitation, those described, for example in U.S. Patent Nos. 8,365,071 ; and 7,255,814.
• the nitrogen-containing compounds used herein are selected from me!amine, benzoguanamine, tris(hydroxyethyl)isocyanurate, allantoine, glycouril, dicyandiamide, guanidine and carbodiimide, and derivatives thereof.
• the nitrogen-containing compounds used herein may be selected from melamine derivatives, which include, without limitation, (i) melamine cyanurate, (ii) condensation products of melamine, (iii) reaction products of phosphoric acid with melamine, and (iv) reaction products of phosphoric acid with condensation products of melamine.
• melamine derivatives include, without limitation, melem, melam and melon, as well as higher derivatives and mixtures thereof.
• Condensation products of melamine can be produced by any suitable methods (e.g., those described in PCT Patent Publication No. W09616948).
• Reaction products of phosphoric acid with melamine or reaction products of phosphoric acid with condensation products of melamine are herein understood compounds, which result from the reaction of melamine with a phosphoric acid or the reaction of a condensation product of melamine (e.g., melem, melam, or melon) with a phosphoric acid.
• Examples include, without limitation, dime!amine phosphate, dimelamine pyrophosphate, melamine phosphate, melamine polyphosphate, melamine pyrophosphate, melam polyphosphate, melon polyphosphate, and melem polyphosphate, as are described, e.g., in PCT Patent Publication No. WO9839308.
• the at least one nitrogen-containing compound comprised in the composition disclosed herein is a melamine polyphosphate.
• the at least one nitrogen-containing compound may be present at a level of about 1-20 wt%, or about 3-15 wt%, or about 5-12 wt%.
• the flame-retardant polymer compositions disclosed herein may further comprise one or more inorganic reinforcing agents or fillers.
• inorganic reinforcing agents or fillers include, without limitation, glass fibers, glass flakes, kaolin, clay, talc, wollastonite, calcium carbonate, silica, carbon fibers, potassium titanate, and combinations of two or more thereof.
• glass fibers are included in the
• the inorganic reinforcing agents or fillers may be present in the flame-retardant composition at a level of up to about 60 wt%, or about 5-50 wt%, based on the total weight of the composition.
• suitable additives also may be included in the flame-retardant polymer compositions.
• Such other additives may include, without limitation, impact modifiers, plasticizers, ultraviolet light stabilizers, heat stabilizers, antioxidants, antistatic agents, nucleating agents, flow enhancers, processing aids, lubricants, colorants (including dyes, pigments, carbon black, and the like), and combinations of two or more thereof.
• the flame-retardant polymer compositions disclosed herein may be prepared by melt-blending the components using any known methods.
• the component materials may be mixed to uniformity using a melt-mixer such as a single or twin-screw extruder, blender, kneader, Banbury mixer, etc. to give a resin composition.
• part of the materials may be mixed in a melt-mixer, and the rest of the materials may then be added and further melt-mixed until uniform.
• the flame-retardant polymer compositions disclosed herein may be formed into articles using any known melt-processing means such as injection molding, blow molding, extrusion, or thermoforming. Articles molded using injection molding are most preferred.
• articles formed of the reinforced polymer compositions disclosed herein include, without limitation, electrical or electronic parts, such as lamp holders, electrical coil skeletons, electric plug-in units, connectors, switches, laptop housings, etc.
• MSP-1 metal salt of phosphinsc acid-1 : an aluminum
• diethylphosphinate based halogen-free flame retardant obtained from Clariant under the trade name Exolit 1 OP1230;
• SP-2 metal salt of phosphinic acid-2
• diisobutylphinate based halogen-free flame retardant prepared as follows: (a) charging 318 g sodium hypophosphite monohydrate and 637 g of acetic acid into a 3 L three-necked flask equipped with condenser, additional funnel, magnetic stirrer and thermometer; (b) slowly adding 149 g of 95% sulfuric acid into the mixture while substantial precipitation was observed; (c) adding a solution of 436 g of tert-butyl alcohol, 120 g of acetic acid, and 22.5 g of tert-butyi peroxide into the mixture at temperature of 100°C over the course of seventeen hours; (d) drying the mixture in a rotary evaporator under vacuum at 95°C to remove water and solvent, followed by washing three times with a 2.7% sodium carbonate aqueous solution; (e) separating the top oily phase from the rest followed by drying in a rotary evaporator under vacuum at 95°C; (f) collecting and crystallizing
• MPP melarnine polyphosphate
• rrselamine polyphosphate obtained from BASF under the trade name Melapur ] 200/70.
• a polymer composition (all components listed in Table 1 ) was prepared by compounding in a 32 mm ZSK twin screw extruder. The barrel temperatures were set at about 250°C and screw speed at 400 rpm. After exiting the extruder, the blended compositions were cooled and cut into resin pellets.
• composition in each of the examples was molded into 4-mm thick testing bars using an injection molding machine with a melting temperature set at 250°C and mold temperature at 80°C and the tensile modulus, tensile strength, and elongation at break measurements of the test bars were measured and the results are tabulated in Table 1 .
• test bars were molded for the composition in each of CE1 -CE4 and E1-E2. The test bars were then conditioned at 23°C and 50% relative humidity for 48 hours before the UL-94 fiammability rating thereof were measured and the results are tabulated in Table 1 .

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• 2013
  • 2013-06-28 CN CN201310270062.XA patent/CN104250440A/zh active Pending
• 2014
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