WO2014016386A1 - Préparation de compositions ignifuges anticorrosives de polyamide, contenant des phosphinates - Google Patents

Préparation de compositions ignifuges anticorrosives de polyamide, contenant des phosphinates Download PDF

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Publication number
WO2014016386A1
WO2014016386A1 PCT/EP2013/065752 EP2013065752W WO2014016386A1 WO 2014016386 A1 WO2014016386 A1 WO 2014016386A1 EP 2013065752 W EP2013065752 W EP 2013065752W WO 2014016386 A1 WO2014016386 A1 WO 2014016386A1
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Prior art keywords
polyamide
melamine
composition
flame retardant
comprises mixing
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PCT/EP2013/065752
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English (en)
Inventor
Alexander KÖNIG
Christoph Fleckenstein
Heinz Herbst
Siqi Xue
Original Assignee
Basf Se
Basf Schweiz Ag
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Publication of WO2014016386A1 publication Critical patent/WO2014016386A1/fr

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    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a process for the preparation of non-halogenated flame retardant thermoplastic polyamide compositions having reduced corrosion effects on melt processing equipment.
  • Polyamide resins possess excellent mechanical properties, mouldability, and chemical resistance and have therefore been used in automotive parts, electric/electronic components, mechanical components, and many other applications. Articles made from polyamide resins possess desirable physical properties. However, in certain applications, it is desirable that polyamide resin compositions have to be flame retarded to meet the UL-94 standard. This need has promoted research into a variety of methods for imparting flame retardance to polyamide resins.
  • a common method of imparting flame retardance to thermoplastic resin compositions involves incorporating as a flame retardant a halogenated organic compound, such as brominated polystyrene, along with an antimony compound that acts as a synergist for the flame retardant.
  • halogenated flame retardants tend to decompose or degrade at the temperatures used to mould polyamide compositions.
  • the degradation products can corrode the barrels of compounding extruders, the surfaces of molding machines, and other melt processing equipment when halogenated flame retardants come in contact with at elevated temperatures. This problem can be particularly pronounced in the case of semiaro- matic polyamide compositions, as these materials often have melting points that are significantly higher than those of many aliphatic polyamides.
  • the degradation products of halogenated flame retardants can also result in molded articles that have poor surface appearance.
  • non-halogenated flame retardants such as phosphate or phosphinate compounds with triazine derivatives has been disclosed in WO 96/09344.
  • U.S. Pat. Spec. 5, 773,556 discloses compositions comprising polyamide and phosphinate or diphosphinate.
  • U.S. Pat. Spec. 6,255,371 discloses compositions comprising poly- mers, such as polyamide or polyester, with a flame retardant comprising phosphinate or diphosphinate and melamine derivatives, such as condensation products of mel- amine.
  • thermoplastic polymers such as polyamide 6 or 6,6, with a flame retardant comprising phosphinate or diphos- phinate and a synthetic inorganic compound and/or a mineral product, such as zinc borate.
  • the following invention relates to a process for the preparation of an anticorrosive polyamide flame retardant composition, which comprises mixing together
  • R 1 and R 2 represents hydrogen or a linear or branched CrC 8 alkyl radical, or a phenyl radical
  • Both of R 1 and R 2 represent phenyl
  • R 3 represents a linear or branched Ci-Cioalkylene, arylene, alkylarylene, or arylalkylene radical; and, optionally, c) Additional flame retardants and further additives suitable for the
  • a further embodiment of the invention relates to a process for the preparation of an anticorrosive polyamide flame retardant composition, which comprises mixing together a) A polyamide substrate melting at a temperature above 280°C; and b) A salt of a phosphinic acid as represented by the structural formula
  • R 1 and R 2 represent phenyl
  • R 3 represents a linear or branched Ci-Cioalkylene, arylene, alkylarylene, or arylalkylene radical; and, optionally, c) Additional flame retardants and further additives suitable for the preparation of high-melting polyamide flame retardant compositions;
  • the polyamide flame retardant compositions obtained according to the process of the invention exhibit excellent flame retardant properties at low concentrations of the components a) and b).
  • Dependent on the concentrations of component a) in the polymer substrate a), V-0 ratings according to UL-94 (Underwriter's Laboratories Subject 94) and other excellent ratings in related test methods are attained.
  • compositions of the invention are characterized by their excellent anti- corrosive and mechanical properties, such as high values of Izod Impact Strength and low amounts of melt volume rate (MVR).
  • a preferred embodiment of the invention relates to a process, which comprises mixing together
  • a particularly preferred embodiment relates to process, which comprises mixing together
  • a highly preferred embodiment relates to a process, which comprises mixing together a) Polyamide 6/6T; and
  • composition as prepared by the process defined above, comprises the following components: Component a)
  • the flame retardant composition as prepared by the process of the present invention comprises a high melting polyamide component a) comprising at least one polyamide melting at temperatures above 280°C, particularly a polyamide with aromatic groups.
  • the high melting polyamide component a) comprises about 20 to 100 , or preferably about 40 to 100 wt.-%, or more preferably about 60 to 100 wt.-% of at least one polyamide with aromatic groups, wherein the weight percentage amounts are based on the total weight the polyamide component a).
  • the high-melting thermoplastic polyamides are homopolymers, copolymers, terpoly- mers, or higher polymers, particularly those derived from monomers containing aromatic groups.
  • monomers containing aromatic groups are terephthalic acid and its derivatives, isophthalic acid and its derivatives, such as p- and m-xylylenediamine. It is preferred that about 5 to about 75 mole percent of the monomers used to produce the polyamide used in the present invention contain aromatic groups, and more preferred that about 10 to about 55 mole percent of the monomers contain aromatic groups.
  • the aromatic polyamides having aromatic groups may be derived from dicarboxylic acids or their derivatives, such as adipic acid, sebacic acid, azelaic acid, dodecanedoic acid, terephthalic acid, isophthalic acid or their derivatives and other aliphatic and aromatic dicarboxylic acids and aliphatic C 6 -C 2 oalkylenediamines, aromatic diamines, and/or alicyclic diamines.
  • dicarboxylic acids or their derivatives such as adipic acid, sebacic acid, azelaic acid, dodecanedoic acid, terephthalic acid, isophthalic acid or their derivatives and other aliphatic and aromatic dicarboxylic acids and aliphatic C 6 -C 2 oalkylenediamines, aromatic diamines, and/or alicyclic diamines.
  • Preferred diamines include hexamethylenediamine; 2- methylpentamethylenediamine; 2-methyloctamethylenediamine; trimethylhexa- methylenediamine; 1 ,8-diaminooctane; 1 ,9-diaminononane; 1 ,10-diaminodecane; 1 , 12-diaminododecane; and m-xylylenediamine. It may also be derived from one or more lactams or amino acids, such as 1 1 -aminododecanoicacid, caprolactam, and laurolactam.
  • Examples of preferred semiaromatic polyamides include poly(m-xylylene adipamide) (polyamide MXD,6), poly(dodecamethylene terephthalamide) (polyamide 12,T), poly(decamethylene terephthalamide) (polyamide 10,T), poly(nonamethylene terephthalamide) (polyamide 9,T), hexamethylene adipamide/hexamethylene terephthalamide copolyamide (polyamide 6,T/6,6), hexamethylene terephthalamide/2- methylpentamethylene terephthalamide copolyamide (polyamide 6.T/D.T); hexamethylene adipamide/hexamethylene terephthalamide/hexamethytene isophthalamide copolyamide (polyamide 6,6/6,T/6,l); poly(caprolactam-hexamethylene terephthalamide) (polyamide 6/6, T); hexamethylene terephthalamide/hexamethylene iso
  • the polyamide component a) may further comprise one or more aliphatic and/or alicyclic polyamides.
  • the aliphatic and/or alicyclic polyamides may be derived from aliphatic and/or alicyclic monomers, such as one or more of adipic acid, sebacic acid, azelaic acid, dodecanedoic acid, or their derivatives and the like, aliphatic C 6 -C 2 oalkyl- enediamines, alicyclic diamines, lactams, and amino acids.
  • Preferred diamines include bis(p-aminocyclohexyl)methane; hexamethylenediamine; 2-methylpentamethylene- diamine; 2-methyloctamethylenediamine; trimethylhexamethylenediamine; 1 ,8-diami- nooctane; 1 ,9-diaminononane; 1 ,10-diaminodecane; 1 ,12-diaminododecane; and m- xylylenediamine.
  • Preferred lactams or amino acids include 1 1 -aminododecanoic acid, caprolactam, and laurolactam.
  • Preferred aliphatic polyamides include aliphatic polyamides, such as polyamide 6; polyamide 6,6; polyamide 4,6; polyamide 6,10; polyamide 6,12; polyamide 1 1 ;
  • polyamide 12 polyamide 9,10; polyamide 9,12; polyamide 9,13; polyamide 9,14;
  • Polyamide component a) is present in the composition in about 30.0 to about 90.0 wt.-%, or more preferably in about 30.0 to about 80.0 wt.-%, or yet more preferably in about 30.0 to about 70.0 wt.-%, whereby the weight percentage amounts are based on the total weight of the composition.
  • the other hydrogen atom may be substituted by phenyl or other organic substituents, such as CrC 8 alkyl.
  • phosphinic acid also comprises within its scope the tautomeric form HP(OH) 2 , wherein the hydrogen atom which is directly attached to the phosphorus atom is substi- tuted by phenyl.
  • salt of phosphinic acid comprises within its scope preferably a metal salt, for example an alkali metal or alkaline earth metal salt, e.g. the sodium, potassium, magnesium or calcium salt or the iron(ll), iron(lll), zinc or boron salt.
  • a metal salt for example an alkali metal or alkaline earth metal salt, e.g. the sodium, potassium, magnesium or calcium salt or the iron(ll), iron(lll), zinc or boron salt.
  • R 1 and R 2 defined as CrC 8 alkyl is straight or, where possible branched CrC 8 alkyl and is for example methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl or 2- ethylhexyl.
  • R 3 defined as CrCi 0 alkylene is straight chain or, where possible branched CrCi 0 alk- ylene, e.g. methylene, ethylene, 1 ,2- or 1 ,3- propylene or 1 ,2-, 1 ,3- or 1 ,4-butylene.
  • R 3 defined as C 2 -Ci 0 alkylene interrupted by phenylene is, for example a bivalent group
  • R 3 defined as phenylene is 1 ,2-, 1 ,3- or 1 ,4-phenylene.
  • R 3 defined as (Ci-C 4 alkyl) 1-3 phenylene is, for example, 1 ,2-, 1 ,3- or 1 ,4-phenylene substituted by 1 -3 methyl or ethyl groups.
  • R 3 defined as phenyl-Ci-C 4 alkylene is, for example, one of the above-mentioned CrC 8 alkyl groups substituted by phenyl.
  • the composition comprises the aluminium salt of diphenylphosphinic acid.
  • the term salt comprises non-metallic salts, e.g. the acid addition salts obtainable by reaction of the above-defined phosphinic acid with ammonia, amines or amides, e.g. the (CrC 4 alkyl) 4 N + , (CrC 4 alkyl) 3 NH + ,
  • the ammonium, (Ci-C 4 alkyl) 1-4 ammonium or (2-hydroxy- ethyl) 1-4 ammonium, e.g. tetramethylammonium, tetraethylammonium, or the 2-hydro- xyethyltrimethylammonium, or the melamine or guanidine salt are particularly preferred.
  • the salt of a phosphinic acid (I) is represented by the formula
  • R 1 and R 2 represents hydrogen or a linear or branched CrC 8 alkyl radical, or a phenyl radical
  • Both of R 1 and R 2 represent phenyl.
  • M represents (C C 4 alkyl) 4 N, (Ci-C 4 alkyl) 3 NH, (C 2 -C 4 alkylOH) 4 N, (C 2 -C 4 alkylOH) 3 NH, (C 2 -C 4 alkylOH) 2 N(CH 3 ) 2!
  • n is a numeral from 1 -3 and indicates the number of positive charges on M; and n is a numeral from 1 -3 and indicates the number of phosphinic acid anions corresponding to M m+ .
  • the salt of a phosphinic acid (I) of Component a) is represented by the formula
  • the instant invention further pertains to the method of preparation of flame retardant compositions, which comprise, in addition to the components a) and b) defined above, optional components, such as additional flame retardants and/or further additives se- lected from the group consisting of tetraalkylpipendine additives, smoke suppressants, polymer stabilizers, fillers, reinforcing agents and so-called anti-dripping agents that reduce the melt flow of thermoplastic polymers and reduce the formation of drops at higher temperatures.
  • optional components such as additional flame retardants and/or further additives se- lected from the group consisting of tetraalkylpipendine additives, smoke suppressants, polymer stabilizers, fillers, reinforcing agents and so-called anti-dripping agents that reduce the melt flow of thermoplastic polymers and reduce the formation of drops at higher temperatures.
  • Such additional flame retardants are phosphorus containing flame retardants, for ex- ample selected from the group consisting of phosphorus and/or nitrogen containing flame retardants, organo-halogen containing flame retardants and inorganic flame retardants.
  • the process comprises mixing together components a) and b) with at least one additional nitrogen containing flame retardant com- pound c) selected from the group consisting of melamine polyphosphate, ammonium polyphosphate, melamine ammonium phosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate, a condensation product of melamine with phosphoric acid and other reaction products of melamine with phosphoric acid and mixtures thereof.
  • additional nitrogen containing flame retardant com- pound c) selected from the group consisting of melamine polyphosphate, ammonium polyphosphate, melamine ammonium phosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate, a condensation product of melamine with phosphoric acid and other reaction products of melamine with phosphoric acid and mixtures thereof.
  • Other condensation products of melamine like melam, melem and melon are also part of the preferred embodiment.
  • the process comprises mixing together Components a) and b) with melamine polyphosphate as additional flame retardant compound.
  • the process comprises mixing together Components a) and b) and further additives c) suitable for the preparation of high-melting poly- amide compositions selected from the group consisting of tetraalkylpiperidine additives, polymer stabilizers, fillers, reinforcing agents and so-called anti-dripping agents that reduce the melt flow of thermoplastic polymers and reduce the formation of drops at higher temperatures.
  • Phosphorus containing flame retardants are, for example, resorcinol phenylphosphate oligomer (Fyrolflex ® RDP, Akzo Nobel), triphenyl phosphate, bisphenol A phenylphosphate oligomer (Fyrolflex® BDP), tris(2,4-di-tert-butylphenyl)phosphate, ethylenedia- mine diphosphate (EDAP), tetra(2,6-dimethylphenyl) resorcinol diphosphate, diethyl- N,N-bis(2-hydroxyethyl)-aminomethyl phosphonate, hydroxyalkyi esters of phosphorus acids, salts of hypophosphoric acid (H 3 P0 2 ), particularly the Ca 2+ , Zn 2+ , or Al 3+ salts, tetrakis(hydroxymethyl)phosphonium sulphide, triphenylphosphine, triphenyl phosphine oxide, tetra
  • Nitrogen containing flame retardants are, for example, isocyanurate flame retardants, such as polyisocyanurate, esters of isocyanuric acid or isocyanurates.
  • isocyanurate flame retardants such as polyisocyanurate, esters of isocyanuric acid or isocyanurates.
  • Representative examples are hydroxyalkyi isocyanurates, such as tris-(2-hydroxyethyl)isocyanurate, tris(hydroxymethyl)isocyanurate, tris(3-hydroxy-n-proyl)isocyanurate or triglycidyl isocyanurate.
  • Nitrogen containing flame-retardants furthermore include melamine-based flame retardants.
  • Representative examples are: melamine cyanurate, melamine borate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine am- monium polyphosphate, melamine ammonium pyrophosphate, dimelamine phosphate and dimelamine pyrophosphate.
  • benzoguanamine allantoin, glycoluril, urea cyanurate, ammonium polyphosphate, and a condensation product of melamine from the series melem, melam, melon and/or a higher condensed compound or a reaction product of melamine with phosphoric acid or a mixture thereof.
  • organo-halogen flame retardants are, for example:
  • organohalogen flame retardants mentioned above are routinely combined with an inorganic oxide synergist. Most common for this use are zinc or antimony oxides, e.g. Sb 2 0 3 or Sb 2 0 5 . Boron compounds are suitable, too.
  • Representative inorganic flame retardants include, for example, aluminium trihydroxide (ATH), boehmite (AIOOH), magnesium dihydroxide (MDH), hydrotalcite, zinc borates, CaC0 3 , (organically modified) layered silicates, (organically modified) layered double hydroxides, and mixtures thereof.
  • the above-mentioned additional flame retardant classes are advantageously contained in the composition of the invention in an amount from about 0.5% to about 75.0% by weight of the organic polymer substrate; for instance about 10.0% to about 70.0%; for example about 25.0% to about 65.0% by weight, based on the total weight of the composition.
  • the invention relates to compositions which additionally comprise as additional component so-called anti-dripping agents.
  • Suitable additives that inhibit the formation of drops at high temperatures include glass fibres, polytetrafluoroethylene (PTFE), high temperature elastomers, carbon fibres, glass spheres and the like.
  • PTFE polytetrafluoroethylene
  • compositions which addi- tionally comprise as additional components fillers and reinforcing agents.
  • suitable fillers are, for example, glass powder, glass microspheres, silica, mica, wollastonite and talcum.
  • Stabilizers are preferably halogen-free and selected from the group consisting of ni- troxyl stabilizers, nitrone stabilizers, amine oxide stabilizers, benzofuranone stabilizers, phosphite and phosphonite stabilizers, quinone methide stabilizers and monoacrylate esters of 2,2'-alkylidenebisphenol stabilizers.
  • the composition according to the invention may additionally contain one or more conventional additives, for example selected from the group consisting of pigments, dyes, plasticizers, antioxidants, thixotropic agents, levelling assistants, basic co-stabilizers, metal passivators, metal oxides, organophosphorus compound, UV-absorbers and further light stabilizers and mixtures thereof, especially pigments, phenolic antioxidants, calcium stearate, zinc stearate and UV absorbers of the 2-hydro- xy-benzophenone, 2-(2'-hydroxyphenyl)benzotriazole and/or 2-(2-hydroxyphenyl)- 1 ,3,5-triazine and benzoate groups, such as 2,4-Di-tert-butylphenyl 3,5-di-tert-butyl-4- hydroxybenzoate (TINUVIN 120) or hexadecyl 3,5-bis-tert-butyl-4-hydroxybenzoate (Cytec Cyasorb®UV 2908.
  • additives for
  • Preferred additional additives for the compositions as defined above are processing stabilizers, such as the above-mentioned phosphites and phenolic antioxidants, and light stabilizers, such as benzotriazoles.
  • Preferred specific antioxidants include octade- cyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX 1076), pentaerythritol- tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (IRGANOX 1010), tris(3,5-di- tert-butyl-4-hydroxyphenyl)isocyanurate (IRGANOX 31 14), 1 ,3,5-trimethyl-2,4,6- tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (IRGANOX 1330), triethyleneglycol- bis[3-(3- tert-
  • Specific processing stabilizers include tris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS 168), 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphas- piro[5.5]undecane (IRGAFOS 126), 2,2',2"-nitrilo[triethyl-tris(3,3',5,5'-tetra-tert-butyl- 1 ,1 '-biphenyl-2,2'-diyl)]phosphite (IRGAFOS 12), and tetrakis(2,4-di-tert-butylphenyl)- [1 ,1 -biphenyl]-4,4'-diylbisphosphonite (IRGAFOS P-EPQ).
  • compositions comprise as an optional component the additional flame retardants defined above and additives selected from the group consisting of polymer stabilizers and tetraalkylpiperidine derivatives.
  • additional flame retardants selected from the group consisting of polymer stabilizers and tetraalkylpiperidine derivatives.
  • tetraalkylpiperidine derivatives are selected from the group consisting of
  • the oligomeric compound which is the condensation product of 4,4'-hexame- thylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1 -cyclo- hexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine,
  • n is a numeral from 1 to 15.
  • the additives mentioned above are preferably contained in the composition in an amount of 0.01 to 10.0%, especially 0.05 to 5.0%, relative to the weight of the polyam- ide substrate of Component a).
  • thermoplastic polymers include polyolefin homo- and copolymers, copolymers of olefin vinyl monomers, styrenic homopolymers and copolymers thereof and polyesters.
  • resins can be applied to blend, e. g. urethane resins, acryl resins, fluoro resins, silicon resins, imide resins, amide imide resins, epoxy resins, urea resins, alkyd resins and melamine resins.
  • Additional polymers can be ethylene copolymerisate, e. g. copolymers of ethylen, 1 - octene, 1 -butene, such as the one as described in WO 2008/074687.
  • the molecular weights are particularly up to 500 000 g/mol, more particulary in the range of 15000 to 400000 g/mol.
  • Further thermoplastic resins are described in JP-A 2009-155436.
  • copolymers from ethylen, n-butylacrylate, acrylic acid and maleic acid anhydride which is inter alia known as Lupolen® KR1270 from BASF SE.
  • Rubbers can be ethylene-propylene-diene rubbers (EPDM), styrene- butadiene rubbers (SBR), butadiene rubber, nitrile rubber (NBR), hydrin rubber (ECO) or/and acrylate rubbers (ASA). Silicon based rubbers can be applied.
  • EPDM ethylene-propylene-diene rubbers
  • SBR styrene- butadiene rubbers
  • NBR nitrile rubber
  • ECO hydrin rubber
  • ASA acrylate rubbers
  • the components defined above are ground to a fine powder with an average particle size below 100 ⁇ prior to their application in polymer substrates as it is known that the flame retardant properties are improved by small particle sizes.
  • the incorporation of the components defined above into the polyamide is carried out by known methods, such as dry blending in the form of a powder.
  • the additive compo- nents a) and b) and optional further additives may be incorporated, for example, before or after molding. They may be added directly into the processing apparatus (e.g. extruders, internal mixers, etc.), e.g. as a dry mixture or powder.
  • the addition of the additive components to the polymer substrate can be carried out in customary mixing machines in which the polyamide is melted and mixed with the addi- tives. Suitable machines are known to those skilled in the art. They are predominantly mixers, kneaders and extruders.
  • the process is preferably carried out in an extruder by introducing the additive during processing, particularly at elevated temperatures at or above 280°C.
  • Particularly preferred processing machines are single-screw extruders, contra-rotating and co-rotating twin-screw extruders, planetary-gear extruders, ring extruders or co- kneaders.
  • Processing machines provided with at least one gas removal compartment can be used to which a vacuum can be applied.
  • the screw length is 1 - 60 screw diameters, preferably 35-48 screw diameters.
  • the rotational speed of the screw is preferably 10 - 600 rotations per minute (rpm), preferably 25 - 300 rpm.
  • the maximum throughput is dependent on the screw diameter, the rotational speed and the driving force.
  • the process of the present invention can also be carried out at a level lower than maximum throughput by varying the parameters mentioned or employing weighing machines delivering dosage amounts.
  • the additive components a) and b) optional further additives can also be added to the polymer in the form of a master batch ("concentrate") which contains the components in a concentration of, for example, about 1.0% to about 40.0% and preferably 2.0% to about 20.0% by weight incorporated in a polymer.
  • concentration a master batch
  • the polymer is not necessarily of identical structure than the polymer where the additives are added finally.
  • the polymer can be used in the form of powder, granules, solutions, and sus- pensions or in the form of lattices.
  • Incorporation can take place prior to or during the shaping operation.
  • the materials containing the additives of the invention described herein preferably are used for the production of molded articles, for example roto-molded articles, injection molded articles, profiles and the like, and especially a fibre, spun melt non-woven, film or foam.
  • molded articles for example roto-molded articles, injection molded articles, profiles and the like, and especially a fibre, spun melt non-woven, film or foam.
  • antioxidant Irganox 1098 BASF SE
  • impact modifier Lupolen KR1270® BASF SE
  • und lubricant Alugel®30DF Barlocher
  • thermoplastic compositions are processed by a twin-screw extruder ZSK 25- F41 , Leistritz with a screw velocity of 380 min "1 , a throughput of 30 kg/h and a vacuum of 200 mbar.
  • the temperature of the extruder is held at 320°C.
  • the blended compositions are cooled and cut into pel- lets. After drying the pellets are injected molded at 320-350°C to the desired specimen geometry.
  • the testing is performed according to standards of Underwriter laboratories and samples with dimensions of 125 mm x 13 mm in three different thickness sizes respectively. Before testing the samples are conditioned for 48 h at 23°C and
  • the LOI test is performed according to ISO 4589-2.
  • the oxygen index test measures the minimum concentration of oxygen in a flowing mixture of oxygen and nitrogen that will just support flaming combustion. Polymers with a LOI of 23 or lower are estimated as highly combustible.
  • a sample is placed in the holder at the center of the base of the test column (450-500 mm x 75-100 mm).
  • the flow valves are adjusted to obtain the desired initial oxygen concentration and total flow rate.
  • the oxygen and nitrogen flow into the dispersion chamber and through the glass bead bed the gases thus are mixed and dispersed evenly over the cross section of the test column.
  • the specimen 125 mm x 6.5 mm x 1.6 mm is ignited, so the entire top tip of the specimen is burning like a candle.
  • a gas flame at the end of a tube with a small orifice is used to ignite the specimen.
  • the oxygen concentration is above the oxygen index if the specimen burns for at least 3 minutes after the igniter is removed, or if the specimen burns down 50 mm.
  • the concentration is below the oxygen index if the specimen stops flaming before the criteria (3 min. or 50 mm) are satisfied.
  • the procedure is repeated with a new specimen and a higher or lower oxygen concentration until the lowest con- centration of oxygen that will satisfy the criteria is determined.
  • the concentration in percentage is reported as the oxygen index.
  • Phosphorus-containing flame retardants are able to disproportionate in the presence of water and oxygen from air forming water-soluble phosphor-containing compounds.
  • 80 g of the respective compound with the geometry of 50x6x4mm are stored in 150 ml water of 60°C in a 300 ml beaker. The volume of water is kept constant. After a definite storage time (14/30/50/100 days) the phosphor content of the aqueous solution in mg/l is determined by ICP-OES (inductively coupled plasma - optical emission spectroscopy).
  • test compositions 10 kg are processed by an Arburg 270S injection mold- ing machine.
  • the screw diameter is 25 mm, screw speed 100/min, cycle time 30 sec, injection time 0.5 sec, cylinder temperature 275-285°C, nozzle temperature 290°C.
  • the respective mold has to following geometry: 50 mm x 50 mm x 0.4 mm.

Abstract

La présente invention concerne un procédé de préparation de compositions thermoplastiques ignifuges de polyamide, présentant des effets de réduction de la corrosion sur un équipement de traitement de masses fondues. Les ingrédients actifs consistent en des phosphinates.
PCT/EP2013/065752 2012-07-27 2013-07-25 Préparation de compositions ignifuges anticorrosives de polyamide, contenant des phosphinates WO2014016386A1 (fr)

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US201261676352P 2012-07-27 2012-07-27
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EP12178236 2012-07-27
EP12178236.1 2012-07-27

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CN116656125A (zh) * 2023-05-19 2023-08-29 江苏金发科技新材料有限公司 一种尼龙材料及其制备方法

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