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WO2005059030A1 - Matieres moulees a base de polyoxymethylene et leur utilisation - Google Patents

Matieres moulees a base de polyoxymethylene et leur utilisation Download PDF

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Publication number
WO2005059030A1
WO2005059030A1 PCT/EP2004/014395 EP2004014395W WO2005059030A1 WO 2005059030 A1 WO2005059030 A1 WO 2005059030A1 EP 2004014395 W EP2004014395 W EP 2004014395W WO 2005059030 A1 WO2005059030 A1 WO 2005059030A1
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WIPO (PCT)
Prior art keywords
pigments
carbon atoms
radicals
compositions according
nitrogen
Prior art date
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PCT/EP2004/014395
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German (de)
English (en)
Inventor
Stefan Wulf
Klaus Kurz
Christine KÖSTLER
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Ticona Gmbh
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Publication date
Priority claimed from DE200410008722 external-priority patent/DE102004008722A1/de
Application filed by Ticona Gmbh filed Critical Ticona Gmbh
Priority to EP04816306A priority Critical patent/EP1704184A1/fr
Publication of WO2005059030A1 publication Critical patent/WO2005059030A1/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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals

Definitions

  • the present invention relates to new polyoxymethylene molding compositions with good internal sliding properties and low formaldehyde emissions.
  • Typical formaldehyde scavengers for POM molding compositions are melamine, melamine-formaldehyde condensates (MFK), aminopyridines, guanamines or allantoin.
  • the efficiency of the formaldehyde scavengers depends, among other things, on the amount of additives that are mixed into the molding compositions. Basically, therefore aiming for the highest possible amount of these additives.
  • high amounts of additives can impair the processing properties of the molding compositions or lead to a deterioration in the quality of the products produced, for example as a result of the increased formation of mold coatings.
  • Typical lubricants are unmodified or oxidized polyolefin waxes or esters or amides of long-chain carboxylic acids. So far, ester waxes or amide waxes have been used. Typical representatives of these compounds are, for example, stearates or montanates which have been reacted with ethanediol, propanediol or ethylenediamine.
  • inter lubricants i.e. additives that are used in the POM molding composition, in contrast to “external lubricants”, which e.g. are used as mold release agents and are used as coatings for molds.
  • POM molding compositions to which polyester amides have been added are also known.
  • RU-A-2,039,772 describes casting compounds, the POM, branched Polycarbonate contains selected inorganic additives and ester amide wax.
  • US-A-4,439,565 describes oligomeric polyester amides with sterically hindered amine side groups, which can be used as stabilizers against thermal or radiation-induced degradation in polymers.
  • DE-A-1, 768,384 describes bis-oxalic acid ester amides as stabilizers for polymers. In the
  • GB-A-1, 165, 236 describes a process for stabilizing POM, in which inter alia formaldehyde acceptors, for example polyesteamides, are added.
  • DE-A-10052 763 describes nucleated POM molding compositions with an increased crystallization rate. These can contain amides of long-chain fatty acids or bis-esters of long-chain fatty acids as lubricants.
  • the invention provides POM molding compositions which contain selected additives which on the one hand have nitrogen atoms with sufficient basicity so that the formaldehyde emission of the molding composition is reduced without other disadvantages for the POM, e.g. increased tendency to yellowing or formation of mold coverings, which also have residues derived from long-chain carboxylic acids, so that an additional sliding effect is imparted and thus the mechanical damage to the molten POM molding composition is reduced, which is one of the causes of the
  • the object of the present invention is to provide new POM molding compositions which, in addition to a low emission of formaldehyde during production and processing, have excellent sliding properties.
  • the present invention relates to compositions comprising a) at least one polyoxymethylene homo- and / or copolymer, and b) at least one ester wax containing at least one ester group derived from a carboxylic acid containing six to one hundred carbon atoms and at least one primary, secondary or tertiary amino group and / or at least a nitrogen-containing heterocycle and / or at least one amide wax derived from aliphatic monoamines having six to thirty carbon atoms or a heterocycle containing an amino group containing nitrogen and a carboxylic acid containing six to one hundred carbon atoms.
  • the polyoxymethylenes (POM), as described, for example, in DE-A 29 47 490, are generally unbranched linear polymers which are generally at least 80%, preferably at least 90%,
  • polyoxy-methylene Contain oxymethylene units (-CH 2 -O-).
  • polyoxy-methylene includes both homopolymers of formaldehyde or its cyclic oligomers, such as trioxane or tetroxane, and corresponding copolymers.
  • Homopolymers of formaldehyde or trioxane are those polymers whose
  • Hydroxyl end groups are chemically stabilized against degradation in a known manner, e.g. B. by esterification or by etherification.
  • Copolymers are polymers of formaldehyde or its cyclic oligomers, in particular trioxane, and cyclic ethers, cyclic acetals and / or linear polyacetals.
  • these polymers have at least 50 mol% of recurring units -CH 2 -O- in the main polymer chain.
  • the homopolymers are generally prepared by polymerizing formaldehyde or trioxane, preferably in the presence of suitable catalysts.
  • POM copolymers are preferred, in particular those which, in addition to the repeating units -CH 2 -O-, also contain up to 50, preferably from 0.1 to 20 and in particular 0.5 to 10 mol% of repeating units
  • R 1 to R 4 independently of one another are a hydrogen atom, a C to C 4 alkyl group or a halogen-substituted alkyl group having 1 to 4 C atoms and R 5 is a -CH2-, -O-CH 2 -, ad- to C 4 alkyl or C to C 4 haloalkyl substituted methylene group or a corresponding oxymethylene group and n has a value in the range from 0 to 3.
  • cyclic ethers are those of
  • Examples include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 1,3-dioxane, 1,3-dioxolane and 1,3-dioxepane as cyclic ethers and linear oligo- or polyformals, such as polydioxolane or polydioxepane, mentioned as comonomers.
  • Copolymers of 99.5-95 mol% of trioxane and 0.5 to 5 mol% of one of the aforementioned comonomers are used particularly advantageously.
  • polyoxymethylenes are oxymethylene terpolymers which for example by reacting trioxane, one of the cyclic ethers described above and with a third monomer, preferably
  • Preferred monomers of this type are ethylene diglycide, diglycidyl ether and diether from glycidylene and formaldehyde, dioxane or trioxane in a molar ratio of 2: 1, and diether from 2 mol of glycidyl compound and 1 mol of an aliphatic diol having 2 to 8 carbon atoms, such as, for example, the diglycidyl ether of ethylene glycol , 1, 4-butanediol,
  • the preferred POM copolymers have melting points of at least 150 ° C. and molecular weights (weight average) M w in the range from 5,000 to 200,000, preferably from 7,000 to 150,000.
  • End-group stabilized POM polymers which have C-C bonds or the methoxy end groups at the chain ends are particularly preferred.
  • the used POM-polymers generally have a melt index (MVR value at 190 ° C / 2, 16 kg) of 2 to 50 cm 3/10 min (ISO 1133).
  • Component b) of the compositions according to the invention are ester waxes derived from at least one carboxylic acid containing six to one hundred carbon atoms, which by esterification of a mono- or polyvalent Alcohol containing at least one primary, secondary or tertiary amino group and / or by esterification of a mono- or polyhydric alcohol containing at least one nitrogen-containing heterocycle; or component b) is selected amide waxes with an amide group which are derived from aliphatic monoamines with six to twenty
  • the carboxylic acids typically have one to two and in particular one
  • Carboxyl group and preferably eight to fifty, in particular twenty to thirty-five, carbon atoms.
  • the carboxylic acids can be aromatic, heterocyclic, araliphatic, cycloaliphatic or aliphatic, the heterocyclic, araliphatic, cycloaliphatic or aliphatic compounds also being unsaturated or, in particular, saturated. It is preferably aliphatic carboxylic acids, in particular saturated aliphatic carboxylic acids.
  • carboxylic acids are lauric acid, myristic acid,
  • the amino alcohols required for the preparation of component b) to be used according to the invention can be aromatic, heterocyclic, araliphatic, cycloaliphatic or aliphatic, the heterocyclic, araliphatic, cycloaliphatic or aliphatic compounds also being unsaturated, preferably ethylenically unsaturated, or in particular saturated. They are preferably aliphatic amino alcohols, in particular saturated aliphatic amino alcohols.
  • component b) containing nitrogen atoms and at least one alcohol group can be prepared Heterocycles are used.
  • the heterocycles preferably have one nitrogen atom or two nitrogen atoms or one nitrogen atom and one oxygen atom. They are typically five- to seven-membered heterocycles that can be unsaturated or saturated.
  • heterocyclic radicals are Pyrrolyi, oxazolyl, imidazolyl, isoxazolyl, pyrazolyl, oxadiazolyl, triazolyl, indolyl, isoindolyl, benzoxazolyl, benzimidazolyl, benzisoxazolyl, benzopyrazolyl, benzotriazolyl, carbazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl , Quinazolinyl, cinnolinyl, naphthyridinyl, pyridopyrimidinyl, purinyl, pteridinyl,
  • Substituents with an alcohol group preferably a methylol group or a 1-hydroxyethyl group.
  • substituents are halogen, alkyl, alkoxy, hydroxyl, amino (unsubstituted, mono- or disubstituted), carboxyl, alkoxycarbonyl, alkylcarbonyl,
  • Haloalkyl and oxo An example of a nitrogen-containing heterocyclic radical containing oxo groups is 2,5-dioxo-4-imidazolidinyl.
  • Heterocycles can also arise from the reaction of amino alcohols with long-chain carboxylic acids.
  • Tris when implementing Tris
  • the amino alcohols typically have two to fourteen carbon atoms, especially two to six carbon atoms.
  • Examples of amino alcohols are 2-aminophenol, 4-amino-cyclohexanol, aminoethanol, diethanolamine, tris (hydroxymethyl) aminomethane, 3-amino-propanol or 4-amino-butanol.
  • the nitrogen-containing heterocycles can have several ring nitrogen atoms and / or hydroxy functionalities, preferably one to three hydroxyl groups and one or two ring nitrogen atoms.
  • the aliphatic amines required for the production of component b) to be used according to the invention can be unsaturated or, in particular, saturated.
  • the amines have six to twenty two carbon atoms, especially ten to eighteen carbon atoms.
  • amines are fatty amines (also called taigamines), laurylamine, myristylamine, palmitylamine, stearylamine, oleylamine, arachidylamine or behenylamine.
  • heterocyclic aliphatic amines required for the production of component b) to be used according to the invention can be unsaturated or saturated.
  • Preferred components b) are compounds of the formulas I, II, III, IV, V and / or
  • R 10 , R 12 and R 14 are independently monovalent aliphatic, cycloaliphatic, heterocyclic, aromatic or araliphatic radicals having six to one hundred carbon atoms, or R 10 and R 12 or R 10 and R 14 or R 12 and R 14 together form a divalent aliphatic, cycloaliphatic, heterocyclic, aromatic or araliphatic radical with six to one hundred carbon atoms, R 9 , R 11 , R 13 and R 6 independently of one another are divalent aliphatic, cycloaliphatic, heterocyclic, aromatic or araliphatic radicals,
  • R 9a and R 11a independently of one another are a covalent bond or divalent aliphatic, cycloaliphatic, heterocyclic, aromatic or araliphatic radicals
  • R 7 , R 8 , R 15 , R 17 and R 18 are independently hydrogen or monovalent aliphatic, cycloaliphatic, heterocyclic, aromatic or araliphatic
  • R 7 and R 8 or R 17 and R 18 or R 15 and R 18 together can form a saturated or unsaturated heterocycle containing at least one nitrogen atom, which may optionally have further ring hetero atoms, in particular a further nitrogen atom or oxygen atom, and
  • R 19 is a monovalent aliphatic radical having six to thirty carbon atoms or a heterocyclic radical containing nitrogen.
  • radicals are alkyl, these are generally saturated alkyl radicals with one to one hundred carbon atoms.
  • the alkyl radicals can be straight-chain or branched.
  • alkyl radicals can also carry inert substituents, for example alkoxy radicals with preferably one to six carbon atoms, or halogen atoms, such as chlorine, or the alkyl radicals can chain heteroatoms, such as
  • R 10 , R 12 and R 14 are alkyl radicals having eight to fifty, in particular twenty to thirty-five, carbon atoms.
  • R 7 , R 8 , R 15 , R 17 and R 18 are alkyl radicals having one to ten, in particular one to six, carbon atoms.
  • R 19 alkyl radicals have six to twenty-two, preferably ten to eighteen, carbon atoms.
  • radicals are cycloalkyl, these are generally saturated but also unsaturated cycloalkyl radicals having five to eight, preferably five or six, ring carbon atoms, which may also have one or two ring heteroatoms, such as nitrogen, sulfur or oxygen, and, if appropriate, one or more alkylene chains can have.
  • the cycloalkyl radicals can also carry inert substituents, for example alkyl or alkoxy radicals with preferably one to six carbon atoms, or halogen atoms, such as chlorine.
  • Cyclopentyl or cyclohexyl are preferred.
  • radicals mean aryl, these are generally aromatic hydrocarbon radicals with one or two aromatic nuclei.
  • radicals are heterocyclic radicals, these are saturated or unsaturated hydrocarbon radicals, including the aromatic hydrocarbon radicals, which can have one, two or three ring heteroatoms, such as nitrogen, sulfur or oxygen. Typically, there are two interconnected ring systems or preferably one ring system. Heterocycles containing nitrogen or nitrogen and oxygen are preferred.
  • aryl radicals or heterocyclic radicals can also carry inert substituents, for example alkyl or alkoxy radicals having preferably one to six carbon atoms, or halogen atoms, such as chlorine.
  • the preferred aryl radical is phenyl.
  • Preferred heterocyclic radicals are 4-methylene- ⁇ 2 -oxazolinyl, 1, 3,5-triazinyl or 2,5-dioxy-4-imidazolidinyl.
  • radicals are aralkyl, these are generally aromatic hydrocarbon radicals having one or two aromatic nuclei, which may also have one or two ring heteroatoms, such as nitrogen, sulfur or oxygen, and which furthermore have at least one alkylene chain.
  • the aralkyl radicals can also carry inert substituents, for example alkyl or alkoxy radicals with preferably one to six carbon atoms, or halogen atoms, such as chlorine.
  • any radicals mean divalent alkyl radicals (alkylene), these are generally saturated alkylene radicals having one to twenty carbon atoms.
  • the alkylene radicals can be straight-chain or branched.
  • the alkylene radicals can also carry inert substituents, for example alkoxy radicals having preferably one to six carbon atoms, or halogen atoms, such as chlorine, or the alkylene radicals can have heteroatoms in the chain, such as oxygen atoms or -NH groups, or heterocyclic, aromatic or cycloaliphatic groups.
  • Alkylene radicals having one to ten carbon atoms are preferred. Methylene, ethylene or propylene are particularly preferred.
  • radicals mean divalent cycloalkyl radicals (cycloalkylene), these are generally saturated or unsaturated cycloalkylene radicals having five to eight, preferably five or six, ring carbon atoms, which may also have one or two ring heteroatoms, such as nitrogen, sulfur or Oxygen and optionally one or more alkylene chains.
  • the cycloalkylene radicals can also carry inert substituents, for example alkyl or alkoxy radicals with preferably one to six
  • Cyclopentylene or cyclohexylene are preferred.
  • radicals mean divalent aryl radicals (arylene), these are generally aromatic hydrocarbon radicals with one or two aromatic nuclei.
  • radicals mean divalent heterocyclic radicals, they are divalent saturated or divalent unsaturated
  • Hydrocarbon residues including aromatic hydrocarbon residues, which may have one, two or three ring heteroatoms such as nitrogen, sulfur or oxygen. Typically, there are two interconnected ring systems or preferably one ring system. Heterocycles containing nitrogen or nitrogen and oxygen are preferred.
  • arylene radicals or heterocyclic radicals can also carry inert substituents, for example alkyl or alkoxy radicals having preferably one to six carbon atoms, or halogen atoms, such as chlorine.
  • phenylene especially 1, 3- and 1, 4-phenylene, biphen-4,4'-diyl, diphenylmethane-4,4'-diyl, naphthylene or especially 4,4-bis-methylene- ⁇ 2 - and oxazolindiyl 1, 3,5-triazinediyl.
  • radicals mean divalent aralkyl radicals (aralkylene), these are generally aromatic hydrocarbon radicals with one or two aromatic nuclei, which may also have one or two ring heteroatoms, such as May have nitrogen, sulfur or oxygen and which furthermore have an alkylene chain.
  • aralkylene radicals can also carry inert substituents, for example alkyl or alkoxy radicals with preferably one to six
  • Preferred components b) are derived from acids from montan waxes, in particular by reaction with amino alcohols, in particular with diethanolamine or with triethanolamine and / or with primary long-chain monoamines
  • compositions are particularly preferred in which component b) has ester groups or amide groups which are derived from monovalent carboxylic acids having eight to thirty-five carbon atoms, in particular from lauric acid, palmitic acid, oleic acid, stearic acid, behenic acid or from acids from montan wax.
  • Compositions are particularly preferred in which component b) is derived from diethanolamine, from triethanolamine or from 4,4-bis (hydroxymethyl) - ⁇ 2 - derived oxazoline, which are esterified with monovalent carboxylic acids with eight to thirty-five carbon atoms.
  • the invention further relates to the use of ester waxes containing at least one of six to one hundred carbon atoms
  • the components b) used according to the invention can be obtained by processes known per se by reacting amino alcohols of the formulas Ia to Va and / or primary amines of the formula Via with one or more mono- and / or dicarboxylic acids of the formulas X or XI
  • R 7 , R 8 , R 9 , R 9a , R 10 , R 11 , R 11a , R 13 , R 15 , R 16 , R 17 , R 18 and R 19 have the meaning defined above, wherein R 10 also R Can be 12 or R 14 , and wherein R 10 is a divalent aliphatic, cycloaliphatic, heterocyclic, aromatic or araliphatic radical having six to one hundred carbon atoms.
  • the compounds of the formulas X and / or XI are used in such an amount that the free alcohol groups of the compounds of the Formulas la to Va or the free amide group of the compound of the formula Via are each reacted by a carboxyl group or carboxyl derivative group of the compound of the formula X and / or XI.
  • the reaction is typically carried out in an organic solvent, for example in dipolar aprotic solvents, such as dimethyl sulfoxide (DMSO), or in aromatic hydrocarbons, such as toluene or xylene, which are liquid at reaction temperatures.
  • dipolar aprotic solvents such as dimethyl sulfoxide (DMSO)
  • aromatic hydrocarbons such as toluene or xylene
  • the reaction is usually carried out in the presence of a catalyst of the ester and
  • the reaction temperatures are usually 0 to 220 ° C, preferably 30 to 150 ° C.
  • the first stage of the reaction usually takes place at lower temperatures, for example at 0 to 50 ° C.
  • the second stage of the reaction usually takes place at higher temperatures, for example at 50 to 150 ° C. It is of course also possible to carry out both reaction stages at the same temperature.
  • compositions according to the invention usually contain 75 to 99.99% by weight, preferably 80 to 99.8% by weight, of POM homo- or copolymer
  • Component a (Component a)) and 0.01 to 5% by weight, preferably 0.2 to 0.5% by weight of component b), these details each relating to the overall composition.
  • compositions according to the invention may also contain other additives known per se.
  • processing aids such as antioxidants, acid scavengers and others Formaldehyde scavengers, UV stabilizers, adhesion promoters, other lubricants, nucleating agents or mold release agents; Fillers, such as glass balls, calcium carbonate, talc, wollastonite or silicon dioxide; Reinforcing materials such as carbon fibers, aramid fibers or glass fibers; Antistatic agents or additives which impart a desired property to the molding composition, such as dyes and / or pigments and / or impact modifiers and / or additives which impart electrical conductivity, for example conductivity carbon blacks or metal particles, and mixtures of these additives, but without restricting the scope to the limit the examples mentioned.
  • processing aids such as antioxidants, acid scavengers and others Formaldehyde scavengers, UV stabilizers, adhesion promoters, other lubricants, nucleating agents or mold release agents
  • Fillers such as glass balls, calcium carbonate, tal
  • the proportion of these additives in the compositions according to the invention is usually 0.2 to 50% by weight, preferably 0.5 to 30% by weight, based on the total composition.
  • a preferred embodiment relates to compositions comprising, in addition to components a) and b), dyes and / or pigments.
  • Pigments are particularly preferably used, in particular titanium dioxide, very particularly preferably combined with carbon black.
  • compositions according to the invention particularly preferably contain titanium dioxide with further inorganic and / or organic pigments.
  • compositions according to the invention likewise particularly preferably contain titanium dioxide, carbon black and other inorganic and / or organic pigments.
  • the molding compositions colored according to the invention are distinguished by a surprisingly high stability against decomposition and release of formaldehyde during processing.
  • inorganic and / or organic dyes and / or pigments can be used.
  • inorganic pigments are iron oxide pigments, lead chromate pigments, ultramarine pigments, iron blue pigments, cobalt blue pigments, rutile pigments, in particular titanium dioxide, cadmium pigments, bismuth vanadate pigments, cerium sulfide pigments, complex inorganic colored pigments ( so-called
  • organic pigments examples include azo pigments such as monoazo yellow and mono orange pigments; Diazo pigments, ß-naphthol pigments, naphthol AS pigments, benzimidazolone pigments, diazo condensation pigments, metal complex pigments,
  • Isoindolinone and isoindoline pigments polycyclic pigments such as phthalocyanine pigments, quinacridone pigments, perylene and perinone pigments; Thioindigo pigments, anthraquinone pigments such as anthrapyrimidine pigments, flavanthrone pigments, pyranthrone pigments and anthanthrone pigments; Dioxazine pigments, triaryl carbonium pigments, quinophthalone pigments and diketo-pyrrolo-pyrrole
  • These pigments can be used either individually or as a mixture or together with polymer-soluble dyes.
  • antioxidants are phenolic compounds, such as N, N ' -bis-3- (3', 5 ' -ditert.butyl-4 ' -hydroxyphenyl) -propionylhydrazine, 1, 6-hexanediol-bis-3- (305 ' -di-tert.butyl-4'-hydroxyphenyl) propionate, 3,6-dioxaoctane-1,8-diol-bis-3- [3 ' -tert.butyl-4 ' - hydroxy-5 ' - (methylphenyl )] - propionate, N, N ' -hexamethylene-bis-3- (3 ' , 5 ' -di-tert.butyl- 4 ' -hydroxyphenyl) -propionamide, tetrakis [methylene-3- (3 ' , 5 ' -di-tert-butyl-4. '- hydroxyphenyl) -
  • esters and amides of a long-chain aliphatic carboxylic acid and an aliphatic alcohol are examples of further lubricants.
  • Polyethylene waxes preferably oxidized polyethylene waxes.
  • PE-UHMW ultra high molecular weight polyethylene
  • PTFE polytetrafluoroethylene
  • graft copolymers which is a product of a graft reaction of an olefin polymer and an acrylonitrile / styrene copolymer.
  • impact modifiers are polyurethanes with elastomers
  • grafted polymers containing, in addition to non-polar, also polar polymer segments, for example styrene-acrylonitrile copolymer grafted onto polyethylene, such as LDPE-SAN as described in EP-A-354.802 and EP-A-420.564, or particularly preferably polymers with a core shell - Structure which have a rubber-elastic core based on polybutadiene and a hard shell, as described in EP-A-156,285 and EP-A-668,317.
  • the starting materials (POM powder, antioxidant, hydrolysis stabilizer, optionally further stabilizers and internal lubricant: a total of 50 g) were compounded in an extruder and processed into granules.
  • the housing temperature of the kneading chamber of a_Brabender PlastiCorder was set to 200 ° C and a hopper (accessory of the Brabender kneader) was placed on the kneading chamber. As soon as the housing temperature had reached 190 ° C, the kneader was running
  • the granules (50 g in total) are filled into the funnel and then pressed into the kneading chamber by a displacer (wedge-shaped punch) with a bearing weight of 5 kg.
  • the mixture started to melt and as soon as the When the melting process was completed (short-term drop in torque), the filling funnel was removed and instead the cover with the purge gas supply line and exhaust pipe was put on. The formaldehyde content of the exhaust gas was measured continuously and the experiment was ended after a total of 60 minutes (from filling the granulate mixture).
  • VDA 275 determined (VDA recommendation no.275, Automotive Engineering Documentation July 1994).
  • Test specimen production The polyacetal granules were injection-molded into platelets with the dimensions 80 * 50 * 1 mm.
  • An Kraus Maffei injection molding machine An Kraus Maffei injection molding machine
  • test specimens were stored for 24 hours in a standard climatic cabinet at 23 ° C and 50 relative air humidity.
  • test Two test specimens were hung in a 1 liter glass bottle over 50 ml of electric water on a stainless steel hook and stored for 3 hours in a forced-air drying cabinet at 60 ° C. The test specimens were removed from the test bottle. 5 ml of sample solution were pipetted into a test tube, the test tube was annealed at 95 ° C. for 10 minutes. Now 3 ml of acetylacetone and 3 ml of a 20% ammonium acetate solution were added to the test tube. With the reagents, the formaldehyde formed the diacetyldihydrolutidine complex, the absorption of which was determined photometrically at 412 nm.
  • the formaldehyde concentration in the sample solution was calculated from the absorption.
  • the type Hostaform ® C9021 (copolymer 1, Ticona GmbH) was used as the POM in one test series, the type C27021 (copolymer 2, Ticona GmbH) in a second test series, and the type T1020 (terpolymer, Ticona GmbH) in a third test series.
  • Irganox 245 (CIBA) was used as an antioxidant in all test series and tricalcium citrate was used as a hydrolysis stabilizer.
  • Type C27021 was a pigmented product, while the other two types were unpigmented.
  • the table below shows the type and amount of the internal lubricant used, the melt flow index of the granulate, the amount of formaldehyde released during Brabender degradation and the formaldehyde emission of the POM molding compound determined in accordance with VDA 275.
  • Licowax C is an amide wax with two amide groups based on ethylenediamine and stearic acid (Clariant GmbH); NC 133 is an ester amide wax derived from diethanolamine and acids from montan waxes (Clariant GmbH); FH-G 370 is an amide wax derived from taigamines and acids from montan waxes with an amide group (Clariant GmbH); FH-G 408 is an ester wax (Clariant GmbH) derived from 4,4-bis (hydroxymethyl) - ⁇ 2 oxazoline and acids from montan waxes; FH-R 227 is an ester wax derived from triethanolamine and acids from montan waxes (Clariant GmbH)

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Abstract

L'invention concerne des compositions contenant a) au moins un homopolymérisat de polyoxyméthylène et/ou un copolymérisat de polyoxyméthylène et b) au moins une cire-ester contenant au moins un groupe ester dérivé d'un acide carboxylique contenant entre six et cent atomes de carbone et au moins un groupe amino primaire, secondaire ou tertiaire et/ou au moins un hétérocycle contenant de l'azote et/ou des cires d'amide dérivées de monoamines aliphatiques ayant entre six et vingt atomes de carbone ou d'un hétérocycle contenant de l'azote présentant des groupes amino et d'un acide carboxylique contenant entre six et cent atomes de carbone. Le constituant b) se prête à être utilisé comme capteur de formaldéhyde dans des matières moulées à base de polyoxyméthylène.
PCT/EP2004/014395 2003-12-18 2004-12-17 Matieres moulees a base de polyoxymethylene et leur utilisation WO2005059030A1 (fr)

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DE10359372 2003-12-18
DE10359372.1 2003-12-18
DE200410008722 DE102004008722A1 (de) 2004-02-23 2004-02-23 Polyoxymethylen Formmassen und deren Verwendung
DE102004008722.9 2004-02-23

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10030208B2 (en) 2013-10-21 2018-07-24 Celanese Sales Germany Gmbh Intrinsic low friction polyoxymethylene
US10196577B2 (en) 2015-09-30 2019-02-05 Celanese Sales Germany Gmbh Low friction squeak free assembly
US11827760B2 (en) 2017-03-10 2023-11-28 Celanese Sales Germany Gmbh Polyester polymer compositions

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