Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/12—Powdering or granulating
  • C08J3/122—Pulverisation by spraying
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L13/00—Compositions of rubbers containing carboxyl groups
  • C08L13/02—Latex
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L21/00—Compositions of unspecified rubbers
• • 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
• • 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
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08L9/10—Latex
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2321/00—Characterised by the use of unspecified rubbers
  • C08J2321/02—Latex
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/14—Peroxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
  • C08L11/02—Latex
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L21/00—Compositions of unspecified rubbers
  • C08L21/02—Latex
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
  • C08L9/02—Copolymers with acrylonitrile
  • C08L9/04—Latex
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
  • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
  • Y10T428/1393—Multilayer [continuous layer]

Definitions

• the invention relates to polyamide-elastomer blends having improved hydrolysis resistance.
• the elastomer is present in particular in the form of a microgel.
• the polyamide-elastomer mixtures according to the invention can be processed into molded parts which are used, for example, in the automotive sector, in particular as media-carrying lines.
• Flexible polyamides that contain no plasticizers can basically be prepared in various ways.
• a first process for flexibilizing polyamide is based on the incorporation of polyether or polyester segments.
• a second variant is based on a compounding process in which polyamides are flexibly adjusted by adding ethylene / propylene or ethylene / butylene copolymers.
• both the polymerization process and the compounding process have the disadvantage that the products have reduced resistance to chemicals and show increased swelling in fuels and oils. Furthermore, these products have the disadvantage of poor hydrolysis resistance at elevated temperatures.
• Another method uses the flexibilizing
• weight percentages relate to the total amount of components (a) to (c),
• components (a) to (c) based on 100 parts by weight of components (a) to (c), from 0 to 100 parts by weight of one or more additives.
• the elastomer b) prepared by spray-drying the latex obtained in the emulsion polymerization preferably has an average particle diameter in the range from 2 ⁇ m to 300 ⁇ m, preferably from 2 ⁇ m to 200 ⁇ m, in particular in the range from 5 to 150 ⁇ m.
• the average particle diameter can be determined, for example, from the particle size distribution as d 50 value determined by laser diffraction, in particular also in the latex, for example with a Mastersizer 2000. Particularly preferred are the
• the polyamide-elastomer mixtures according to the invention have a high resistance to hydrolysis. This could be demonstrated by the fact that tensile bars made from the polyamide-elastomer mixture in a water / glycol (60:40) mixture at 135 ° C. and a storage time of 500 h have a residual elongation at break of at least 20% (relative to the initial value ) on- ,
• the partially crystalline polyamide (a) is selected from the group consisting of the polyamides PA46, PA6, PA66, PA69, PA610, PA612, PA614,
• According to the invention are preferably 40 to 85 wt .-%, particularly preferably 50 to 78 wt .-% of component (a), based on the sum of components (a) to (c), contained in the polyamide-elastomer mixture.
• partially crystalline in connection with the polyamide (a) in the context of the invention means a polymer which simultaneously has amorphous and crystalline regions (cf., for example, Hans Batzer: "Polymere
• the polyamide (a) preferably has an amino end group concentration in the range from 20 to 120 ⁇ eq / g, preferably from 30 to 100 ⁇ eq / g.
• the carboxy-end group concentration of the polyamide (a) is preferably not more than 30 ⁇ eq / g, more preferably not more than 20 ⁇ eq / g.
• the polyamide (a) present in accordance with the invention preferably has a solution viscosity (measured in m-cresol solution, 0.5% by weight, 20 ° C.) in the range from 1.75 to 2.4, in particular from 1.8 to 2 , 3 on.
• the elastomer b which is also referred to as microgel, is prepared by emulsion polymerization.
• the term "elastomer” means according to the invention in particular that it is a crosslinked, even partially crosslinked, ie branched polymeric material which preferably has a glass transition temperature of below 10 0 C, preferably of below 0 0 C.
• the elastomer b) is preferred by emulsion polymerization of
• conjugated dienes (bl) monomers are preferably used here from the group consisting of butadiene, isoprene, 2-chlorobutadiene and 2,3-dichlorobutadiene. Particularly preferred is butadiene.
• the amount of acrylonitrile as component b2) is in the range from 10 to 40% by weight, more preferably in the range from 28 to 40% by weight, based on the total amount of components bl) to b4).
• the polyfunctional radically polymerizable monomers (b3) are selected from divinylbenzene, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, butanediol-1,4-di (meth) acrylate, and mixtures thereof.
• the stated polyfunctional radically polymerizable monomers b3) are used in the preparation of the elastomer (b) in particular the crosslinking.
• crosslinking of the elastomer (b) can also be carried out without the use of component b3) by emulsion polymerization of components b1) and b2) and subsequent crosslinking in the presence of a radical initiator.
• Suitable free-radical initiators are selected, for example, from organic peroxides, in particular dicumyl peroxide, t-butylcumyl peroxide, bis (t-butylperoxy-isopropyl) benzene, di-t-butyl peroxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2 5-dimethylhexyne-3,2,5-dihydroperoxide, dibenzoylperoxide, bis (2,4-dichlorobenzoyl) peroxide, t-
• Butyl perbenzoate and organic azo compounds in particular azo-bis-isobutyronitrile and azo-bis-cyclohexanenitrile and di- and Polymercaptoverbindun- gene, especially dimercaptoethane, 1,6-dimercaptohexane, 1, 3, 5-trimercaptotriazine and mercapto-terminated Polysulfidkautschuke, in particular captoterminated reaction products of bis-chloroethylformal with sodium polysulfide, etc.
• the crosslinking in the preparation of the elastomer b) can also be carried out without the addition of said polyfunctional free-radically polymerizable monomers b3) by continuing the polymerization up to high conversions, in particular of conversions ⁇ 70 mol%, preferably ⁇ 80 mol%, based carried on the total amount of the monomer mixture used, preferably at temperatures of ⁇ 10 0 C, more preferably ⁇ 20 0 C, or in mono- merzulaufmaschineckermaschinen by polymerization at high internal conversions.
• Another possibility is to carry out the polymerization in the absence of regulators and / or at elevated temperature, in particular at temperatures ⁇ 10 ° C. Under these conditions, the double bonds which remain when using dienes as monomer in the polymer (b), also accessible for crosslinking reactions.
• the elastomer (b) used according to the invention may further comprise 0 to 20% by weight of a radically polymerizable monomer b4) which is different from components b1) to b3).
• the radically polymerizable monomer b4) is selected from: styrene, esters of acrylic and methacrylic acid, such as ethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, as well as hydroxyl-containing (meth) acrylates, such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate, tetrafluoroethylene, vinylidene fluoride, hexafluoropropene, and double bond-containing Carbox
• the elastomer b) is preferably made of nitrile rubber (NBR) and is prepared by emulsion polymerization, in which case crosslinking takes place during the polymerization.
• NBR nitrile rubber
• the nitrile rubber is in the form of crosslinked particles, also referred to as NBR microgel.
• the inventively preferred NBR microgels generally comprise repeating units of at least one ⁇ , ⁇ -unsaturated nitrile, at least one conjugated diene and optionally one or more further copolymerizable monomers.
• the conjugated diene can be of any nature. Preference is given to using (C 4 -C 6 ) -conjugated dienes. Particular preference is given to 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, piperylene, 1,3-pentadiene or mixtures thereof. Particularly preferred are 1,3-butadiene and isoprene or mixtures thereof. Very particular preference is 1, 3-butadiene.
• any known ⁇ , ⁇ -unsaturated nitrile can be used, are preferred (C 3 -C 5 ) - ⁇ , ß-unsaturated nitriles such as acrylonitrile, methacrylonitrile, 1-chloroacrylonitrile, ethacrylonitrile o- mixtures thereof. Particularly preferred is acrylonitrile.
• a particularly preferred nitrile rubber is thus a copolymer of acrylonitrile and 1,3-butadiene.
• conjugated diene and the ⁇ , ⁇ -unsaturated nitrile it is also possible to use one or more further copolymerizable monomers, e.g. ⁇ , ß- unsaturated mono- or dicarboxylic acids, their esters or amides.
• further copolymerizable monomers e.g. ⁇ , ß- unsaturated mono- or dicarboxylic acids, their esters or amides.
• ß-unsaturated mono- or dicarboxylic acids for example, fumaric acid, maleic acid, acrylic acid, methacrylic acid, crotonic acid and itaconic acid can be used. Preference is given to maleic acid, acrylic acid, methacrylic acid and itaconic acid.
• nitrile rubbers are also commonly referred to as carboxylated nitrile rubbers or, for brevity, "XNBR".
• esters of the ⁇ , ⁇ -unsaturated carboxylic acids are alkyl esters, alkoxyalkyl esters, hydroxyalkyl esters or mixtures thereof.
• alkyl esters of the ⁇ , ⁇ -unsaturated carboxylic acids are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth ) acrylate, 2-ethylhexyl (meth) acrylate, Oc- tyl (meth) acrylate and lauryl (meth) acrylate.
• n-butyl acrylate is used.
• alkoxyalkyl esters of the ⁇ , ⁇ -unsaturated carboxylic acids are methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate and methoxyethyl (meth) acrylate.
• methoxyethyl acrylate is used.
• Particularly preferred hydroxyalkyl esters of the ⁇ , ⁇ -unsaturated carboxylic acids are hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxy (butyl (meth) acrylate.
• esters of the ⁇ , ⁇ -unsaturated carboxylic acids are, for example, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, glycidyl (meth) acrylate, epoxy (meth) acrylate and urethane (meth) acrylate.
• monomers are vinylaromatics such as styrene, ⁇ -methylstyrene and vinylpyridine.
• the proportions of conjugated diene and ⁇ , ⁇ -unsaturated nitrile in the nitrile rubbers preferably used according to the invention can vary within wide limits.
• the proportion of or the sum of the conjugated dienes is usually in the range of 20 to 95 wt.%, Preferably in the range of 40 to 90 wt .-%, particularly preferably in the range of 60 to 85 wt.%, Based on the total polymer.
• the proportion of or the sum of the ⁇ , ß-unsaturated nitriles is usually at 5 to 80 wt.%, Preferably at 10 to 60 wt .-%, particularly preferably at 15 to 40 wt .-%, based on the total polymer.
• the proportions of the monomers in each case add up to 100% by weight.
• the additional monomers can be present in amounts of from 0 to 40% by weight, preferably from 0.1 to 40% by weight, particularly preferably from 1 to 30% by weight, based on the total polymer.
• corresponding proportions of the conjugated diene (s) and / or of the ⁇ , ⁇ -unsaturated nitriles are replaced by the proportions of these additional monomers, with the proportions of all monomers remaining in each case adding up to 100% by weight.
• esters of (meth) acrylic acid are used as additional monomers, this usually takes place in amounts of from 1 to 25% by weight.
• ⁇ , ⁇ -unsaturated mono- or dicarboxylic acids are used as additional monomers, this is usually carried out in amounts of less than 10% by weight.
• the nitrogen content is determined in the inventively preferred nitrile rubber microgels according to DIN 53 625 Kjeldahl. Due to the crosslinking the nitrile rubber microgels are ethyl ketone in methyl at 20 0 C> 85 wt.% Insoluble.
• the glass transition temperatures of the crosslinked Ni trilkautschuke or Nitrilkautschukmikrogele are usually in the range -70 0 C to + 1O 0 C, preferably at - 60 0 C to 0 0 C.
• Preferred elastomers according to the invention are b) nitrile rubbers which have repeating units of acrylonitrile, 1,3-butadiene and optionally of one or more further copolymerisable monomers. Preference is likewise given to nitrile rubbers which have repeat units of acrylonitrile, 1,3-butadiene and one or more ⁇ , ⁇ -unsaturated mono- or dicarboxylic acids, their esters or ⁇ mides, and in particular repeat units of an alkyl ester of an ⁇ , ⁇ -unsaturated carboxylic acids preferably methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-
• Emulsion polymerizations are generally carried out using emulsifiers.
• emulsifiers for this purpose, a wide range of emulsifiers are known and accessible to the person skilled in the art.
• emulsifiers for example, anionic emulsifiers or neutral emulsifiers can be used.
• Preference is given to used nische emulsifiers, particularly preferably in the form of water-soluble salts.
• anionic emulsifiers it is possible to use modified resin acids which are obtained by dimerization, disproportionation, hydrogenation and modification of resin acid mixtures which contain abietic acid, neoabietic acid, palustric acid, levopimaric acid.
• a particularly preferred modified resin acid is disproportionated rosin acid (Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, Volume 31, pp. 345-355).
• anionic emulsifiers and fatty acids can be used. These contain 6 to 22 C atoms per molecule. They can be fully saturated or contain one or more double bonds in the molecule.
• fatty acids are caproic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid.
• the carboxylic acids are usually based on origin-specific oils or fats such. Castoroil, cottonseed, groundnut oil, linseed oil, coconut fat, palm kernel oil, olive oil, rapeseed oil, soybean oil, fish oil and beef tallow, etc. (Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, Volume 13, pp. 75-108).
• Preferred carboxylic acids are derived from coconut fatty acid and beef tallow and are partially or completely hydrogenated.
• Such carboxylic acids based on modified resin acids or fatty acids are used as water-soluble lithium sodium, potassium and ammonium salts.
• the sodium and potassium salts are preferred.
• Anionic emulsifiers are also sulfonates, sulfates and phosphates bonded to an organic radical.
• Suitable organic radicals are aliphatic, aromatic, alkylated aromatics, fused aromatics, and methlyene-bridged aromatics, wherein the methylene-bridged and fused aromatics may additionally be alkylated.
• the length of the alkyl chains is 6 to 25 C atoms.
• the length of the alkyl chains bonded to the aromatics is between 3 and 12 C atoms.
• the sulfates, sulfonates and phosphates are used as lithium, sodium, potassium and ammonium salts.
• the sodium, potassium and ammonium salts are preferred.
• sulfonates, sulfates and phosphates are Na lauryl sulfate, Na alkyl sulfonate, Na alkylarylsulfonate, Na salts methylenverbschreibter aryl sulfonates, Na salts alkylated Naphthalinsulfonate and the Na salts of methyltenverbschreibter Napthalinsul- fonate, which also be oligomerized can, wherein the degree of oligimerization is between 2 to 10.
• alkylated naphthalenesulfonic acids and the methylene-bridged (and optionally alkylated) naphthalenesulfonic acids are usually in the form of isomer mixtures which may also contain more than 1 sulfonic acid group (2 to 3 sulfonic acid groups) in the molecule.
• Particular preference is given to Na lauryl sulfate, Na alkylsulfonate mixtures having 12 to 18 C atoms, Na Alkylarylsulfonates, Na-diisobutylene naphthalene sulfonate, methylene-bridged polynaphthalenesulfonate mixtures and methylene-bridged arylsulfonate mixtures.
• Neutral emulsifiers are derived from addition products of ethylene oxide and propylene oxide on compounds with sufficiently acidic hydrogen. These include, for example, phenol, alkylated phenol and alkylated amines. The average degrees of polymerization of the epoxides are between 2 and 20. Examples of neutral emulsifiers are ethoxylated nonylphenols having 8, 10 and 12 ethylene oxide units. The neutral emulsifiers are usually not used alone, but in combination with anionic emulsifiers.
• the emulsifiers are used in an amount of from 0.2 to 15 parts by weight, preferably from 0.5 to 12.5 parts by weight, more preferably from 1.0 to 10 parts by weight, based on 100 parts by weight of the monomer mixture used.
• the emulsion polymerization is generally carried out using said emulsifiers. If, after completion of the polymerization, latices are obtained which, owing to a certain instability, tend to premature self-coagulation, the said emulsifiers can also be added to the Nachstabilmaschine the latexes. This may be necessary in particular before the removal of unreacted monomers by treatment with steam and before latex storage or before the spray drying is carried out.
• the emulsion polymerization is preferably carried out in such a way that, in particular, the preferred nitrile rubber according to the invention crosslinks during the polymerization. Therefore, the use of molecular weight regulators is generally not necessary. Nevertheless, it is still possible to use molecular weight regulators, the nature of which is not critical, however.
• the regulator is then usually used in an amount of from 0.01 to 3.5 parts by weight, preferably from 0.05 to 2.5 parts by weight, per 100 parts by weight of the monomer mixture.
• Suitable molecular weight regulators are mercaptan-containing carboxylic acids, mercaptan-containing alcohols, xanthogen disulphides, thiuram disulphides, halogenated hydrocarbons, branched aromatic or aliphatic hydrocarbons and also linear or branched mercaptans. These compounds usually have 1 to 20 carbon atoms (see Rubber Chemistry and Technology (1976), 49 (3), 610-49 (üraneck, CA): "Molecular weight control of elastomers prepared by e-muision polymerization” and DC Blackley, Emulsion Polymerization, Theory and Practice, Applied Science Publishers Ltd London, 1975, pp. 329-381).
• Examples of mercaptan-containing alcohols and mercaptan-containing carboxylic acids are monothioethylene glycol and mercaptopropionic acid.
• xanthogen disulphides are dimethylxanthogen disulphide, diethylxanthogen disulphide, and diisopropylpolyxanthogen disulphide.
• thiuram disulfides are tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetrabutylthiuram disulfide.
• halogenated hydrocarbons are carbon tetrachloride, chloroform, methyl iodide, diiodomethane, difluorodijodomethane, 1,4-diiodobutane, 1,6-diiodohexane, ethyl bromide, ethyl iodide, 1,2-dibromotetrafluoroethane, bromotrifluoroethene, bromodifluoroethene.
• branched hydrocarbons are those from which an H radical can easily be split off.
• examples thereof are toluene, ethylbenzene, cumene, pentaphenylethane, triphenylmethane, 2,4-diphenyl, 4-methyl-1-pentene, dipentene and terpenes, such as e.g. Limonene, ⁇ -pinene, ⁇ -pinene, ⁇ -carotene and ⁇ -carotene.
• linear or branched mercaptans examples include n-hexyl mercaptan or else mercaptans containing 12-16 carbon atoms and at least three tertiary carbon atoms, wherein the sulfur is attached to a is bound to these tertiary carbon atoms.
• mercaptans can be used either singly or in mixtures.
• Suitable compounds are, for example, the addition compounds of hydrogen sulfide to oligomerized propene, in particular tetrameric propene, or to oligomerized isobutene, in particular trimeric isobutene, which are frequently referred to in the literature as tertiary dodecylmercaptan ("t-DDM").
• alkylthiols or (isomeric) mixtures of alkylthiols are either commercially available or can be prepared by a process which is adequately described in the literature (see, for example, JP 07-316126, JP 07-316127 and JP 07-316128 and GB 823,823 and GB 823,824.)
• the individual alkylthiols or mixtures thereof are usually used in an amount of from 0.05 to 3 parts by weight, preferably from 0.1 to 1.5 parts by weight, based on 100 parts by weight of the monomer mixture.
• the metering of the molecular weight regulator or of the molecular weight regulator mixture takes place either at the beginning of the polymerization or else in portions during the course of the polymerization, with the portionwise addition of all or individual components of the regulator mixture during the polymerization being preferred.
• polymerization initiators which decompose into free radicals (free-radical polymerization).
• the peroxo compounds include hydrogen peroxide, peroxodisulfates, peroxodiphosphates, hydroperoxides, peracids, peracid esters, peracid anhydrides and peroxides having two organic radicals.
• Suitable salts of peroxodisulfuric acid and peroxodiphosphoric acid are the sodium, potassium and ammonium salts.
• Suitable hydroperoxides are e.g. t-butyl hydroperoxide, cumene hydroperoxide and p-menthane hydroperoxide.
• Suitable peroxides with two organic radicals are dibenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl perbenzoate, t-butyl peracetate, etc.
• Suitable azo compounds are azobisisobutyronitrile, azobisvaleronitrile and azobis-cyclohexanenitrile.
• Hydrogen peroxide, hydroperoxides, peracids, peracid esters, peroxodisulfate and peroxodiphosphate are also used in combination with reducing agents.
• Suitable reducing agents are sulfenates, sulfinates, sulfoxylates, dithionite, sulfite, metabisulfite, disulphite, sugars, urea, thiourea, xanthates, thioxanthogenates, hydrazinium salts, amines and amine derivatives such as aniline, dimethylaniline, monoethanolamine, diethanolamine or triethanolamine.
• Initiator systems consisting of an oxidizing and a reducing agent are called redox systems.
• redox systems When using redox systems are often used in addition salts of transition metal compounds such as Iron, cobalt or nickel in combination with suitable complexing agents such as sodium ethylenediamtetraacetat, sodium nitrilotriacetate and trisodium phosphate or Tetrakaliumdiphsophat.
• suitable complexing agents such as sodium ethylenediamtetraacetat, sodium nitrilotriacetate and trisodium phosphate or Tetrakaliumdiphsophat.
• Preferred redox systems are, for example: 1) potassium peroxodisulfate in combination with triethanolamine, 2) ammonium peroxodiphosphate in combination with sodium metabisulfite (Na 2 S 2 ⁇ 5 ), 3) p-menthane hydroperoxide / sodium formaldehyde sulfoxylate in combination with Fe II sulfate (FeSO 4 x 7H 2 O), sodium ethylenediamine acetate and trisodium phosphate; 4) cumene hydroperoxide / sodium formaldehyde sulfoxylate in combination with Fe-II sulfate (FeSO 4 .7H 2 O), sodium ethylenediaminoacetate and tetrapotassium diphosphate.
• the amount of oxidizing agent is preferably 0.001 to 1 part by weight based on 100 parts by weight of monomer.
• the molar amount of reducing agent is between 50% to 500% based on the molar amount of the oxidizing agent used.
• the molar amount of complexing agent refers to the amount of transition metal used and is usually equimolar with this.
• the portionwise addition of all and individual Components of the activator system during the polymerization is preferred.
• the reaction rate can be controlled.
• the polymerization time is generally in the range of 5 hours to 30 hours and depends essentially on the acrylonitrile content of the monomer mixture, the activator system and the polymerization temperature.
• the polymerization temperature is generally in in the range of 0 to 100 0 C, preferably in the range of 20 to 8O 0 C.
• the polymerization is generally stopped.
• stoppers In the polymerization, the highest possible polymerization conversions are sought in order to crosslink the nitrile rubber. For this reason, the use of stoppers can be dispensed with. If stoppers are nevertheless used, for example, dimethyldithiocarbamate, Na nitrite, mixtures of dimethyldithiocarbamate and Na nitrite, hydrazine and hydroxylamine and salts derived therefrom such as hydrazinium sulfate and hydroxylammonium sulfate, diethylhydroxylamine, diisopropylhydroxylamine, water-soluble salts of hydroquinone, sodium dithionite, Phenyl- ⁇ -naphthylamine and aromatic phenols such as tert-butyl catechol, or phenothiazine.
• stoppers are nevertheless used, for example, dimethyldithiocarbamate, Na nitrite, mixtures of dimethyldithiocarbamate and Na nit
• the water used in the emulsion polymerization amount of water is in the range of 70 to 300 wt. - Parts, preferably in the range of 80 to 250 wt. - Parts, particularly preferably in the range of 90 to 200 parts by weight of water based on 100 parts by weight of the monomer mixture.
• salts can be added to the aqueous phase during the emulsion polymerization.
• Typical salts are salts of monovalent metals in the form of potassium and sodium hydroxide, sodium sulfate, sodium carbonate, sodium bicarbonate, sodium chloride and potassium chloride. Preference is given to sodium and potassium hydroxide, sodium bicarbonate and potassium chloride.
• the amounts of these electrolytes are in the range 0 to 1 parts by weight, preferably 0 to 0.5 parts by weight based on 100 parts by weight of the monomer mixture.
• the polymerization can be carried out either batchwise or continuously in a stirred tank cascade.
• the polymerization is usually started with from 10 to 80% by weight, preferably from 30 to 50% by weight, of the total amount of initiator.
• the addition of individual components of the initiator system is possible. If you want to produce chemically uniform products, acrylonitrile or butadiene are postdosed, if the composition is outside the azeotropic butadiene / acrylonitrile ratio. Preference is given to replenishing NBR-types with acrylonitrile contents of 10 to 34 and 40 to 50% by weight of acrylonitrile (W. Hofmann, Rubber Chem. Technol. 36 (1963) 1). The replenishment takes place - as indicated for example in DD 154 702 - preferably computer-controlled on the basis of a computer program.
• a post-stabilization of the latex with emulsifier can take place.
• the abovementioned emulsifiers in amounts of 0.1 to 2.5% by weight, preferably 0.5 to 2.0% by weight, based on 100 parts by weight of nitrile rubber.
• one or more anti-aging agents can be added to the latex.
• phenolic, aminic and other anti-aging agents are suitable.
• Suitable phenolic anti-aging agents are alkylated phenols, styrenated phenol, hindered phenols such as 2, ⁇ -di-tert. Butylphenol, 2,6-di-tert-butyl-p-cresol (BHT), 2, 6-di-tert. Butyl-4-ethylphenol, sterically hindered phenols containing ester groups, thioether-containing sterically hindered phenols, 2,2'-methylene-bis- (4-methyl- ⁇ -tert-butylphenol) (BPH) and sterically hindered thiobisphenols.
• BHT 2,6-di-tert-butyl-p-cresol
• BPH 2,2'-methylene-bis- (4-methyl- ⁇ -tert-butylphenol)
• thiobisphenols 2,2'-methylene-bis- (4-methyl- ⁇ -tert-butylphenol)
• a discoloration of the rubber is of no importance, also aminic aging inhibitor z.
• DTPD diaryl-p-phenylenediamines
• ODPA octylated diphenylamine
• PAN phenyl- ⁇ -naphthylamine
• PBN phenyl-ß-naphthylamine
• phenylenediamines are W-isopropyl-W-phenyl-p-phenylenediamine, NI, 3-dimethylbutyl-W-phenyl-p-phenylenediamine (6PPD), AJ-1, 4-dimethylpentyl-7,7-phenyl-p-phenylenediamine ( 7PPD), _V, _V'-bis-1, 4- (1, 4-dimethylpentyl) -p-phenylenediamine (77PD), etc.
• phosphites such as tris (nonylphenyl) phosphite, polymerized 2,2,4-trimethyl-1,2-dihydroquinoline (TMQ), 2-mercaptobenzimidazole (MBI), methyl-2-mercaptobenzimidazole (MMBI), Zinc methylmercaptobenzimidazole (ZMMBI).
• TMQ 2,2,4-trimethyl-1,2-dihydroquinoline
• MBI 2-mercaptobenzimidazole
• MMBI methyl-2-mercaptobenzimidazole
• ZMMBI Zinc methylmercaptobenzimidazole
• TMQ, MBI and MMBI are mainly used for NBR grades that are vulcanized peroxide.
• the elastomers used according to the invention b) it is generally to can not pass through high-energy radiation crosslinked elastomers or ver ⁇ crosslinked microgels, since their use to compatibility problems with the polyamide matrix, and consequently to deterioration in mechanical properties.
• the spray drying of the latices is generally carried out in conventional spray towers.
• the heated preferably at 30 to 100 0 C heated latex via pumps in the spray tower and sprayed preferably located at the top of the tower nozzles at pressures of 50 to 500 bar, preferably 100 to 300 bar.
• Hot air with an inlet temperature of preferably 100 to 200 ° C is supplied in countercurrent and the water evaporates.
• the powder sinks down and the dry powder is discharged at the foot of the tower.
• Release agent, and optionally used other additives, such as aging inhibitors, antioxidants such as, optical brighteners, etc., are preferably also blown as dry powders to the head of the tower is ⁇ .
• the latices supplied to the spray tower preferably have solids concentrations of from 10 to 60, more preferably from 20 to 50% by weight, more preferably from 30 to 50% by weight, based on the latex (determined according to ISO 126: 2005).
• This type of workup yields, in particular, spherical or almost spherical microgel particle agglomerates whose average diameter is preferably 300 .mu.m, more preferably 200 .mu.m, more preferably ter does not exceed 100 microns (see, for example, Figure 1).
• the elastomer (b) used according to the invention which in this form is mixed with the polyamide (a) and optionally additionally with the polyamide (c) and optionally further additives, thus preferably consists of almost spherical particles, which preferably have a mean diameter in the Range of 2 to 300 microns, more preferably in the range of 2 to 200 microns, more preferably in the range of 5 to 150 microns and in particular in the range of 5 to 100 microns possess.
• microgel latexes in particular by coagulation, co-coagulation with a further latex polymer and by latex coagulation of the latexes, filtration, subsequent crumb washing, drying and subsequent grinding result in comparatively coarse, irregularly shaped microgel particles, generally having a much larger average Diameter (see Figures 2 and 3).
• the release agents are preferably selected from silicic acids, in particular having a BET specific surface area of more than 5 m 2 / g, calcium carbonate, magnesium carbonate, silicates, such as talc and glimmer, fatty acid salts, in particular alkali and alkaline earth metal salts, such as salts of fatty acids having more than 10 carbon atoms, in particular calcium and magnesium salts of such fatty acids, such as calcium stearate, magnesium stearate and aluminum zinc stearate, calcium phosphate, aluminum oxide, barium sulfate, zinc oxide, titanium dioxide, high-molecular-weight polymers Glass transition temperature, for example, greater than 60 0 C, such as polyesters, polyolefins and starch, hydrophilic polymers, such as polyvinyl alcohol, polyalkylene oxide compounds, in particular polyethylene oxide compounds, such as polyethylene glycols or polyethylene glycol, polyacrylic acid, polyvinylpyrrolidone and cellulose derivatives, fluorohydr
• calcium carbonate is added as a release agent in the workup of the Elastomerlatex.
• the elastomer (b) can also be converted into the desired, advantageous starting form (spray-dried microgel) without addition of a separate release agent and thus incorporated into the polyamide matrix.
• elastomer (b) in the polyamide-elastomer mixture are preferably 5 to 40 wt .-%, more preferably 10 to 30 wt.% Of the elastomer (b) in the polyamide-elastomer mixture, based on the sum of components a) to c) included.
• polyamide (c) it is possible in particular to comprise both partially crystalline (as defined above) polyamides and amorphous or microcrystalline polyamides.
• the polyamide molding composition in addition to component (a), also contains up to 20% by weight, in particular up to 15% by weight, based on the sum of components a) to c) of at least one amorphous or microcrystalline polyamide ( Component c)) based on aliphatic, cycloaliphatic or aromatic diamines, dicarboxylic acids and / or aminocarboxylic acids, preferably having 6 to 36 carbon atoms, and mixtures of such homopolyamides and / or copolyamides.
• the molding compositions preferably contain 2 to 20 wt .-%, in particular 3 to 15 wt .-% component (c) based on the sum of components a) to c).
• amorphous or microcrystalline polyamides (component c) and / or copolyamides used according to the invention, preference is given to the following systems:
• the cycloaliphatic diamines are preferably MACM, IPD and / or PACM, with or without additional substituents.
• the aliphatic dicarboxylic acid is preferably an aliphatic dicarboxylic acid having 2 to 36, preferably 8 to 20, linear or branched carbon atoms, more preferably having 10, 12, 13, 14, 16 or 18 carbon atoms.
• MACM stands for the ISO designation bis (4-amino-3-methyl-cyclohexyl) -methane, which is sold under the trade name 3, 3'-dimethyl-4-4'-diaminodicyclohexylmethane as Laromin C260 type (CAS no. 6864-37-5), preferably having a melting point between -10 0 C and 0 0 C, is commercially available.
• MACM12 stands for an aliphatic linear C12 dicarboxylic acid (DDS, dodecane diacid) with which the diamine MACM is polycondensed.
• TPS stands for isophthalic acid and PACM stands for ISO designation Bis- (4-amino-cyclohexyl) -methane, which under the trade name 4, 4 '-Diaminodicyclohexyl- methane as dicykano type (CAS No. 1761-71-3), preferably having a melting point between 30 0 C and 45 0 C, is commercially available.
• Polyamides selected from the group: MACM9-18, PACM9-18, MACMI / 12, MACMI / MACMT, MACMI / MACMT / 12, 6I 6T / MACMI / MACMT / 12, 3-6T, 6I6T, TMDT,
• the abovementioned preferably amorphous or microcrystalline polyamides (component c) preferably have a glass transition temperature of greater than 40 ° C., more preferably greater than 60 ° C., more preferably greater than 90 ° C., very particularly preferably greater than 110 ° C., in particular greater than 130 0 C and most of all vorzugt of greater than 150 0 C.
• the relative solution viscosity is preferably in the range of 1.3 to less than 1.75 (measured in m-cresol, 0.5 wt .-%), preferably in the range from 1.4 to 1, 70 and in particular between 1.5 and 1.70.
• the polyamides c) preferably have a heat of fusion in the range of 4 to 40 J / g, in particular in the range of 4 to 25 J / g (determined by DSC), the amorphous polyamides have heat of fusion less than 4 J / g.
• the polyamide elastomer composition according to the invention may contain, based on 100 parts by weight of components a) to c), from 0 to 100 parts by weight of one or more customary additives. That is, when, for example, 0 parts by weight of the conventional additives are present for 100 parts by weight of the components a) to c), the composition is generally 100% by weight of the components a) to c), or if, for example, 100 parts by weight of the usual additives per 100 parts by weight of the components a) to c) are present, the composition generally consists of 50 wt .-% of the components a) to c).
• the polyamide elastomer composition according to the invention consists of the components a) to c) and the existing existing conventional additives.
• the polyamide elastomer composition according to the invention in particular of 0 to 50% by weight of the additives and from 50 to 100% by weight of the components a) to c), based on the total amount of the polyamide elastomer composition.
• the optional additives are generally commercially available additives. They are selected in particular from the release agents mentioned above, anti-aging agents, such as antioxidants, and optical brighteners, flame retardants, light stabilizers, nucleating agents, antifungal agents, microbe protection agents, hydrolysis protectants, etc., which are preferably added in the preparation of component b). In addition, they may be conventional additives, such as inorganic or organic fillers, such as e.g. Glass fibers, inorganic or organic pigments, e.g. Soot, or dyes, antistatic agents, antiblocking agents, etc.
• anti-aging agents such as antioxidants, and optical brighteners, flame retardants, light stabilizers, nucleating agents, antifungal agents, microbe protection agents, hydrolysis protectants, etc.
• inorganic or organic fillers such as e.g. Glass fibers, inorganic or organic pigments, e.g. Soot, or dyes, antistatic agents, antiblocking agents, etc.
• Polyamide elastomer composition in principle at any stage of their preparation, including the preparation of the individual components a) to c) are added.
• the abovementioned release agents are expediently added during the production of component b) in the case of spray drying, in which case it is additionally possible, in particular, to add anti-aging agents, such as antioxidants.
• the present invention also provides a molded article obtainable from a polyamide-elastomer blend as described above.
• Such moldings preferably have an elongation at break of at least 20%, in particular of at least at least 30%, relative to the initial value and measured on tensile bars in a water / glycol (60:40) mixture at 135 0 C with a storage period of 500 h.
• the moldings In the dry state, the moldings preferably have an elongation at break of at least 150%.
• the moldings show a high flexibility, which is shown in a preferred tensile modulus on ISO test bars in the dry state in the range of 300 to 1500 MPa.
• the molding has a notched impact strength from -30 0 C, as measured by ISO test bars of at least 10 kJ / m 2.
• the molding preferably has an oil swell in IRM 903 after 4d at a temperature of 125 0 C of a maximum of 3%.
• the MVR (MEIT volume rate) at 275 0 C and a load of 21.6 kg is in the range of 50 to 200 cm 3/10 min.
• the polyamide-elastomer mixture according to the invention is used in particular for producing molded parts or smooth, corrugated or partially corrugated mono- or multilayer pipes which are in contact with water, oil, glycol, methanol, ethanol or fuel-containing liquid media , These include in particular vents for crankshaft housings, Mono- and multilayer lines in the underpressure and overpressure area, as well as coolant lines in contact with water and / or glycol, or lines in the automotive sector that carry oil or are in contact with oil.
• Microgel Type A (non-inventive): copolymer of butadiene: 68.8%, acrylonitrile: 26.7%, HEMA: 1.5%, TMPTMA: 3.0%, prepared according to the teaching of EP 1 152 030 A2; Polymerization conversion: 99%; worked up by coagulation with aqueous calcium chloride solution, drying and subsequent grinding with release agent Calcium carbonate (added during grinding - 5 wt .-%, based on the total mass of microgel and release agent) ( Figure 3)
• Microgel B (non-inventive) and C (inventive) were prepared from the same latex.
• the preparation of the latex was carried out by copolymerization of the monomers butadiene and acrylonitrile in a weight ratio of 62/38 and 0.37 parts by weight of tert-dodecylmercaptan (Phillips Petroleum Corp.) without addition of crosslinking agent and without addition of another monomer.
• the polymerization was (0.025 wt. Parts by) at 3O 0 C by the addition of ammonium and triethanolamine (0.018 wt. Parts by) started.
• the polymerization was carried out partly adiabatic. At 45 ° C.
• the latex had a solids content of 48.5% by weight, a pH of 10.6 and an average particle diameter of 198 nm; the gel content and the swelling index (each determined in toluene) were: 90.5% by weight and 7.6.
• the glass transition temperature was -18 ° C and the width of the glass step was 7 ° C.
• the latex was admixed with 1.15% by weight of Wingshay L Antioxidant (butylated reaction product of p-cresol with dicyclopentadiene from Eliokem)
• Microgel type B (not inventive: worked up by coagulation with aqueous calcium chloride solution, washing, drying and subsequent grinding with addition of the release agent calcium carbonate (5% by weight, based on the total mass of microgel and release agent) (FIG. 2)
• Microgel Type C (Inventive): The working up of the latex was carried out by spray drying with the addition of the release agent calcium carbonate (5% by weight, based on the total mass of microgel and release agent) (FIG. 1) (Commercially available microgel Baymod N VPKA 8641 from Lanxess GmbH ).
• Polyamide (a) and (c) and microgel (b) were dosed together in the feeder of a twin-screw extruder (ZSK 30, Coperion) and at cylinder temperatures of 200 to 280 0 C, a screw speed of 180 U / min and a throughput of 12 kg / h compiled.
• the strands emerging at the nozzle were cooled in a water bath and subsequently granulated. After drying at 80 ° C., the molding compositions were sprayed into moldings and test specimens.
• modulus, tear strength and elongation at break were determined according to ISO 527 on ISO tensile bars, ISO / CD 3167, type Al, 170x20 / 10x4 mm at a temperature of 23 0 C. The mechanical values were determined in the dry state.
• the relative viscosity ( ⁇ rel) was determined on a 0.5% m-cresol according to DIN EN ISO 307 at 20 0 C.
• nb not determined nm: not measurable o. B.: without breakage
• the hydrolysis resistance was determined in comparison to the mixtures of the comparative examples. This was done storage in a water-glycol mixture with a mixing ratio of 60 to 40 at 135 0 C and a defined storage period. As Gykol the commercially available coolant additive Havoline XLC was used. For storage, tension bars with a thickness of 4 mm were used. It can be seen in FIG. 4 that the mixture according to the invention has a significantly higher residual elongation at break (relative to the starting value) than the mixtures known from the prior art. By using the spray dried half-life in the hydrolysis test was doubled on average.

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