DE19817809A1 - Molding compositions, useful for production of tubing and containers for fuel, fuel pumps and cable sheathing - Google Patents

Abstract

The use of molding compositions comprising at least a thermoplastic polyketone and a thermoplastic polyurethane to improve low temperature toughness is claimed.

Description

The invention relates to the use of thermoplastic molding compositions based thermoplastic polyketones (olefin-carbon monoxide copolymers) and poly urethanes to improve low-temperature toughness.

The production of molding compounds from thermoplastic polyketones and poly Urethanes are known (US-A 4,851,482 (= EP-A 339747)). It is described that the molding compounds have good toughness and rigidity as well Resistance to solvents and abrasion. The Low temperature toughness is not mentioned.

From US-A 4,935,304 wire and cable sheaths are made from a mixture thermoplastic polyketones and polyurethanes known, among others, good Have toughness. Low-temperature toughness is also not mentioned.

US-A 5,166,252 discloses reinforced blends of thermoplastic polyketones and polyurethanes with a combination of properties from u. a. Heat resistance, Impact resistance, improved rigidity. The toughness behavior also takes place here no mention at low temperatures.

It has now been found that thermoplastic molding compositions made from polyketones and Polyurethanes to improve low-temperature toughness and / or toughness can be used at low temperatures. The molding compounds show excellent low-temperature toughness and excellent Low-temperature fracture behavior under impact and shock loads.  

Polyketone / TPU blends are therefore particularly suitable for applications in which a excellent toughness level at low temperatures is required, such as for example in the automotive and electrical / electronics sectors.

The present invention therefore relates to the use of molding compositions containing

• A) thermoplastic polyketone and
• B) thermoplastic polyurethane

to improve low-temperature toughness.

The invention particularly relates to the use of thermoplastic Molding compounds from A) thermoplastic polyketone and B) thermoplastic poly urethane for the production of articles with improved low-temperature toughness.

The thermoplastic molding compositions generally contain component A) in Amounts from 99 to 1, preferably 95 to 5, particularly preferably 80 to 50 Parts by weight and component B in amounts of 1 to 99, preferably 5 to 95, particularly preferably 20 to 50 parts by weight. The sum of the parts by weight of A) and B) results in 100. The molding compositions can further additives - as described later ben - included.

The polyketone polymers which are used as component A have one linear alternating structure and contain essentially 1 molecule of carbon monoxide per molecule of unsaturated hydrocarbon. Suitable ethylenically saturated hydrocarbons as monomers for the construction of the polyketone polymer have up to 20 carbon atoms, preferably up to 10 carbon atoms and are aliphatic such as ethylene and other α-olefins, e.g. B. propylene, 1-  Butene, 1-isobutylene, 1-hexene, 1-octene and 1-dodecene, or are arylaliphatic and contain an aryl substituent on a carbon atom of the linear chain. Examples of arylaliphatic monomers are styrene, α-methylstyrene, p-ethyl styrene and m-isopropyl styrene.

Preferred polyketone polymers are copolymers of carbon monoxide and ethylene or terpolymers of carbon monoxide, ethylene and a second ethylenically saturated hydrocarbon with at least 3 carbon atoms, especially one α-olefin such as B. propylene.

Terpolymers of at least 2 monomer units, of which are particularly preferred one is ethylene and the other is a second hydrocarbon. Preferably be about 10 to 100 monomer units of the second hydrocarbon puts.

The polymer chain of the preferred polyketone polymer is represented by the following formula

[CO (CH ₂ CH ₂ )] _x [CO (G)] _y (I)

in which
G is a monomer unit based on an ethylenically unsaturated hydrocarbon with at least 3 carbon atoms, preferably 3 to 10 carbon atoms, which is polymerized due to the ethylenic double bond and
the ratio y: x is not more than about 0.5.
y = 0 for copolymers of carbon monoxide and ethylene.

If y is different from 0, terpolymers are used and the unit -CO- (CH ₂ CH ₂ ) and -CO- (G) unit are statistically distributed over the polymer chain.

The preferred ratio of y: x is 0.01 to 0.1.

Polyketone polymers with an average molecular weight (number average) of unge about 1,000 to 200,000, especially 20,000 to 90,000, determined by Gelper meation chromatography are preferred.

For further characterization and for the production of the polyketone polymers refer to US-A 5,166,252.

A polyketone polymer or a mixture of polyketone polymers can be used become.

The polyketone polymers can also contain stabilizers, processing aids, Flow aids, antistatic agents, flame retardants, dyes, amount of pig, reinforcement Kungsstoffe such. B. glass fibers or mineral fillers or other usual Contain additives.

The thermoplastic polyurethanes used as component B are made from linear polyols, mostly polyester or polyether polyols, organic Diisocyanates and short-chain diols (chain extenders) built. For Catalysts can also be added to accelerate the formation reaction become. The molar ratios of the structural components can be wide Range can be varied, whereby the properties of the product can be adjusted. Molar ratios of polyols to chain extenders of 1: 1 have proven successful to 1: 12. This results in products in the range from 70 Shore A to 75 Shore D. The structure of the thermoplastically processable polyurethane elastomers can either  step by step (prepolymer process) or by the simultaneous reaction of all Components take place in one stage (one-shot process). In the prepolymer process an isocyanate-containing prepolymer is formed from the polyol and the diisocyanate, which is implemented in a second step with the chain extender. The TPU can be produced continuously or batchwise. The most popular Technical manufacturing processes are the belt process and the extruder process.

The thermoplastically processable polyurethanes are obtainable by implementing the polyurethane-forming components

• C) organic diisocyanate,
• D) linear hydroxyl-terminated polyol with a molecular weight of 500 to 5000,
• E) Diol or diamine chain extenders with a molecular weight of 60 to 500,

the molar ratio of the NCO groups in C) to that of isocyanate reactive groups in D) and E) is 0.9 to 1.2.

Examples of organic diisocyanates C) are aliphatic, cycloaliphatic, araliphatic, heterocyclic and aromatic diisocyanates in Consider as described in Justus Liebigs Annalen der Chemie, 562, pp. 75-136 become.

Examples include: aliphatic diisocyanates such as hexamethylene diisocyanate, cycloaliphatic diisocyanates, such as isophorone diisocyanate, 1,4- Cyclohexane diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate and 1-methyl-2,6- cyclohexane diisocyanate and the corresponding isomer mixtures, 4,4'- Dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate and 2,2'- Dicyclohexylmethane diisocyanate and the corresponding isomer mixtures,  aromatic diisocyanates, such as 2,4-tolylene diisocyanate, mixtures of 2,4- Tolylene diisocyanate and 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and 2,2'-diphenylmethane diisocyanate, mixtures of 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylinethane diisocyanate, urethane-modified liquid 4,4'-diphenylmethane diisocyanates and 2,4'-diphenyl methane diisocyanates, 4,4'-diisocyanatodiphenylethane (1,2) and 1,5-naphthylene diiso cyanate. 1,6-Hexamethylene diisocyanate, isophorone are preferably used diisocyanate, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate isomer mix with a 4,4'-diphenylmethane diisocyanate content of <96 wt .-% and esp special 4,4'-diphenylmethane diisocyanate and 1,5-naphthylene diisocyanate. The The diisocyanates mentioned can be used individually or in the form of mixtures with one another come into use. You can also use up to 15% by weight (calculated on the total amount of diisocyanate) of a polyisocyanate are, for example triphenylmethane-4,4 ', 4' '- triisocyanate or polyphenyl-poly methylene polyisocyanates.

As component D) linear hydroxyl-terminated polyols with one molecule Lar weight from 500 to 5000 used. Due to production, these often contain small ones Amounts of nonlinear compounds. One often speaks of "im essential linear polyols ". Preferred are polyester, polyether, polycarbonate Diols or mixtures of these.

Suitable polyether diols can be prepared by one or several alkylene oxides with 2 to 4 carbon atoms in the alkylene radical with one Starter molecule, which contains two active hydrogen atoms bound. As Alkylene oxides are, for. B. called: ethylene oxide, 1,2-propylene oxide, epichlorohydrin and 1,2-butylene oxide and 2,3-butylene oxide. Ethylene oxide, Propylene oxide and mixtures of 1,2-propylene oxide and ethylene oxide are used. The Alkylene oxides can be used individually, alternately in succession or as mixtures be used. Examples of suitable starter molecules are. Water,  Amino alcohols, such as N-alkyl-diethanolamines, for example N-methyl-diethanol amine, and diols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol and 1,6- Hexanediol. If appropriate, mixtures of starter molecules can also be used become. Suitable polyether diols are also those containing hydroxyl groups Polymerization products of tetrahydrofuran. It can also be trifunctional Polyethers in proportions of 0 to 30% by weight, based on the bifunctional polyethers, are used, but at most in such an amount that a thermoplastic processable product is created. Have the essentially linear polyether diols Molecular weights from 500 to 5000. They can be used both individually and in the form of Mixtures with each other are used.

Suitable polyester diols can, for example, from dicarboxylic acids with 2 to 12 Carbon atoms, preferably 4 to 6 carbon atoms, and polyhydric alcohol fetch are manufactured. Examples of suitable dicarboxylic acids are: ali phatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, suberic acid, Azelaic acid and sebacic acid and aromatic dicarboxylic acids, such as phthalic acid, Isophthalic acid and terephthalic acid. The dicarboxylic acids can be used individually or as Mixtures, e.g. B. in the form of a succinic, glutaric and adipic acid mixture used become. To prepare the polyester diols, it may be advantageous if instead of the dicarboxylic acids, the corresponding dicarboxylic acid derivatives, such as carbon acid diesters with 1 to 4 carbon atoms in the alcohol radical, carboxylic anhydrides or To use carboxylic acid chlorides. Examples of polyhydric alcohols are glycols with 2 to 10, preferably 2 to 6 carbon atoms, such as ethylene glycol, Diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2,2- Dimethyl-1,3-propanediol, 1,3-propanediol and dipropylene glycol. Depending on the desired properties can be the polyhydric alcohols alone or optionally used in a mixture with each other. Are also suitable Esters of carbonic acid with the diols mentioned, especially those with 4 to 6 Carbon atoms such as 1,4-butanediol or 1,6-hexanediol, condensation products of hydroxycarboxylic acids, for example hydroxycaproic acid and polymerization  products of lactones, for example optionally substituted caprolactones. Preferred polyester diols are ethanediol polyadipates, 1,4- Butanediol polyadipate, ethanediol-1,4-butanediol polyadipate, 1,6-hexanediol neopentyl glycol pelyadipate, 1,6-hexanediol-1,4-butanediol polyadipate and poly-caprolactone. The polyester diols have molecular weights from 500 to 5000 and can be used individually or in the form of mixtures with one another.

Chain extenders E) are diols or diamines with one molecular weight from 60 to 500, preferably aliphatic diols with 2 to 14 Carbon atoms such as B. ethanediol, 1,6-hexanediol, diethylene glycol, Dipropylene glycol and especially 1,4-butanediol. However, diesters are also suitable the terephthalic acid with glycols having 2 to 4 carbon atoms, such as. B. Terephthalic acid-bis-ethylene glycol or terephthalic acid-bis-1,4-butanediol, hydroxy alkylene ethers of hydroquinone, such as. B. 1,4-di (-hydroxyethyl) hydroquinone, ethoxylated bisphenols, (cyclo) aliphatic diamines, such as. B. isophoronediamine, Ethylenediamine, 1,2-propylene-diamine, 1,3-propylene-diamine, N-methyl-propylene-1,3- diamine, N, N'-dimethyl-ethylenediamine and aromatic diamines such as e.g. B. 2.4- Tolylene diamine and 2,6-tolylene diamine, 3,5-diethyl-2,4-tolylene diamine and 3.5- Diethyl-2,6-toluenediamine and primary mono-, di-, tri- or tetraalkyl-substituted 4,4'-diaminodiphenylmethane. Mixtures of the chains mentioned above can also be used can be used longer. Smaller amounts of triplets can also be used be added.

In addition, conventional monofunctional compounds can also be used in small amounts are used, e.g. B. as a chain terminator or mold release. Exemplary alcohols such as octanol and stearyl alcohol or amines such as butylamine may be mentioned and stearylamine.

To produce the thermoplastic polyurethanes, the structural components, optionally in the presence of catalysts, auxiliaries and additives, in  are reacted in amounts such that the equivalence ratio of NCO groups to the sum of the NCO-reactive groups, especially the OH Groups of the low molecular weight diols / triols and polyols 0.9: 1.0 to 1.2: 1.0, preferably 0.95: 1.0 to 1.10: 1.0.

Suitable catalysts according to the invention are those according to the prior art known and customary tertiary amines, such as. B. triethylamine, Dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethyl-piperazine, 2- (Dimethylamino-ethoxy) ethanol, diazabicyclo (2,2,2) octane and the like and in particular organic metal compounds such as titanium acid esters, iron compounds, Tin compounds, e.g. B. tin diacetate, tin dioctoate, tin dilaurate or tin dialkyl saloons of aliphatic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate or similar. Preferred catalysts are organic metal compounds, especially titanium acid esters, iron or tin compounds.

In addition to the TPU components and the catalysts, other aids can also be used and additives are added. Lubricants such as fat may be mentioned, for example acid esters, their metal soaps, fatty acid amides and silicone compounds, antiblock medium, inhibitors, stabilizers against hydrolysis, light, heat and discoloration, Flame retardants, dyes, pigments, inorganic or organic fillers and Reinforcing agents. Reinforcing agents are, in particular, fibrous reinforcing agents substances such as inorganic fibers, which are manufactured according to the prior art and can also be applied with a size. Details of the The auxiliaries and additives mentioned can be found in the specialist literature, for example J.H. Saunders, K.C. Fresh: "High Polymers", Volume XVI, Polyurethane, Parts 1 and 2, Interscience Publishers 1962 and 1964, R. Gächter, H. Müller (Ed.): Taschenbuch der Plastic additives, 3rd edition, Hanser Verlag, Munich 1989, or DE-A 29 01 774.

It can be a thermoplastic polyurethane or a mixture of thermoplastic Polyurethanes are used.  

Other additives that can be incorporated into the TPU are stabilizers, ver work aids, antistatic agents, flame retardants, dyes, pigments, commercial plasticizers such as phosphates, phthalates, adipates, sebacates and Alkyl sulfonic acid esters, reinforcing materials such. B. glass fibers or mineral Fillers and other common additives.

The TPU can continuously in the so-called extruder process, for. B. in one Multi-shaft extruder. The dosage of the TPU components C), D) and E) can simultaneously, i.e. H. in the one-shot process, or in succession, d. H. after a prepolymer process. The prepolymer can be batchwise presented, as well as continuously in a part of the extruder or in a separate upstream prepolymer unit are manufactured.

The thermoplastic molding compositions optionally containing other known ones Additives such as stabilizers, dyes, pigments, lubricants and mold release agents, ver Strengthening agents, nucleating agents and antistatic agents are manufactured by the respective constituents are mixed in a known manner and at temperatures from 200 ° C to 330 ° C in common units such as internal kneaders, extruders, double Wave screws melt-compounded or melt-extruded. In which Melt compounding or melt extrusion step can be other additives such as e.g. B. reinforcing materials (e.g. glass fibers, mineral fillers), stabilizers, Dyes, pigments, lubricants and mold release agents, nucleating agents, Add compatalizers and other additives.

The article can be manufactured, for example, by a granulate, which beforehand by compounding polyketone and TPU, if necessary with others Additives were obtained, or the respective granules of components A and B, if necessary with further additives, separated into the compounding or Extrusion system given and processed together.  

The thermoplastic molding compounds made of polyketone and TPU are used in manufacturing of articles of any kind. For example, molded bodies, hollow bodies and called jackets.

Polyketone / TPU blend are particularly suitable for applications where a excellent toughness level at low temperatures is required, such as for example in the automotive, electrical and electronics sectors.

Examples of applications include: fuel lines and fuel storage tanks of any kind, fuel rails, fuel pump reservoirs, power fabric pump housing, hubcaps, tank sockets, snap locks of any kind, Cable jackets, hoses and pipes.

In addition to the good low-temperature toughness, polyketone / TPU blends stand out especially due to excellent fuel barrier properties, low Gas permeability, very good chemical resistance and very good paintability out.  

Examples

The following components are used in the examples:

• A) Linear alternating terpolymer made of carbon monoxide, ethylene and propylene (Carilon®DP P 1000, Shell International Chemicals Ltd., London, UK)

Thermoplastic polyurethanes

• B1) Desmopan® 8600 polytetramethylene glycol
  1,4-butanediol
  Methylene diphenyl diisocyanate
• B2) Desmopan® 955 U polytetramethylene glycol
  1,4-butanediol
  Methylene diphenyl diisocyanate
• B3) Desmopan® 385 poly-butanediol-1,4-adipate
  1,4-butanediol
  Methylene diphenyl diisocyanate
• B4) Texin® DP 7-3005 polytetramethylene glycol
  1,4-butanediol
  Desmodur W® (methylene dicyclohexyl diisocyanate)
• B5) Texin® SS 90 polytetramethylene glycol
  Hexanediol-1,6
  Isophoronediamine
  Isophorone diisocyanate

The Desmopan products are from Bayer AG, Leverkusen, Germany Texin products from Bayer Corporation, Pittsburgh, USA. Desmodur W® is a Product of Bayer AG, Leverkusen, Germany.

The components are mixed on an extruder of the type ZSK 32/1 230 to 250 ° C. The moldings are placed on an Arburg injection molding machine 320-210-500 at melt temperatures of 230 to 250 ° C and mold temperatures manufactured from 20 to 50 ° C. Composition and properties are based on the Tables 1 to 5.

The behavior in the case of impact stress in the Izod impact test on unskilled (Izod impact strength a _ic , ISO 180) and notched (Izod impact strength a _iA , ISO 180) test specimens and the behavior in the case of impact stress in the puncture test (impact work W _tot an 60 mm Round discs with a thickness of 3 mm, ISO 6603-2) were examined.

In addition, the surface of the molded parts was assessed visually.

As can be seen from Tables 1 to 5, the molding compositions according to the invention perform for molded parts with very good toughness values and very good toughness behavior especially at low temperatures. The puncture attempt supplements as an experiment with biaxial impact stress. Biaxial In practice, shock loads occur more often than pure impact bending or Impact tensile stresses.

They also have surfaces just as good as the unmodified polyketone.  

Claims (1)

Use of molding compositions made from at least one thermoplastic polyketone and at least one thermoplastic polyurethane to improve the low temperature toughness.