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EP1709097A1 - Stabilisateurs a base de polyisocyanates - Google Patents

Stabilisateurs a base de polyisocyanates

Info

Publication number
EP1709097A1
EP1709097A1 EP05700885A EP05700885A EP1709097A1 EP 1709097 A1 EP1709097 A1 EP 1709097A1 EP 05700885 A EP05700885 A EP 05700885A EP 05700885 A EP05700885 A EP 05700885A EP 1709097 A1 EP1709097 A1 EP 1709097A1
Authority
EP
European Patent Office
Prior art keywords
groups
radical
stabilizers
active ingredient
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05700885A
Other languages
German (de)
English (en)
Inventor
Bernd Bruchmann
Hauke Malz
Andreas Eipper
Dietrich Scherzer
Simon Schambony
Harald Schäfer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1709097A1 publication Critical patent/EP1709097A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/3844—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing one nitrogen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates

Definitions

  • the invention relates to stabilizers based on polyisocyanates.
  • Plastics e.g. Polyolefins, polyamides, polyurethanes, polyacrylates, polycarbonates, polyesters, polyoxymethylenes, polystyrenes and styrene copolymers are used in many areas of everyday life. Examples of these applications are foils and fibers, applications in the interior of automobiles, such as upholstery and cover materials, dashboards or airbags, or applications in the exterior of automobiles, such as tires, bumpers or protective strips, as well as cable sheaths, housings, shoe soles, dispersions, paints for the Metal, wood, plastic, paper or leather coating or paints.
  • plastics are exposed to a wide variety of stresses.
  • Plastics used in the engine compartment of a motor vehicle withstand high temperatures.
  • Plastic films or varnishes that are exposed to sunlight are subject to the harmful effects of UV light.
  • UV light and thermal stress generally lead to discoloration of the plastics and / or to a deterioration in the property profile of the plastics. Due to the impairment of the optical appearance and the mechanical properties of the plastic, the product made from them can ultimately no longer be used for the desired purpose.
  • plastics Due to their different chemical structure, plastics generally have different stabilities against damage from UV light and thermal stress or against damage from environmental influences. However, it is desirable to make the application area of all plastics as wide as possible, i.e. improve the stability of plastics against environmental influences such as heat, sunlight and UV light.
  • plastics are often affected by high processing temperatures and / or high shear forces.
  • plastics can be mixed with an antioxidant (AO) and a hinder earth amine light stabilizer (HALS) or protected against UV damage by a mixture of a UV absorber and a phenolic antioxidant or by a mixture of a phenolic antioxidant, a HALS and a UV absorber.
  • AO antioxidant
  • HALS hinder earth amine light stabilizer
  • a problem with stabilizers is their migration behavior in the plastic, i.e. their volatility and tendency to bloom, bleed, or wash out. It has been shown that stabilizers whose molecular weight is too low evaporate from the plastic. This is particularly a problem when the surface / volume ratio of a molded plastic part is very large. Evaporation of the stabilizer, the so-called "fogging", can be used in certain applications, e.g. in the interior of the automobile lead to limit values for the total amount of volatile constituents being exceeded and the plastic being rejected for this application.
  • stabilizers are usually oligomerized, polymerized, or attached to an organic anchor group to increase the molecular weight.
  • an organic anchor group is an organic radical whose task is to increase the molecular weight of the stabilizer.
  • One or more stabilizers can be connected to such an anchor group.
  • the mobility of the stabilizer in such a way that its effectiveness decreases, since the stabilizer can no longer compensate for concentration differences caused by degradation reactions by diffusion.
  • Another problem is washing out a stabilizer by contacting the plastic with a liquid. This leads not only to a reduction in the stabilizer content in the plastic, but also to contamination of the liquid with the stabilizer. This problem arises particularly in applications in the food sector.
  • the stabilizer in applications in dispersions or lacquers, it may be necessary for the stabilizer to be emulsified or dissolved in a liquid in order to ensure an even distribution.
  • Polymeric or oligomeric stabilizers based on diols or polyols are known from DE-A 101 20 838, the stabilizing components being linked to the diols or polyols via ester linkages.
  • a disadvantage of these oligomeric or polymeric stabilizers is the lack of resistance of the ester bond, which can be split back under hydrolysis conditions.
  • EP-A 0 615 991, EP-A 0 615 992, DE-A 197 30 666 and DE-A 198 04 980 describe thermosetting polyurethane coating systems in which the stabilizing component is incorporated into the polymer matrix.
  • DE-A 197 30 666 and DE-A 198 04 980 polyisocyanates containing uretdione groups are partially reacted with a monomeric stabilizer, the remaining NGO groups ensuring the incorporation of the stabilizer into the polyurethane network.
  • 3,627,735 describes the production of fiber products, a stabilizer consisting of a 1: 1 adduct of 4,4'-diphenylmethane diisocyanate and p-aminophenol being incorporated into the linear fiber polymer via side chains.
  • WO 99/67227 discloses triazine carbamates as UV absorbers, which can be coupled with di- or polyisocyanates.
  • systems are created with a high melting point, which are difficult to process or incorporate into a polymer matrix.
  • the object of the present invention is to provide stabilizers which are effective against various damage mechanisms and have advantageous properties.
  • the stabilizers are said to be effective against UV radiation, heat, hydrolysis, oxidation or damage to ozone and to have one or more of the following advantageous properties, namely low volatility, not prone to blooming or bleeding, not washed out of the polymer, readily miscible and can be incorporated, - have a high concentration of active ingredients based on the total weight of the stabilizer, can be emulsified or dissolved in a liquid component, depending on the application, can be easily synthesized using the same or similar processes.
  • the stabilizers according to the invention can contain exactly one active substance group or several different active substance groups, for example several different sterically hindered phenols or a sterically hindered phenol and a HALS compound.
  • the several different groups of active substances can be selected from different classes of active substances (sterically hindered phenols, sterically hindered amines (HALS stabilizers), benzotriazoles, benzophenones, aromatic amines and phosphites).
  • Properties of the stabilizers that are modified by the auxiliary groups are, for example, the emulsifiability or solubility in polar or non-polar solvents and / or the incorporation into a plastic or a plastic mixture.
  • the invention further relates to the use of the stabilizers for stabilizing dispersions, paints, coatings, dyes, adhesives, foods, pharmaceuticals and cosmetics.
  • varnishes are varnishes for metal, wood, plastic, paper and leather coating. Paints for the metal coating are, for example, vehicle paints, automotive refinish paints, coil coatings, can coatings, aircraft paints and industrial paints.
  • the polyisocyanates (I) contain on average 2-10, preferably 2.2-8 isocyanate groups per molecule.
  • Suitable di- and polyisocyanates are the aliphatic, cycloaliphatic and aromatic isocyanates known from the prior art.
  • Preferred di- or polyisocyanates are 4,4-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, the mixtures of monomeric diphenylmethane diisocyanates and oligomeric diphenylmethane diisocyanates (polymer MDI), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1, 5- and 2,6-naphthylene diisocyanate, 1,3- and 1,4-phenylene diisocyanate, diphenyl diisocyanate, toluidine diisocyanate, triisocyanatotoluene, tetramethylene diisocyanate nat, hexamethylene diisocyanate, isophorone diisocyanate, 2,4'-
  • Mixtures of two or more of the aforementioned polyisocyanates are preferably used.
  • Suitable polyisocyanates are furthermore compounds which are derived from the di- or polyisocyanates mentioned above or their mixtures by linking using urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide, uretonimine , Oxadiazinetrione or iminooxadiazinedione structures can be produced.
  • urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide, uretonimine , Oxadiazinetrione or iminooxadiazinedione structures can be produced.
  • Polyisocyanates are preferably used which contain urethane, allophanate, urea, biuret, isocyanurate, uretonimine, oxadiazinetrione or Contain iminoxadiazinedione structures.
  • Mixtures of the aforementioned polyisocyanates can also be used.
  • the linking of the di- or polyisocyanates via urethane groups is preferably carried out using alcohols or alcohol mixtures with a functionality of 2 or more.
  • examples include the reaction of 3 moles of hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate or diphenylmethylene diisocyanate with 1 1 mole of triol, for example glycerol or trimethylolpropane, or the reaction of two moles of an oligomeric diphenylmethane diisocyanate (polymer MDI) with 1 1 mole of diol Example called ethylene glycol, butanediol, hexanediol or a polyoxyalkylene diol. In these reactions, branched polyisocyanates with a functionality greater than 2 are formed. See also Becker and Braun, Plastic Handbook No. 7, Polyurethane, Carl-Hanser-Verlag Kunststoff 1993, page 91.
  • Polyisocyanates containing allophanate groups are produced from polyisocyanates containing urethane groups by reacting the urethane groups with further isocyanate groups. See also Becker and Braun, plastic Manual No. 7, Polyurethane, Carl-Hanser-Verlag Kunststoff 1993, page 94. Another way of preparation is the reaction of oxadiazinetrions with alcohols according to EP 825211.
  • An example of the preparation of an allophanate is the reaction of hexamethylene diisocyanate or isophorone diisocyanate with monoalcohols mentioned that lead to oligoisocyanates with a functionality greater than 2 according to GB 994 890, EP 496 208, EP 524 500 or EP 524 501.
  • Polyisocyanates containing urea and biuret groups can be prepared, for example, by reacting isocyanates with water or with amines. See also Becker and Braun, Kunststoff-Handbuch No. 7, Polyurethane, Carl-Hanser-Verlag Kunststoff 1993, page 95. The reaction of hexamethylene diisocyanate or isophorone diisocyanate with water or water-generating substances, as described in DE- A 28 08 801, DE-A 34 03 277 or DE-A 15 43 178 are described. In these reactions, branched polyisocyanates with a functionality greater than 2 are formed.
  • Polyisocyanates containing isocyanurate structures are obtained by catalytically or thermally cyclizing three isocyanate groups.
  • di- or polyisocyanates are used as starting compounds, higher oligomeric polyisocyanates are generally formed in addition to the actual trimers. The total functionality of these polyisocyanates is therefore greater than 3.
  • Examples include the production of branched polyisocyanates by isocyanuration of hexamethylene diisocyanate or Isophorone diisocyanate called, as it can be carried out according to DE-A 29 16 201 or DE-A 38 10 908.
  • Polyisocyanates containing uretonimine groups are obtained by further reacting polyisocyanates containing carbodiimide groups with isocyanate groups. See also Becker and Braun, Plastic Handbook No. 7, Polyurethane, Carl-Hanser-Verlag Kunststoff 1993, page 94.
  • Polyisocyanates containing oxadiazinetrione groups are obtained by reacting di- or polyisocyanates with carbon dioxide, as described, for example, in DE-A 16 70 666.
  • Polyisocyanates containing iminooxadiazinedione groups are to be regarded as asymmetrical relatives of the polyisocyanates containing isocyanurate groups. The preparation of these compounds is described for example in DE-A 197 34 048.
  • aliphatic or cycloaliphatic branched di- or polyisocyanates are used.
  • the stabilizers according to the invention contain one or more active ingredient groups (II), these active ingredient groups being coupled to the polyisocyanates via functional groups A which are reactive with the NCO groups of the polyisocyanates.
  • Active substance groups (II) in the sense of the present invention are groups which protect a plastic or a plastic mixture against harmful environmental influences. Examples are primary and secondary antioxidants, hindered amine light stabilizers, UV absorbers, hydrolysis protection agents, quenchers and flame retardants.
  • a stabilizer according to the invention can contain one or more, also different, active ingredient groups.
  • the number of active ingredient groups and the ratio of the active ingredient groups to one another are variable and only limited by the number of NCO groups of the polyisocyanates (I).
  • NCO groups of the polyisocyanates (I) are variable and only limited by the number of NCO groups of the polyisocyanates (I).
  • Such active ingredient groups (II) can be coupled to the NCO groups of the polyisocyanates (I) that slow down or stop the oxidative degradation of a plastic.
  • One class of active ingredients that act as antioxidants are sterically hindered phenols.
  • the stabilizers according to the invention contain a sterically hindered phenol of the general formula (1) as active ingredient group (II)
  • X and Y are each independently a hydrogen atom or a straight-chain, branched or cyclic alkyl radical having 1 to 12 carbon atoms, and Z is a radical of the formula
  • R 1 is a single bond, a linear or branched divalent organic radical having 1 to 100 carbon atoms, preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms, or R 1 is a divalent radical of the formula - (R 2 -C -R 3 ) m -, where R 2 and R 3 can be the same or different from one another and, independently of one another, each have a single bond, a linear or branched divalent organic radical having 1 - 50 C atoms, are preferably 1-10 carbon atoms, in particular 1-4 carbon atoms, and m is a number from 1-100, preferably from 1-10 and particularly preferably from 1-4.
  • C and C 1 are each independently a single bond, an oxygen atom, a sulfur atom, an -NH or an -NR group, an ester group (-C (O) O- or -O (O) C-), an amide group (-NHC (O) - or -C (O) NH-), a urethane group (- OC (O) NH- or -HNC (O) O-) or a urea group (-HNC (O) N- or -NC (O) NH-).
  • A is a functional group with which the active ingredient group is bound to the anchor group.
  • A are primary or secondary amino groups, hydroxyl, thiol, Carboxyl or epoxy groups.
  • Preferred functional groups A are hydroxyl groups, thiol groups and primary or secondary amino groups.
  • the stabilizers preferably contain as a phenolic active ingredient group a sterically hindered phenol of the formula (1a) in bound form,
  • active ingredient groups (II) is derived from phosphorus compounds which e.g. find use as a secondary antioxidant.
  • the stabilizers according to the invention contain a phosphite of the general formula (2) as active ingredient group (II)
  • W 1 , W 2 and W 3 are independently of one another a straight-chain, branched or cyclic alkyl radical having 1 to 30 carbon atoms or a substituted or an unsubstituted aryl radical having 3 to 30 carbon atoms.
  • W 2 and W 3 can also be hydrogen independently of one another, the meaning of Z is as defined above.
  • the stabilizers according to the invention contain benzotriazoles of the general formula (3) in bound form as active ingredient group (II).
  • Z is Z as defined above and X is a straight-chain, branched or cyclic alkyl radical having 1 to 12 carbon atoms.
  • the stabilizers contain benzophenones of the general formula (4) in bound form as active ingredients.
  • Z ⁇ and Z 2 are independently Z or CX, where X represents a hydrogen atom, a straight-chain or branched alkyl radical or a cycloalkyl radical having 1-12 C atoms, and C and Z are as defined above.
  • X represents a hydrogen atom, a straight-chain or branched alkyl radical or a cycloalkyl radical having 1-12 C atoms, and C and Z are as defined above.
  • Another group of active ingredients that stabilize polymers against the effects of UV light are the so-called hindered amine (light) stabilizers (HAS or HALS).
  • HALS hindered amine
  • HALS hindered amine
  • the activity of the HALS compounds is based on their ability to form nitroxyl radicals which intervene in the mechanism of the oxidation of polymers. HALS are considered to be highly efficient UV stabilizers for most polymers.
  • the stabilizers according to the invention contain, as active ingredient group (II), a sterically hindered amine which is capable of forming nitroxyl radicals in bound form.
  • the stabilizers according to the invention contain HALS active compounds of the general formula (5) in bound form as active compound groups:
  • X 1 , X 2 , Y 1 , Y 2 and X 3 independently of one another are a hydrogen atom, a straight-chain or branched alkyl radical or a cycloalkyl radical with 1 to 12 carbon atoms and X 3 furthermore an acyl radical with 2 to 18 carbon atoms Alkoxy radical having 1 to 19 carbon atoms and an aryloxycarbonyl radical having 7 to 12 carbon atoms, and Z is as defined above.
  • Aromatic amines are all compounds that have a substituted or unsubstituted amino group that are directly linked to an aromatic system. Depending on the substitution, aromatic amines serve as antioxidants or as an active ingredient against the harmful effects of ozone.
  • the stabilizers according to the invention contain aromatic amines of the general formula (6) in bound form as active ingredient group (II).
  • X 1 , X 2 , X 3 and X 4 are independently a hydrogen atom, a straight-chain or branched alkyl radical or a cycloalkyl radical having 1 to 12 carbon atoms or Z, where Z is as defined above, and
  • X 5 and X 6 are independently a hydrogen atom, a straight-chain or branched alkyl radical or a cycloalkyl radical with 1 to 12 carbon atoms or Z, where Z is as defined above.
  • the stabilizers according to the invention can have one or more auxiliary groups (III).
  • (III) represents an auxiliary group which influences the processing, incorporation, emulsifiability or solubility of the stabilizer in the interests of the user.
  • an auxiliary group which increases the emulsifiability of the stabilizer.
  • hydrophobicity of the product when used in hydrocarbon-containing solvents, it can be advantageous to increase the hydrophobicity of the product by preferably incorporating hydrophobic radicals as an auxiliary group. At the same time, it may be important for the processing of the stabilizer to lower the glass temperature and viscosity.
  • auxiliary group can then also be deployed here, the Accumulation of the stabilizer molecules in aggregates is prevented and thus reduces viscosity.
  • solubility of the stabilizer in the interest of the user can also be influenced by the choice of the auxiliary group. In this way, for example, the transfer from the plastic into the food can be reduced or the distribution of the stabilizer in the case of different polymer blends can be directed in favor of one of the two blend components. Due to the diverse tasks that can be assigned to the auxiliary group (III), the type of structure of the auxiliary group (III) is very diverse.
  • the auxiliary group (III), like the active ingredient group (II), is bound to the polyisocyanate (I) via functional groups B which react with the NCO groups of the polyisocyanate (I).
  • groups B are primary or secondary amino groups, hydroxyl, thiol, carboxyl and epoxy groups. Hydroxyl and thiol groups and primary or secondary amino groups are preferred.
  • auxiliary groups with a hydrophobic effect can have the following schematic structure:
  • S. in this context is a non-polar residue, e.g. a straight-chain, branched or cyclic alkyl radical having 1 to 10000 carbon atoms, preferably 2-500 C atoms, in particular 4-50 C atoms.
  • S are straight-chain or branched aliphatic structures or aromatic structures, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, stearyl, oleyl -, Palmityl, oligobutyl, oligobutadienyl, oligosisobutyl, polybutyl, polybutadienyl, polyisobutyl, phenyl, naphthyl or nonylphenyl radicals.
  • aliphatic structures or aromatic structures such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, stearyl, oleyl -, Palmityl, oligobutyl, oligobut
  • auxiliaries having a hydrophobic effect are stearic acid, oleic acid, palmitic acid, stearic acid chloride, octylamine, stearylamine, polyisobutyleneamine, dipentylamine, diisopentylamine, dihexylamine, octyl alcohol, stearyl alcohol, hexadecanol, octadecanol, polyisobylphenol alcohol, octadylphenol alcohol, octadyl phenol alcohol Benzyl alcohol or phenylethanol.
  • BS hydrophobic effect
  • (III) can have the following schematic structure.
  • BT T in this context is a hydophilizing group, for example a diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, oligoethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, oligopropylene glycol monomethyl ether, polypropylene glycol monomethyl ether or a poly (propylene ether) glycol monomethyl ether.
  • hydrophilizing effects residues of aminocarboxylic acids, hydroxycarboxylic acids, mercaptocarboxylic acids, aminosulfonic acids, hydroxysulfonic acids, mercaptosulfonic acids, hydroxyamine, hydroxyammonium or hydroxyphosphonium compounds.
  • auxiliaries which have a hydophilizing action are diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, oligoethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, oligopropylene glycol monomethyl ether, polypropylene glycol monomethyl ether poly (ethylene) (propylene) glycol monomethyl ether, 2-methoxy-methoxyethyl, 2-methoxy-methoxy-3-methoxyethylamine propylemin), 9-amino-3,6-dioxanonan-1-ol or higher molecular weight polyalkylene oxide amines, commonly known under the name Jeffamine ® from Huntsman, lactic acid, mercaptoacetic acid, Hydroxypivalin Text- acid, glycine, beta-alanine, taurine, diethanolamine , Dipropanolamine, dibutanolamine, N, N-dimethylethanolamine or N, N-diethylethanolamine.
  • the stabilizers according to the invention are usually prepared by means of a polyaddition reaction in such a way that at least one polyisocyanate (I) as an anchor group, optionally with the use of an organic solvent, is placed in a reaction vessel under an inert gas atmosphere, preferably under nitrogen, and brought to the reaction temperature with stirring. Then at least one active ingredient (II) is added continuously or batchwise at the reaction temperature.
  • the amount of active ingredient (II) depends on the number of NCO groups in the polyisocyanate (I) and is preferably chosen so that the ratio of the number of moles of isocyanate groups to the number of moles of groups A of the active ingredient which are reactive with these is essentially 1: 1.
  • the stabilizers according to the invention can still have up to 20 mol%, preferably up to 10 mol%, of free NCO groups, ie NCO groups which have not reacted with an active ingredient (II) or an auxiliary (III).
  • the stabilizers according to the invention preferably have essentially no free NCO groups.
  • the reaction time is generally chosen so that the NCO groups of the polyisocyanates (I) are completely reacted with the reactive groups A of the active compounds and, if appropriate, the reactive groups B of the auxiliary substances.
  • the aforementioned reaction with the active ingredient groups and the auxiliaries can optionally be carried out in the presence of catalysts, in amounts of from 0.0001 to 1% by weight, in particular from 0.001 to 0.1% by weight, in each case based on the amount of the polyisocyanates (I) can be used.
  • catalysts Organometallic compounds, in particular tin, zinc, titanium, bismuth or zirconium organic compounds, are suitable as catalysts for polyaddition reactions.
  • dibutyltin dilaurate, dibutyltin oxide, titanium tetrabutylate, zinc acetylacetonate or zirconium acetylacetonate are particularly preferably used.
  • Strong bases preferably nitrogen-containing compounds, such as tributylamine, chinnuclidine, diazabicyclooctane, diazabicyclononane, diazabicyclonones, diazabicycloundecane or diazabicycloundecene can also be used.
  • nitrogen-containing compounds such as tributylamine, chinnuclidine, diazabicyclooctane, diazabicyclononane, diazabicyclonones, diazabicycloundecane or diazabicycloundecene can also be used.
  • Suitable solvents are those which are inert to the starting materials under reaction conditions.
  • acetone, 2-butanone, ethyl acetate, butyl acetate, tetrahydrofuran, dioxane, benzene, toluene, xylene, ethylbenzene, chlorobenzene, dichlorobenzene, dimethylformamide, dimethylacetamide or N-methylpyrrolidone are suitable.
  • the reaction temperature for the polyaddition reaction is usually -10 to 220 ° C, preferably 0 to 180 ° C.
  • the reaction takes place both at atmospheric pressure and at a pressure above or below atmospheric pressure, for example at a pressure of 2 to 20 bar or at 0.1 to 0.001 bar.
  • Example 1 Preparation of a phenolic active ingredient In a 500 ml round bottom flask with stirrer, gas inlet tube and a distillation bridge 609 g Pluriol E 200 ® (BASF AG), 175 g Ra lox ® 35 (3,5-Bis (1, 1-dimethylethyl) -4 be while introducing dry nitrogen -hydroxybenzylpropion Acid-methylester, Raschig GmbH Ludwigshafen) and 2.8 g Weston ® TNPP (Messrs. General Electric) was added. The mixture is heated to 145 ° C. and 1.8 g of potassium methoxide are added. The resulting methanol is removed via the distillation bridge and collected in a cold trap.
  • Pluriol E 200 ® BASF AG
  • Ra lox ® 35 3,5-Bis (1, 1-dimethylethyl) -4 be while introducing dry nitrogen -hydroxybenzylpropion Acid-methylester, Raschig GmbH Ludwigshafen
  • the reaction mixture is cooled to 80 ° C. Then 2.5 g of 85% phosphoric acid are added to neutralize the product. The mixture is stirred for a further 15 min at 80 ° C. and then washed with water. For this purpose, 1000 ml of distilled water are heated in a beaker to 40 ° C and the 80 ° C warm product is slowly added to the water with vigorous stirring. The aqueous mixture is then stirred for 30 minutes, left to stand until the phases separate and the water phase is decanted from the product. This washing process is repeated again. The product is then dried on a rotary evaporator at approx. 80 ° C and 10 mbar.
  • Example 2 Production of an active ingredient based on benzophenone
  • Tg glass transition temperatures
  • DSC differential scanning calorimetry
  • GPC gel permeation chromatography
  • Tg glass transition temperatures
  • DSC differential scanning calorimetry
  • GPC gel permeation chromatography
  • Example 13 Stabilizer J According to the Invention, Stabilizer System
  • BASONAT ® HI 100 (BASF AG): aliphatic polyisocyanurate based on hexamethylene diisocyanate, the average functionality is approx. 3.7 NCO groups per molecule.
  • BASONAT ® HB 100 (BASF AG): aliphatic polybiuret based on hexamethylene diisocyanate, the average functionality is approximately 3.7 NCO groups per molecule.
  • BASONAT ® HA 300 (BASF AG): aliphatic polyisocyanate based on hexamethylene diisocyanate, the average functionality is approx. 2.8 NCO groups per molecule.
  • LUPRANAT ® M 20 W (Elastogran GmbH): aromatic polyisocyanate based on diphenylmethane diisocyanate, the average functionality is approx. 2.3 NCO groups per molecule.
  • Example 15 Production of a thermoplastic polyurethane (TPU) based on polyether
  • 750 g of a polytetrahydrofuran having a mean molecular weight of 1000 g / mol (Po lyTHF ® 1000, BASF AG) are heated in a tinplate bucket to about 80 ° C.
  • the additives from Table 3 and 93 g of butanediol are then added with stirring.
  • the solution is heated to 75 ° C. with stirring.
  • 450 g of 4,4'-diphenylmethane diisocyanate are added and the mixture is stirred until the solution is homogeneous.
  • the TPU is then poured into a flat dish and annealed on the hot plate for 10 min at 125 ° C, then in the heating cabinet at 100 ° C for 24 h.
  • the plates After the plates have cooled, they are ground into granules in a mill. Then 2% by weight of the yellow dye concentrate 138 (Elastogran GmbH) is homogeneously mixed into the granules and processed on an injection molding machine to give 2 mm injection molding plates.
  • the product has a Shore hardness of 85A.
  • Table 3 provides information on the type and quantity of stabilizers used. Irganox ® and Tinuvin ® are stabilizer brands from Ciba Specialty Chemicals GmbH, Germany. Table 3: Stabilizer mixtures containing stabilizers according to the invention with HALS active ingredient groups
  • the spray plates are exposed according to DIN 75202. After the exposure, a color measurement device from Hunterlab is used to determine the yellowness indices (Yl) of the exposed samples. Table 4 shows the results of the exposure.
  • Example 16 Stabilization of a TPU with a stabilizer according to the invention containing phenolic active ingredient groups in comparison to commercial products
  • a series of tests containing stabilizers I and H from Table 2 is prepared in accordance with the instructions in Example 15. After granulation of the pouring ridges, the product is injection molded into 2 mm test plates without adding the dye concentrate.
  • the comparative stabilizer is the phenolic stabilizer Ralox 35 (Raschig GmbH, Ludwigshafen). This stabilizer has a high concentration of active ingredients (3.4 mol / kg).
  • An important goal of stabilizing polyether TPU is to increase the resistance to thermo-oxidative degradation. This can be achieved, for example, by adding sterically hindered phenols.
  • S 2 rods are punched out of the spray plates and stored at 130 ° C. in a forced air oven. The elongation at break is then determined in accordance with DIN 53504.
  • DIN 53504 the effect of the stabilizers according to the invention is superior to that of the commercial product.
  • the active ingredient group concentration is only 17% of the concentration in trial 16e with the comparative stabilizer, but the elongation at break remains at a high level for a longer time.
  • Table 6 Decrease in elongation at break when the samples are stored in a forced air oven at 130 ° C
  • Example 17 Stabilization of a polyester
  • Irganox ® and Irgaphos® ® are trade names of Ciba Specialty Chemicals GmbH, Germany
  • Ultradur ® B 4520 is a polybutylene terephthalate from BASF AG.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des stabilisateurs constitués (I) d'un ou de plusieurs polyisocyanates avec en moyenne 2 à 10, de préférence 2,1 à 10, idéalement 2,2 à 10 groupes isocyanate par molécule, (II) de 0,1 à 1,0 mole d'un ou de plusieurs groupes d'agents actifs par mole de groupes isocyanate, lesquels groupes d'agents actifs protègent les matières plastiques contre les dommages causés par la chaleur, le rayonnement ultraviolet, l'oxydation, l'hydrolyse ou l'action mécanique lors des opérations de transformation, ces groupes d'agents actifs étant reliés aux polyisocyanates par l'intermédiaire de groupes fonctionnels A pouvant réagir avec des groupes isocyanate et lesdits groupes d'agents actifs étant sélectionnés parmi des phénols, des amines à encombrement stérique (stabilisateurs HALS), des benzotriazoles, des benzophénones, des amines aromatiques et des phosphites, ainsi que (III) de 0 à 0,9 mole d'un ou de plusieurs groupes auxiliaires par mole de groupes isocyanate, lesquels groupes auxiliaires modifient les propriétés du stabilisateur et sont reliés aux polyisocyanates par l'intermédiaire de groupes fonctionnels B pouvant réagir avec les groupes isocyanate.
EP05700885A 2004-01-21 2005-01-13 Stabilisateurs a base de polyisocyanates Withdrawn EP1709097A1 (fr)

Applications Claiming Priority (2)

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DE102004003024A DE102004003024A1 (de) 2004-01-21 2004-01-21 Stabilisatoren auf Basis von Polyisocyanaten
PCT/EP2005/000272 WO2005070987A1 (fr) 2004-01-21 2005-01-13 Stabilisateurs a base de polyisocyanates

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DE102004052874A1 (de) * 2004-11-02 2006-05-04 Basf Ag Stabilisierte thermoplastische Formmassen
BRPI0819699A2 (pt) * 2007-11-28 2015-07-07 Basf Se Mistura uso de uma mistura, plástico, artigo, e, método para estabilizar plásticos contra o efeito de luz, oxigênio e/ou calor
US20100261825A1 (en) * 2009-04-13 2010-10-14 Senkfor Howard L Coating compositions comprising polyurea and an anti-oxidant compound
CA2920987A1 (fr) 2013-08-22 2015-02-26 Basf Se Compositions stabilisees renfermant des polymeres acrylamides et procede de production tertiaire d'huile minerale employant lesdites compositions
PL4110767T3 (pl) 2020-02-26 2025-11-03 Basf Se Mieszanina dodatków do modyfikowania reologii polimerów
EP4584315A1 (fr) 2022-09-07 2025-07-16 Basf Se Modification rhéologique de polymères à l'aide d'un initiateur radicalaire et de thiouréthane
WO2024133667A1 (fr) 2022-12-21 2024-06-27 Basf Se Procédé d'amélioration du traitement du polyéthylène

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DE3800294A1 (de) * 1988-01-08 1989-07-20 Huels Chemische Werke Ag Urethanderivate von gehinderten phenolalkoholen und damit stabilisiertes organisches material
CA2116167C (fr) * 1993-03-15 2007-05-15 Myron W. Shaffer Compositions de revetement a un seul element contenant des polyisocyanates bloques par des groupes oxime ou lactame a proprietes ameliorees de resistance au jaunissement
DE19645165A1 (de) * 1996-11-02 1998-05-07 Huels Chemische Werke Ag Lackpolyisocyanate mit eingebautem HALS-Stabilisator
DE19650045A1 (de) * 1996-12-03 1998-06-04 Huels Chemische Werke Ag Lackpolyisocyanate mit eingebautem HALS-Stabilisator

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