DE4426222A1 - Improvements of, or relating to, organic compounds - Google Patents

Abstract

A compound of the formula I <IMAGE> in which R represents hydrogen, oxygen, -O-R8, C1-8-alkyl; or -COR5; R3 is hydrogen, C1-4-alkyl or <IMAGE> in which R5 represents -C(R3)=CH2, C1-6-alkyl, phenyl, -NR7R8, <IMAGE> , -CH2-C6H5, <IMAGE> or <IMAGE> in which R7 is hydrogen, C1-12-alkyl, C5-6-cycloalkyl, phenyl, phenyl-C1-4-alkyl or C1-12-alkylphenyl and R8 is C1-12-alkyl or hydrogen, each R1 independently represents -CH3 or -CH2(C1-4-alkyl) or both R1 groups together form a -(CH2)5- group; each R2 independently represents -CH3 or -CH2(C1-4-alkyl) or both R2 groups together form a -(CH2)5- group; R15 denotes hydrogen, C1-12-alkyl, C1-12-alkoxy or halogen; n is an integer from 1 up to and including 4; Y is a direct bond, <IMAGE> or <IMAGE> in which x is an integer from 1 up to and including 8; R4 is C1-22-alkyl or C2-22-alkenyl if n = 1, where the alkyl or alkenyl groups are not interrupted or are interrupted by 1 or 2 atoms selected from amongst oxygen and sulphur; or R4 is a group of the formula alpha <IMAGE> or, if Y is a direct bond or denotes <IMAGE> R4 can additionally denote phenyl which is unsubstituted or substituted by 1 or 3 groups selected from amongst C1-4-alkyl, C1-4-alkoxy and halogen, R4 is C1-22-alkylene or C2-22-alkenylene if n = 2, where the alkylene or alkenylene group ... not interrupted or ... by 1 or 2 atoms ... Original abstract incomplete.

Description

The invention relates to new tetraalkylpiperidine Ver bonds that are found in polymeric systems as light stabilizers own.

According to the invention, a compound of formula I

provided wherein R is hydrogen, oxygen, -O-R₈,
C _1-8 alkyl; or -COR₅;
R₃ is hydrogen, C _1-4 alkyl or

means
wherein R₅ for -C (R₃) = CH₂, C _1-6 alkyl, phenyl, -NR₇R₈,

stands,
wherein R₇ is hydrogen, C _1-12 alkyl, C _5-6 cycloalkyl, phenyl, phenyl-C _1-4 alkyl or C _1-12 alkylphenyl and
R₈ is C _1-12 alkyl or hydrogen,
each R₁ independently represents -CH₃ or -CH₂ (C₁₄ alkyl),
or both R₁ groups together form a - (CH₂) ₅ group;
each R₂ independently represents -CH₃ or -CH₂ (C _1-4 alkyl),
or both R₂ groups together form a (CH₂) ₅ group;
R₁₅ represents hydrogen, C _1-12 alkyl, C _1-12 alkoxy or halogen;
n is an integer from 1 to 4 inclusive;
Y a direct bond,

where x is an integer from 1 to 8 inclusive;
R₄ is, if n = 1, C _1-22 alkyl or C _2-22 -Al kenyl; wherein the alkyl or alkenyl groups are not interrupted or interrupted by 1 or 2 atoms selected from oxygen and sulfur; or
R₄ is a group of the formula α

or if Y is a direct bond or

means, R₄ can additionally be phenyl which is unsubstituted or substituted by 1 or 3 groups selected from C _1-4 alkyl, C _1-4 alkoxy and halogen
R₄ is, if n = 2, C _1-22 alkylene or C _2-22 alkenylene, the alkylene or alkenylene groups not being interrupted or interrupted by 1 or 2 atoms selected from oxygen or sulfur; or
R₄ can additionally if Y is a direct bond or

is phenyl, which is unsubstituted or substituted by 1 or 2 groups selected from C _1-4 alkyl, C _1-4 alkoxy or halogen;
If n = 3, R₄ is a trivalent C _1-22 alkane or a trivalent C _2-22 alkene group; wherein the alkane or alkene groups are not interrupted or interrupted by 1 or 2 atoms selected from oxygen or sulfur; or
If Y is a direct bond, R₄ can
or

means, additionally

be;
If n = 4, R₄ is a tetravalent C _1-22 alkane or a tetravalent C _2-22 alkene group, the alkane or alkene groups being uninterrupted or interrupted by 1 or 2 atoms selected from oxygen or sulfur ; or
R₄ can if Y for a direct bond or

stands, in addition

mean.

Preferably R is R ', where R' is hydrogen, C₁₄ alkyl or -CO-R₅ ', where R₅' is -CH = CH₂, C _1-4 alkyl or -CO- -OC _1-4 alkyl .

Preferably each R₁ and each R₂ means methyl.

Preferably R₃ is R₃ 'wherein R₃' is hydrogen or Methyl, particularly preferably hydrogen.

Preferably n is n ', where n' is 1 or 2.

Y is preferably Y ′, where Y ′ is for a direct bond
or

stands.

Preferably R₄ is R₄ 'where R₄', if n = 1, is C _1-12 alkyl which is not interrupted or interrupted by an -S or -O atom; and wherein R₄ 'if n = 2, is C _1-12 alkylene which is not interrupted or interrupted by an -S or -O atom.

Preferably R₁₅ is hydrogen.

In this specification, each alkyl group means preferred have an alkyl group of 1-4 carbon atoms and each Alkyl group with 1-4 carbon atoms is preferably methyl or ethyl.

In this description, each group that is able to to be straight chain or branched, straight chain or branched, unless stated otherwise.

Where a symbol appears more than once in a formula, its meanings are independent of each other.

Preferred compounds of the formula I have the formula I ′

where the symbols are defined above.

Furthermore, according to the invention, a method for manufacturing Provided a compound of formula I that the Reaction of n moles of a compound of formula II

with one mole of a compound of formula III

(Hal-Y) _n -R₄ (III)

wherein Hal is chlorine or bromine; and
wherein the remaining symbols are defined above; at elevated temperature, preferably in the presence of a base (for example K₂CO₃).

Is preferably in a method according to the Invention the temperature in the range of 40 to 150 ° C.

The pH is preferably 5 to 7.

Furthermore, according to the invention, a composition provided a polymeric material and one as above includes defined compound of formula I.

Furthermore, according to the invention, a method for stabilization lization of a paint composition on acrylic, alkyd or Polyester resin base (which, if desired, with melamine / form aldehyde resins, epoxy resins or polyisocyanates can) provided, which the insertion of a defi ned, compound of formula I in the resin.

Furthermore, according to the invention, a paint composition based on acrylic, alkyd or polyester resin (which, if desired, with melamine / formaldehyde resins, epoxy resins or Isocyanates can be crosslinked) provided one or contains several compounds of formula I, defined above.  

Lacquer compositions according to the invention can be metal lische, one or two-layer paint compositions or uni be one or two-layer paint compositions. Preferably is a paint composition, according to the invention, a Stove enamel composition.

Compounds of formula I are protective stabilizers the polymeric material against light decomposition, can be used. The compounds have a particularly good solubility and Miscibility in solvent systems and in liquid polymers as well as in prepolymers, which they have in a wide range of makes polymeric materials usable.

The concentration of compounds of formula I, which in polymeric material used is expedient from 0.01 to 8% by weight, preferably 0.02 to 1% by weight. The verb dung can be added before, during or after the polymerization step can be set and in the solid state, in solution, preferably as a liquid concentrate containing 20 to 80 wt .-% one Compound of the formula I or as a solid concentrate composition, containing 20 to 80 wt .-% of a compound of formula I and 20th to 80 wt .-% of a solid polymeric material, which with the polymeric material to be stabilized, identical or is compatible.

Suitable polymeric materials include plastic mate rialien for example polyethylene, polypropylene, ethylene / propy len copolymers, polyvinyl chloride, polyester, polyamides, poly urethanes, polyacrylonitrile, ABS, terpolymers of acrylates, sty rol and acrylonitrile, styrene / acrylonitrile and styrene / butadiene. Other plastic materials such as polybutylene, polystyrene, chlo rated polyethylene, polycarbonate, polymethyl methacrylate, poly phenylene oxide, polypropylene oxide, polyacetals, phenol / formaldehyde Resins and epoxy resins can also be used. Before drawn plastic materials are polypropylene, polyethylene,  Ethylene / propylene copolymers and ABS. Natural polymers, at for example natural rubber, can also be stabilized like lubricating oils that contain plastic material ten.

The compounds of formula I can be known Procedures are inserted into the material to be stabilized. Mixing the connections is of particular importance with thermoplastic polymers in the melt, for example in a melt mixer or during the formation of molded Articles, including foils, films, tubes, containers, fla fibers, and foams, by extrusion, injection molding, Blow molding, spinning and wire coating.

It is not essential for the polymeric material that it before mixing with the compounds according to the invention, is fully polymerized. The connections can be made with the mono mers, prepolymers or precondensates mixed and the poly Merization or condensation reactions can then be performed. This is actually the preferred one Method of incorporating the compounds into thermosetting Polymers that cannot be mixed in the melt.

The compounds of formula I can be used alone or together use with other stabilizers, such as antioxidants be det. Examples include sterically hindered Phenols, sulfur or phosphorus-containing compounds or their mixtures. Examples are benzofuran-2-one, indolin-2-one and sterically hindered phenols e.g. B. β- (4-hydroxy-3,5-di-tert. butylphenyl) propionyl stearate, methane tetrakis [methylene] 3 (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate), 1,3,3-tris- (2-methyl-4-hydroxy-5-tert.butylphenyl) butane, 1,3,5-tris- (4- tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, bis- (4-tert-butyl-3-hydroxy-2,6-dimethyl) benzyl) dithiol terephthalate, tris- (3,5-di-tert-butyl-4-hydroxy benzyl) isocyanurate, the triester of β- (4-hydroxy-3,5-di-tert.  butylphenyl) propionic acid with 1,3,4-tris- (2-hydroxyethyl) -5- triazine-2,4,6 (1H, 3H, 5H) -trione, bis [3,3-bis- (4'-hydroxy-3-tert. butylphenyl) butyric acid] glycol ester, 1,3,5-trimethyl-2,4,6- tris- (3,5-di-tert-butyl-4-hydroxy-benzyl) benzene, 2,2'-methylene bis- (4-methyl-6-tert-butylphenyl) terephthalate, 4,4-methylene bis- (2,6-di-tert-butyl-phenol), 4,4'-butylidine-bis- (tert-butyl metacresol), 2,2'-methylene-bis- (4-methyl-6-tert.butyl-phenol).

Sulfur-containing antioxidant costabilizers that can include, for example, di-stearyl-thio dipropionate, di-lauryl thiodipropionate, methane tetrakis (methy len-3-hexylthiopropionate), methane tetrakis (methylene-3-dodecyl thiopropionate) and dioctadecyl disulphide. Costabi containing phosphorus Lisators include, for example, trinonylphenyl phosphite, 4,9-di stearyl-3,5,8,10-tetraoxadiphosphaspiroundecane, tris- (2,4-di tert-butylphenyl) phosphite and tetrakis (2,3-di-tert-butylphe nyl) -4,4, -biphenylene-diphosphonite. Other additives, such as amino aryl compounds and U.V. absorbers and light stabilizers, for example 2- (2'-hydroxyphenyl) benzotriazole, 2-hydroxy benzophenone, 1,3-bis (2'-hydroxybenzoyl) benzene, salicylates, Cinnamates, benzoates and substituted benzoates, steric hindered amines and oxalic acid diamides can be used. Other known types of additives, for example Ent Flame retardants and antistatic agents can also be used be added.

Preferably a compound of formula XX

wherein
R₃₀ represents C _6-22 alkyl or C _6-22 alkoxy, R₃₁ and R₃₂ are independently selected from hydrogen, C _1-8 alkyl, C _1-12 alkoxy, C _1-12 alkylthio, phenoxy and Phenylthio
with the proviso that only one of R₃₁ and R₃₂ is alkylthio, phenoxy or phenyl thio and
R₃₃ is hydrogen or C _1-8 alkyl, added to a compound of formula I.

The compounds according to the invention can also be found in photopolymeric substrates containing photoinitiators for the Photopolymerization can be used.

The compounds of formula I are particularly suitable for Use in coatings containing organic polymers, in particular especially in car paints.

Such car paints are generally solutions or Dispersions of organic polymers or polymer precursors in organic solvents. The majority are curable Paints that require the application of heat in general Temperatures above 80 ° C to the paints within an acceptable Time to harden as soon as it is applied to a primer seen metal surface were applied. The hardening level can be accelerated through the use of an acid catalyst become. The effect of this heating can be the che mix reaction between the polymer precursors in a thermo accelerate the curable system or the fusion of To accomplish particles of thermoplastic polymers.

Many car paints are metallized and contain metal scale, usually made of aluminum, for optical effects due to reflection. Such varnishes are often two layered lacquers with a clear top layer over a base paint is applied, which is a pigment and / or metal flakes contains. The compounds of formula I can be found in the deck layer or in the base coat, preferably in the former.  

Such two-layer paintwork requires in particular U.V. Stabilizers in the surface coating after the polymer is in this coating is not protected by light-absorbing pigments and it is, as a result of reflection of light from the bottom metallic layer, which is almost twice as strong radiation, is exposed to normal radiation.

The compounds of formula I are for use as U.V. stabilizers in a wide range of liquid paints suitable, for example those who are on combinations of Melamine - formaldehyde resins with oil-modified polyester resins, of polyacrylate resins with added crosslinking agents, or sown made polyesters; or from self-networkers, or from sown made polyesters; or of self-crosslinked polyacrylates or Polyacrylate resins that are copolymerized with styrene are based.

Other examples are two-component paints that are on one aliphatic or aromatic di-isocyanate and a hydroxy groups containing polyacrylate, polyester or polyether resin are based. These polyurethane two-component paints will be preferably hardened at 60 to 120 ° C. Thermoplastic poly acrylate resins can also be used, the latter are particularly useful in metallized paints like this also polyacrylate resins with added crosslinkers in com combination with melamine-formaldehyde resins, etherified with butanol, are, and also hydroxy group-containing polyacrylate resins be cured with aliphatic diisocyanates. Such poly acrylate resins are e.g. B. in U.S. Patent No. 3,062,753, the content of which is incorporated herein by reference.

The compounds of formula I are particularly useful in acid catalyzed paints in the top layer of a Two-layer metal painting.

The compounds of formula I can paint in any stage can be added to its manufacture and can be in solid form  or added in solution, preferably in the form of a liquid concentrate in a suitable solvent or in in the form of a dispersion in water or an organic Solvent.

In practice, the compounds of formula I as Lö solution in an organic solvent (in liquid form), in which the binder is present in a proportion between 35% by weight (low solids concentration) and 70% by weight (high solids Concentration). The binder of the varnish can become Form of an aqueous emulsion or suspension (water-based paint) are in which the part of the binder 20 to 30 wt .-% matters. However, the compounds of formula I can also known powdered finishes can be added.

The compounds of formula I are said to be liquid or solid paints should be added before baking or curing. The compounds of the formula I are preferably liquid Lacquers are used because it is easy to dose so precisely. It is particularly preferred to use a concentrate (preferred in a hydrocarbon solvent), the one Compound of the formula I in a proportion of at least 40% by weight, preferably 60 to 80 wt .-%, based on the total weight of the Concentrate, contains to the compound of formula I in the Applying stoving lacquers.

The addition of 0.01 to 8% by weight, preferably 0.2 to 4 % By weight of one or more compounds of the formula I gives one clear improvement of the light and weather stability of orga African pigments in stoving lacquers, with the tendency to Hairline cracks and a loss of shine as a result of the decay tion is reduced. This was also the case with metallized Lacquers are found and it will be an excellent, long-term Stability of the clear top layer in the two-layer Preserved metallic paints. In such paints, the connection Formula I to the metallic base coat, the clear top coat  or both, preferably only added to the clear topcoat become. The metallized paint can, like that in the prior art the coating of metal surfaces is common, with a primer be coated. Compounds of formulas III and IV can with suitable monomers (in particular those in Lacquers are used), for example monomers on acrylic and Alkyd base to be copolymerized.

The invention will now be described in the following examples shown, in which all parts and percentages related to Ge important and the temperatures are given in C, unless that The opposite is said.

example 1

The compound of formula 1a

can be made as follows: 638 g of the compound of Formula 1b

30.3 g of K₂CO₃, 2 g of KI and 400 ml of methyl ethyl ketone Heated 70-75 ° and with 27.2 g of 1,8-dibromo-octane, which in 100 ml Methyl ethyl ketone is dissolved, implemented.  

Methyl ethyl ketone is dissolved, implemented.

The yellow suspension formed continues for a further 32 Stirred for hours, diluted with 500 ml of water and the formed Precipitate, the compound of formula 1a, dried in vacuo. The compound is recrystallized from ethanol and that The resulting powder has a melting point of 161-163 °.

Example 2

The compound of formula 2a

can be made as follows:
638 g of the compound of formula 1b (defined in Example 1), 30.3 g of K₂CO₃, 1 g of KI and 400 ml of methyl ethyl ketone are heated to 70-75 °, for 2 hours with 27.1 g of the compound of formula 2b

Cl-CH₂-COO (CH₂) ₆-COOCH₂Cl (2b)

implemented and stirred for a further 6 hours, after which the Solvent is distilled off. The residue is mixed with 300 ml Toluene and 300 ml of water reacted. The toluene phase is two times washed with water, which is then distilled off is concentrated. The resinous residue is mixed with acetone treated and the solid is recrystallized from toluene and hexane lized.

A white powder of the formula 2a is formed, the one  Has a melting point of 142-145 °.

APPLICATION EXAMPLE A

A clear coat consisting of
80 parts of Viacryl SC 344 (a 50% solution of an acrylic resin from Vianova),
13.9 parts of Maprenal MF 80 (a 72% solution of a melamine resin from Hoechst) and
4.1 Sharing Byketol OK (by Byk-Malinckrodt)
is added to 2 parts of a compound of formula 1a (described in Example 1). After a minute, the light stabilizing material thus formed is dissolved in a varnish. This lacquer is applied in the usual way (according to the known two-layer technology) to a metallized or a pigment-containing lacquer layer alone, in the moist state, by spraying, a layer being formed having a thickness of 30 to 40 μm owns. The coating formed is then cured at 140 for 30 minutes. The coating shows a good resistance to UV light and weathering.

APPLICATION EXAMPLE B

A clear coat consisting of
29.5 parts of Setalux C-1502 XX-60 (a 60% solution of an acrylic resin from Synthesis BV)
39.2 parts of Setalux C-1382 BX-45 (a 45% solution of an acrylic resin from Synthesis BV)
21.4 parts of Setamin US-138 BB-70 (a 70% solution of a melamine resin from Synthesis BV)
2.5 parts of Baysilonoil [(a 2% solution in xylene) from Bayer] and
7.4 Parts of Depanol Y (a solvent from Hoechst)
is stirred together with 2.5 parts of a compound of formula 1a (described in Example 1) and 2 parts of an acid catalyst obtained from phosphoric acid (type: Catalyst 269-9 from American Cyanamid) to form a homogeneous mixture. This lacquer is applied in a known manner (according to the known two-layer technique) to a metallized or a pigment-containing lacquer layer, in the moist state, by spraying, a layer having a thickness of 30 to 40 μm being formed. The coating obtained is then cured at 110 ° for 20 minutes. The coating shows a good resistance to UV light and weathering.

APPLICATION EXAMPLE C

A clear coat consisting of
75 parts of Macrynal SH 510 N (a hydroxyl-containing acrylic resin from Bayer)
2 parts of Baysilon oil A [(1% solution in xylene) from Bayer]
0.3 parts of dibutyl zinc dilaurate
0.35 parts of diethanolamine
5.0 parts of ethyl glycol acetate
5.0 parts of Solvesso 100
6.0 parts of xylene and
6.36 parts of butyl acetate

becomes 2.5 parts of a compound of formula 1a (described in Example 1) and 30 parts of Desmodur N 75 (from Bayer) were added.  

The homogeneous mixture formed in this way is known per se se (according to the known two-layer process) on a metallic coated or a pigmented lacquer layer, when wet, by spraying, applied a layer with a thickness from 30 to 40 µm and the coating formed during 20 Minutes is cured at 80 to 90 °. The 2K PUR Varnish shows good resistance to U.V. Light and Weathering.

APPLICATION EXAMPLE D

A uni-white pigmented lacquer consisting of
14.30 parts of Setamin US-132 BB 70 (a 70% solution of a synthetic melamine resin)
57.15 parts of Setal 84 W-70 (a 70% solution of an alkyd resin from synthesis)
7.70 parts of n-butanol
1.85 parts of butylene glycol acetate
9.50 parts of xylene and
25 parts of titanium dioxide (rutile type)
is added to 1.38 parts of the compound of the formula 1a (see Example 1). This lacquer is applied by spraying in a manner known per se onto primed steel sheet, which has been coated with a filler with a layer thickness of 20 to 30 μm, and after standing at room temperature for 30 minutes, the surface of the steel sheet is coated at 120 ° for 30 minutes. The coating obtained shows a very good resistance to UV light and weathering.

In application examples A to D, instead of Compound 1a, an appropriate amount of the compound according to Example 2 can be used.

Claims (1)

A compound of formula I. wherein R is hydrogen, oxygen, -O-R₈, C _1-8 alkyl; or -COR₅;
R₃ is hydrogen, C _1-4 alkyl or means
wherein R₅ for -C (R₃) = CH₂, C _1-6 alkyl, phenyl, -NR₇R₈, stands,
wherein R₇ is hydrogen, C _1-12 alkyl, C _5-6 cycloalkyl, phenyl, phenyl-C _1-4 alkyl or C _1-12 alkyl phenyl and
R₈ is C _1-12 alkyl or hydrogen,
each R₁ is independently -CH₃ or -CH₂ (C _1-4 alkyl)
or both R₁ groups together form a - (CH₂) ₅ group;
each R₂ is independently -CH₃ or -CH₂ (C _1-4 alkyl)
or both R₂ groups together form a - (CH₂) ₅ group;
R₁₅ represents hydrogen, C _1-12 alkyl, C _1-12 alkoxy or halogen;
n is an integer from 1 to 4 inclusive;
Y a direct bond, is
where x is an integer from 1 to 8 inclusive;
R₄ is, if n = 1, C _1-22 alkyl or C _2-22 -Al kenyl; wherein the alkyl or alkenyl groups are not interrupted or interrupted by 1 or 2 atoms selected from oxygen and sulfur; or
R₄ is a group of the formula α or if Y is a direct bond or means, R₄ can additionally mean phenyl which is unsubstituted or substituted by 1 or 3 groups selected from C _1-4 alkyl, C _1-4 alkoxy and halogen,
R₄ is, if n = 2, C _1-22 alkylene or C _2-22 alkenylene, the alkylene or alkenylene groups not being interrupted or interrupted by 1 or 2 atoms selected from oxygen or sulfur; or
R₄ can additionally if Y is a direct bond or is phenyl, which is unsubstituted or substituted by 1 or 2 groups selected from C _1-4 alkyl, C _1-4 alkoxy or halogen;
If n = 3, R₄ is a trivalent C _1-22 alkane or a trivalent C _2-22 alkene group; wherein the alkane or alkene groups are not interrupted or interrupted by 1 or 2 atoms selected from oxygen or sulfur; or
R Y can if Y is a direct bond or means, additionally his,
If n = 4, R₄ is a tetravalent C _1-22 alkane or a tetravalent C _2-22 alkene group, the alkane or alkene groups being uninterrupted or interrupted by 1 or 2 atoms selected from oxygen or sulfur ; or
R₄ can if Y for a direct bond or stands, in addition mean.
Preferably R is R ', where R' is hydrogen, C _1-4 alkyl or -CO-R₅ '.