DE4306747A1 - Phosphite(s) and phosphonite(s) with sterically hindered amino gps. - useful as light and process stabilisers for polyurethane(s), polyolefin(s) and plastics-based powder paints - Google Patents

Abstract

The use of sterically hindered amino gp.-contg. phosphite and phosphonite cpds. (I) as light stabilisers and processing stabilisers for polyurethanes and for polyolefins contg. residues of 2nd- and higher-generation catalysts is claimed; (I) are also useful as stabilisers for acrylate-, epoxy-, urethane- or polyisocyanate-based powder paints. (I) are used in amts. of 0.01-5 (pref. 0.05-2) wt.% in the plastics. ADVANTAGE - (I) are very stable towards hydrolysis (contrast prior-art phosphite and phosphonite stabilisers, esp. in the presence of catalysts and degradation prods. thereof).

Description

The invention relates to the use of sterically hindered amino groups containing phosphite and phosphonite compounds, for light and Processing stabilization of polyurethanes and of polyolefins with second generation catalysts or higher generation catalysts were produced, the catalysts from the polymers not have been removed and powder coatings on acrylate, epoxy, urethane or Polyisocyanate base.

The sterically hindered amino groups containing phosphites or phosphonites preferably correspond to formula I.

wherein

R is hydrogen, oxygen, hydroxyl, C _1-24 -alkyl, C _1-24 -alkoxy, C _1-24 -alkylcarbonyloxy, benzoyloxy or a radical of the formula -COR₅,
the two R₁, independently of one another, methyl or C _1-5 alkyl or together a group of the formula - (CH₂) ₅,
the two R₂, independently of one another, methyl or C _1-5 alkyl or together a group of the formula - (CH₂) ₅,
R₃ and R₄, independently of one another, linear or branched C _1-24 alkyl, C _7-24 aralkyl, C _7-24 alkaryl, C _5-24 cycloalkyl, C _6-24 aryl or a group of the formula a or, only one of R₃ and R₄, a group of formula b

or R₃ and R₄ together represent a radical of the formula

R₅ C _1-6 alkyl, phenyl, benzyl, benzoyl, carboxyl or a group of the formula -C (R₆) = CH₂, -NR₇R₈ or -CO-OC _1-12 alkyl,
R₆ is hydrogen or C _1-4 alkyl,
R₇ is hydrogen, C _1-12 alkyl, C _5-6 cycloalkyl, phenyl, phenyl-C _1-4 alkyl or C _1-12 alkylphenyl,
R₈ is hydrogen or C _1-12 alkyl,
AC _1-24 , C _6-24 cycloalkylene, arylene, C _7-24 aralkylene or a group of the formula c

all X, independently of one another, the direct bond, -N (R₉) -, -O- or -S-, preferably the direct bond or -O-,
R₉ is hydrogen or C _1-4 alkyl,
X₂ is the direct bond, -NR₉, -O-, -S-, C _1-24 alkylene (preferably - (CH₂) _1-4 -), C _6-24 cycloalkylene, arylene, C _7-24 alkarylene or C _7-24 aralkylene,
all R 1, independently of one another, hydrogen, linear or branched C _1-24 alkyl, C _5-24 cycloalkyl, C _7-24 alkaryl, C _7-24 aralkyl or C _6-24 aryl,
R₃a and R₄a, independently of one another, linear or branched C _1-24 alkyl, C _5-24 cycloalkyl, C _7-24 aralkyl, C _7-24 alkaryl or C _6-24 aryl or a group of the formula a and
n 0 or 1
mean.

Preferably means

RR 'and this is hydrogen, C _1-18 alkyl, C _1-18 alkoxy, acryloyl, benzoyloxy or a radical of the formula -COR₅',
R₅ 'is C _1-8 alkyl, C _1-8 alkylcarbonyl or C _1-4 alkoxycarbonyl.

Preferably all R₁₁ R₁₁ 'and this is hydrogen or C _1-8 alkyl, especially hydrogen, methyl, tert-butyl or tert-octyl.

Preferably all R₁ and all R₂ are always methyl.

Preferred compounds of the formula I correspond to the formulas II to VII

wherein

all R₁₀ linear or branched C _1-24 alkyl, C _5-24 cycloalkyl, C _7-24 aralkyl, C _7-24 alkaryl or C _6-24 aryl, aryl preferably being phenyl,
every m independently of one another 0 or 1 and
P is 1, 2 or 3

and the other symbols have the meanings given above; also Mixtures of these compounds are preferred stabilizers. The compounds of formula II, wherein R₁₀ is not phenyl and the X bound to R₁₀ means the direct bond, and the compounds of formula III, wherein X is the direct bond, the compounds of the formula V, where both are m = 1, and the compounds of Formulas IV, VI and VII are new and therefore also the subject of present invention.

R₁₀ preferably means R₁₀ 'and this is C _1-8 alkyl, C _5-11 cycloalkyl, C _7-24 aralkyl or C _7-24 alkaryl.

Particularly preferred compounds of the formula I correspond to the formulas 1 to 9

Mixtures of 1 to 90 percent by weight of a phosphonite Compound of formula I (above) and 99 to 10 weight percent of one Phosphites of the formula VIII

wherein

p 1, 2 or 3 and
X₁ -O- or -NR₆- means

and the rest Symbols have the meanings given above, as light and Processing stabilizers are used.

The compounds of formula I can by condensation of a mole of one Compound of formula X

with 1 mole of a compound of formula XI

or by condensation of 2 moles of a compound of formula X with 1 mole a compound of formula XII

R₄-X-P (Z) ₂ (XII),

wherein in the formulas XI and XII Z represents chlorine, bromine or -N (R₇) ₂ will.

The compounds of formulas I to VII can also according to others, the Methods familiar to those skilled in the art can be produced.

The compounds of formulas I to VII can also according to others, the Methods familiar to those skilled in the art can be produced.

Further stabilizers according to the invention correspond to formula XIII

wherein R 'and X have the meanings given above, R' is preferably R ″ and this is hydrogen or C _1-4 alkyl.

The use according to the invention of the phosphite and phosphonite stabilizers for polyolefins, e.g. B. polypropylene, and all Polyethylene qualities (high and low pressure polyethylene and medium pressure Polyethylene), polybutylene, polypentene, poly-4-methylpentene, Poly-3-methylpentene and the copolymers of these plastics.

The stabilization of polyurethanes should also be mentioned  Isocyanates and polyols, e.g. B. under the names Desmodur, elastane, Lupranat, Tedimon, Scuranat, Hylene, Isonat (-Papi), Multrathan, Nacconate and Sumidur are on the market. Such polyurethanes are e.g. B. in "Kunststoff-Taschenbuch", 23rd edition, (Saechtling), C. Hansen Verlag 1986 (pages 339-410).

The stabilizers are particularly suitable for use in polyolefins, especially α-polyolefins, which with catalysts of the II. to V. Generation were produced and in which the catalysts after the Manufacture was not removed using special methods.

The definition (composition, mode of action) of the catalysts of the II. to V. generation is known (see, e.g., UK patent application 22 57 706 A or the article "New Trends in Polyolefin Catalysts and Influence on Polymer Stability "by R. Mülhaupt, Twelfth Annual International Conference on Advances in the Stabilization and Controlled Degradation of Polymers, Lucerne, 21-23. May 1990, pages 181 to 196).

The powder coatings to be stabilized according to the invention are, for. B. in the book by David A. Bate, "The Science of Powder Coatings-Chemistry, Formulation and Application ", vol. 1, pages 249-277, (SITA 1990).

The stabilizers according to the invention / used according to the invention are very stable against hydrolysis, which with similar phosphite and phosphonite Stabilizers mostly very strong, especially in the presence of the catalysts or their degradation products.

The plastics stabilized according to the invention generally contain 0.01 to 5 percent by weight, preferably 0.05 to 2% of the said phosphite and / or phosphonite stabilizers.

As additional stabilizers, the polymer masses u. a. Antioxidants, e.g. B. hindered phenols, secondary aromatic amines or thioether (described, for example, in "Plastics Additives", Gächter and  Müller, 1985, pp. 8-12), UV stabilizers e.g. B. sterically hindered amines (especially N-unsubstituted, N-alkyl or N-acrylic substituted 2,2,6,6-tetramethylpiperidine compounds), UV absorber [especially 2- (2'-hydroxyphenyl) benzotriazole compounds, 2-hydroxybenzophenone compounds, 1,3-bis (2'-hydroxybenzoyl) benzene salicylates, cinnamic acid derivatives and oxalic acid dianilides], antistatic agents, flame retardants, Plasticizers, nucleic agents, metal deactivators, biocides, fillers and Pigments included.

The stabilizers used according to the invention can the polymers Materials before, during or after their polymerization in solid, molten, added in solvents or as masterbatches will. The solutions generally contain 10 to 80% of the Stabilizer composition, the masterbatches generally also contain 10 to 80, preferably 40 to 70% stabilizer composition, the The rest is a polymer compatible with the polymer to be stabilized.

Mixing the stabilizer compositions with those to be stabilized Polymers is carried out by customary methods, e.g. B. in suitable Mixers for molten material, in melt spinning or film blowing machines, in the extruder or in the production of molded articles, Pipes, fibers or foams.

Among all the alkyl groups mentioned, the C _1-8 , in particular the C _1-4 , alkyl radicals are preferred, and among these again methyl, ethyl and tert-butyl. Preferred alkoxy groups contain 1 or 2 carbon atoms.

In the following examples, unless otherwise stated, the parts by weight and the percentages by weight. The temperatures are given in degrees Celsius.

Example 1 Production of Biphenyl-p, p'-bis (2,2,6,6-tetramethylpiperidyl-4) phosphonite

0.1 mol of biphenyl-p, p'-dichlorophosphine are added dropwise to a suspension of 0.2 mol of 2,2,6,6-tetramethylpiperidin-4-ol in 100 ml of triethylamine at room temperature, with a nitrogen purge. The mixture is then boiled under reflux for 5 hours and the excess triethylamine is removed by extraction twice with 50 ml of toluene at room temperature. The colorless reaction product is precipitated from the remaining solution by adding diisopropyl ether, filtered off, washed with diethyl ether and dried in vacuo.
Yield 56% of theory Th., Γ ^31p : 155: 5 ppm.

Example 2

A polymer powder containing

100 parts of a catalyst from III. Generation of manufactured polypropylene (trade name Moplen FLS-20)
0.05 parts of Irganox 1010 (Ciba-Geigy),
0.1 part calcium stearate and
0.07 parts of biphenyl-p, p'-bis (2,2,6,6-tetramethylpiperidyl-4) phosphonite

is mixed and extruded at 210 °. The product thus obtained is then extruded several times at 270 ° in a Göttfert screw-in extruder (d = 20 mm, 1: d = 20, 50 min ^-1 compression 1: 3), the polymer melt (strand form) is cooled in a water bath and granulated. After the 1st, 3rd and 5th run the "Melt Flow Index" (ASTM D-1238-70, 230 °, 216 kg) and Yellowness Index (ASTM D-1925-70 on the granulate) are measured. The results are shown in the table according to Comparative Example B.

Example 3

The procedure is as described in Example 2, but 0.1 part of biphenyl p, p'-bis (2,2,6,6-tetramethylpiperidyl-4) phosphonite in place of 0.07 Parts of the stabilizer.

Comparative Example A

The procedure is as given in Example 1, but instead of Biphenyl bis (2,2,6,6-tetramethylpiperidyl-4) phosphonite 0.07 part Irgaphos 168 (Ciba-Geigy) to the polymer mass.

Comparative Example B

The procedure is as in Comparative Example A, but 0.1 part of Irgaphos is added 168 to.

table

Example 4

A powder coating made of hydroxyl group-containing polyacrylate and polyisocyanate is mixed with 2% of the stabilizer prepared according to Example 1 and prepared in the usual way, by extrusion, milling and sieving. The powder layer is then directly pretreated on a corresponding one Metal surface (single-layer top coat) or on one with a Primed metal surface (two-layer paint) applied. In the case of two-coat painting, the basecoat can be on an aqueous basis or on a powder coating basis. In the first case according to a dry-on-wet method, in the latter case according to a worked dry-on-dry process.

The stabilizer effect is evaluated by ventilation, e.g. B. in one, UVCON device (UV fluorescent light 313 nm, 8 hours at 70 ° and 4 Hours at 50 °) together with one without stabilizer, but otherwise the same produced paint.

Claims (10)

1. Use of sterically hindered amino groups containing phosphite and phosphonite compounds for light and processing stabilization of polyurethanes and polyolefins, which with catalysts of the II. Generation or higher generation catalysts have been made the catalysts were not removed from the polymers, and powder coatings on acrylate, epoxy, urethane or polyisocyanate Base. 2. Use of compounds of formula I. wherein
R is hydrogen, oxygen, hydroxyl, C _1-24 alkyl, -C _1-24 alkoxy, C _1-24 alkylcarbonyloxy, benzoyloxy or a radical of the formula -COR₅
the two R₁, independently of one another, methyl or C _1-5 alkyl or together a group of the formula - (CH₂) ₅-,
the two R₂, independently of one another, methyl or C _₁-₅- alkyl or together a group of the formula - (CH₂) ₅,
R₃ and R₄, independently of one another, linear or branched C _1-24 alkyl, C _7-24 aralkyl, C _7-24 alkaryl, C _5-24 cycloalkyl, C _6-24 aryl or a group of the formula a or, only one of R₃ and R₄, a group of formula b or R₃ and R₄ together represent a radical of the formula R₅ C _1-6 alkyl, phenyl, benzyl, benzoyl, carboxyl or a group of the formula -C (R₆) = CH₂, -NR₇R₈, -CO-C _1-24 alkyl or -CO-OC _1-12 alkyl ,
R₆ is hydrogen or C _1-4 alkyl,
R₇ is hydrogen, C _1-12 alkyl, C _5-6 cycloalkyl, phenyl, phenyl-C _1-4 alkyl or C _1-12 alkylphenyl,
R₈ is hydrogen or C _1-12 alkyl,
AC _1-24 alkylene, C _6-24 cycloalkylene, arylene, C _7-24 aralkylene or a group of the formula c all X independently of one another, the direct bond, -N (R₉) -, -O- or -S-, preferably the direct bond or -O-,
R₉ is hydrogen or C _1-4 alkyl,
R₂ is the direct bond, -NR₉, -O-, -S-, C _1-24 alkylene (preferably - (CH₂) _1-4 cycloalkylene, arylene, C _7-24 alkarylene or C _7-24 aralkylene,
all R 1, independently of one another, hydrogen, linear or branched C _1-24 alkyl, C _5-24 cycloalkyl, C _7-24 alkaryl, C _7-24 aralkyl or C _6-24 aryl,
R₃a and R₄a, independently of one another, linear or branched C _1-24 alkyl, C _5-24 cycloalkyl, C _7-24 aralkyl, C _7-24 alkaryl or C _6-24 aryl or a group of the formula a and
0 or 1
mean for stabilizing plastics, according to claim 1. 3. Use of compounds of formula I, according to claim 2 wherein
R each independently of one another hydrogen or methyl,
all R₁ and all R₂ methyl,
all X the direct bond or -O-,
all R₁₁ is hydrogen, methyl, tert-butyl or tert-octyl
mean. 4. Use of mixtures of compounds of formula II, according to claims 2 or 3 with a compound of formula VIII wherein
R, R₁ and R₂ have the meanings given in the preceding claims,
R₁₀ linear or branched C _1-24 alkyl, C _5-24 cycloalkyl, C _7-24 aralkyl, C _7-24 alkaryl or C _6-24 aryl, where aryl, preferably phenyl or diphenyl, and
p 1, 2 or 3
mean, wherein the compound of formula VIII is present in amounts of 10 to 99 percent by weight in the total mixture. 5. Use of sterically hindered phosphite-containing amino groups and phosphonite compounds according to one of the preceding claims, in amounts of 0.01 to 5, preferably 0.05 to 2 percent by weight in the plastics mentioned in claim 1. 6. A process for the preparation of the compounds of formula I, according to claim 2, characterized in that 1 mol of a compound of formula X. with 1 mole of a compound of formula XI or 2 moles of a compound of formula X with 1 mol of a compound of formula XIIR₄-XP (Z) ₂ (XII), wherein in formulas XI and XII Z is chlorine, bromine or -N (R₇) ₂ and R₇ is hydrogen, C _{1- 12} alkyl, C _5-6 cycloalkyl, phenyl, phenyl-C _1-4 alkyl or C _1-12 alkylphenyl, condensed. 7. The compound of formula IIa wherein
R ′ is hydrogen, C _1-18 -alkyl, C _1-18 -alkoxy, acryloyl, benzoyloxy or a radical of the formula COR₅,
R₅ C _1-8 alkyl, C _1-8 alkylcarbonyl or C _1-4 alkoxycarbonyl,
R₁₀ 'linear or branched C _1-24 alkyl, C _5-24 cycloalkyl, C _7-24 aralkyl or diphenyl
mean and the symbols R₁, R₂ and X have the meanings given in claim 2. 8. The compounds of formula IIIa wherein
all R₁ and R₂ methyl,
all R ′ are hydrogen or methyl,
AC _1-24 alkylene, C _6-24 cycloalkylene, arylene, C _7-24 aralkylene or a group of the formula c and the two X independently of one another are the direct bond -NH-, -N (C _1-4 -alkyl) -, -O- or -S-, preferably the direct bond or -O-. 9. The compounds of formula Va wherein
all R₁ and R₂ methyl,
all R ′ are hydrogen or methyl,
all X independently of one another the direct bond, -NH-, = N (C _1-4 -alkyl), -S- or -O-, preferably the direct bond or -O- and
p is 1, 2 or 3. 10. The compounds of the formulas IV, VI and VII, wherein
every m independently of one another 0 or 1,
P 1, 2 or 3,
all R ′ are hydrogen or methyl,
all R₁ and R₂ methyl,
all R₁₀ linear or branched C _1-24 alkyl, C _5-24 cycloalkyl, C _7-24 alkaryl or C _6-24 aryl, aryl preferably being phenyl,
all R₁₁, independently of one another hydrogen, linear or branched C _₁-₂₄ alkyl, C _5-24 cycloalkyl, C _7-24 - alkaryl or C _6-24 aryl
mean.