DE2042808B2 - Stabilizer system made from nickel hydroxybenzyl phosphonates, UV absorbers and benzoates - Google Patents

Description

wherein R ¹ denotes hydrogen, a hydroxyl group, halogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and R ² denotes hydrogen, a hydroxyl group or an alkyl radical having 1 to 12 carbon atoms; or b) (2) a benzotriazole of the general formula

OH

wherein R ^{3 is} hydrogen, halogen or an alkyl radical with 1 to 6 carbon atoms, R * is hydrogen, chlorine, an alkyl radical with 1 to 6 carbon atoms, a cycloalkyl or phenylalkyl radical with 7 to 12 carbon atoms, R ^? denotes an alkyl radical with 1 to 12 carbon atoms, cycloalkyl or phenylalkyl radicals with 7 to 12 carbon atoms, such that the sum of the atomic weights of the ^{atoms contained in the groups R 3} , R ⁴ and R ⁵ is at least 107;

as an ultraviolet light absorber and

c) a p-hydroxybenzoate of the general formula

HO

COOE ²

15th where E denotes an alkyl radical with 1 to 6 carbon atoms or a cycloalkyl group, E 'denotes hydrogen, an alkyl radical with 1 to 6 carbon atoms or a cycloalkyl group, and E ² denotes an alkyl radical with 1 to 20 carbon atoms, the phenyl radical, an alkyl-substituted? henyl radical, wherein the alkyl group has 1 to 6 carbon atoms, benzyl or alkyl-substituted benzyl groups, wherein the alkyl group has 1 to 6 carbon atoms, such that there are no more than two alkyl substituents on the phenyl or benzyl groups.

The present invention relates to a synergistic one Stabilizer combination for stabilizing organic material against oxidative or thermal Decomposition by light and heat according to the claim.

From BE-PS 6 22 977 are synergistic stabilizer combinations of heat light stabilizers and a UV absorber r known for organic material, e.g. B. a combination of

0.25% pentaerythritol tetra-0- (3,5-di-t-butyl-

4-hydroxyphenyl) propionate, 0.15% calcium stearate, 0.25% decyl diphenyl phosphite, 0.25% 2-hydroxy-4-benzoxy-benzophenone and 2% titanium dioxide.

When testing the light stability in polypropylene of a 0.1 mm thick film in the Xenotest 1200, 815 Hours needed to get the carbon extinction to 3 o'clock bring.

In contrast, the inventive stabilizer combination consists of the three in the claim specified components a), b) and c). A combination of

0.1% /? - (3,5-Di-t-butyl-4-hydroxyphenyl) -

propionic acid octadecyl ester, 0.15% calcium stearate, 0.25% nickel bis [ethyl- (4-hydroxy-

3,5-di-t-butyl) -benzyl-phosphonate J. 0.25% 2'-hydroxy-3 ', 5'-di-t-butyl-5-chloro

benzotriazole, 0.25% (2 ', 4'-di-t-butyl) -4-hydroxy-

3,5-di-t-butyl benzoate

stabilizes polypropylene in the same test as in the prior art for 2480 hours until the carbon extinction reaches the value 03. This improvement was not to be expected and proves the technical progress. The stabilizer combination according to the invention is

25th

30th

useful for stabilizing organic materials which are normally subject to oxidative or thermal decomposition. Materials that can thus be stabilized include synthetic, organic, polymeric substances such as vinyl resins formed by the polymerization of vinyl halides or by interpolymerization of vinyl halides with unsaturated polymerizable compounds, e.g. vinyl esters, «^ -unsaturated aldehydes and unsaturated hydrocarbons substances such as butadienes and styrene; Poly-a-olefins, such as Polyethylene, polypropylene, polybutylene and polyisoprene, including copolymers of poly- «-Olefins, polyurethanes, like the ones you made from Polyols and organic polyisocyanates; Polyamides such as polyhexamethylene adipamide and Polycaprolactam; Polyesters such as polymethylene or polyethylene terephthalates; Polycarbonates; Polyacetals; Polystyrene; Polyethylene oxide; and copolymers, such as the high-impact polystyrene-containing copolymers of butadiene and styrene and those that are formed by the copolymerization of acrylonitrile, butadiene and / or styrene. Other materials that can be stabilized in accordance with the present invention include lubricants aliphatic esterate, e.g. B. Di- (2-ethyihexyl) azelate or Pentaerythritol tetracaproate, animal and vegetable oils, ζ. B. flaxseed oil, fat, tallow, lard, peanut oil, Cod liver oil, castor oil, palm oil, corn oil or cottonseed oil, hydrocarbon materials such as Petrol, mineral oils, fuels, drying oils, cutting fluids, waxes or resins, fatty acids and Soap.

Those used in the present invention Stabilizers can be incorporated into the substrates e.g. B. be incorporated as follows: Dissolve the stabilizer in any organic solvent with a low boiling point and then adding the solution the substrate or dry mixing of a very finely ground stabilizer with a substrate in powder form or by feeding the stabilizer directly into the extruder in the mixing zone or into the molten polymer in the feed zone of the Auger.

Preferably A ^{1 is} tert-butyl or tert-amyl and 4-, A2 is preferably tert-butyl or tert-amyl.

The term "alkyl" as used in the present description and in the claims means branched or straight-chain, saturated hydrocarbon groups. Typical such alkyl groups are thus methyl, ethyl, propyl, isopropyl, Butyl, tert-butyl, pentyl, tert-pentyl, isopentyl, hexyl, octyl, tert-octyl, decyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl or triacontyl groups.

The preferred compounds of the invention are 3,5-dialkyl-4-hydroxybenzylphosphonates, e.g. B. 3,5-di-tert-butyl-4-hydroxybenzylphosphonates. Details on the preparation of the nickel phosphonates can be found in U.S. Patent No. 3,310,575.

Examples of metal phosphonates are Nickel-bis- (O-butyl-3,5-di-t-butyl-

4-hydroxybenzylphosphonate) Nickel bis ^ O-octadecyl-3-methyl-

4-hydroxy-5-t-butylbenzylphosphonate) Nickel-bis- (0-octadecyl-2-hydroxy-

3,5-di-t-butylbenzylphosphonate)

Nickel-bis-iO-octadecyl-S ^ -di-t-butyl-

4-hydroxybenz} Iphosphonate) Nickel-bis- (O-ethyl-3,5-dimethyI-

4-hydroxybenzylphosphonate) nickel-bis- (O-tetracosyl-3 ^ -diethyl-

4-hydroxybenzylphosphonate) Nickel-bis- (O-triacontyl-3-methyl-

4-hydroxybenzylphosphonate) nickel-bis- (O-methyI-3,5-dihexyI-

4-hydroxybenzylphosphonate) Nickel-bis- (O-octyl-3,6-di-isopropyl-

4-hydroxybenzylphosphonate) nickel-bis- {0-dodecyl-3-butyl-5-isopropyl-

4-hydroxybenzylphosphonate) Nickel-bis- (O-decyl-5-t-butyl-

4-hydroxybenzyl phosphonate).

In a preferred embodiment, R ^{1 is} hydrogen and R ^{2 is} a straight-chain alkyl radical having 8 to 12 carbon atoms. Examples of the Benzo-Phene are the following:

2-hydroxy-4-methoxybenzophenone 2,2'-dihydroxy-4-methoxybenzophenone 2,2-dihydroxy-4-n-octoxybenzophenone 2-hydroxy-4-n-octoxybenzophenone 5-chloro-2-hydroxybenzophenone 4-dodecyloxy-2-hydroxybenzophenone 2-hydroxy-4-decyloxybenzophenone 2,2'-dihydroxy-4,4'-dimethoxybenzophenone 2,2 ', 4,4'-tetrahydroxybenzophenone.

In a preferred embodiment, R ³ denotes hydrogen, chlorine or the methyl group, R ⁴ denotes hydrogen, chlorine, a tert-butyl, tert-amyl, cyclohexyl, benzyl or «-phenylethyl group; and R ⁵ denotes an alkyl radical having 1 to 12 carbon atoms, a cyclohexyl, benzyl or phenylethyl group. Examples of benzotriazoles used according to the invention are:

2- (2'-Hydroxy-5'-methylphenyl) benzotriazoles 2- (2'-Hydroxy-5'-tert-butylphenyl) - 5-chlorobenzotriazole

2- (2'-Hydroxy-5'-amylphenyl) -benzotriazole 2- (2'-Hydroxy-5'-tert-butylphenyl) -benzotriazole 2- (2'-Hydroxy-3 ', 5'-dimethylphenyl) -benztriazole 2- (2'-Hydroxy-3', 5'-dimethylpheny!) - 5-methylbenztiiazole

2- (2'-Hydroxy-5'-methylphenyl) -benztriazole 2- (2'-Hydroxy-5'-tert.-butylphenyl) - 5-chlorobenzotriazole

2- (2'-Hydroxy-5'-amylphenyl) -benztriazole 2- (2'-Hydroxy-5'-tert-butylpnenyl) -benztriazole 2- (2'-Hydroxy-5'-phenyl-phenyl) -

5-chlorobenzotriazole 2- (2'-Hydroxy-5'-cyclohexyl-phenyl) - 5-chlorobenzotriazole

2- (2'-Hydroxy-5'-cyclohexyl-phenyl) -benztriazole 2- (2'-Hydroxy-3 '^' - dichlorophenyl) -benzotriazole 2- (2'-Hydroxy-5'-phenyl-phenyl> -benzotriazole.

Cycloalkyl E or E ¹ is preferably cycloalkyl having 5 to 12 carbon atoms, such as cyclohexyl.

In a preferred embodiment, E and E ¹ denote tert-butyl or tert-amyl groups and E ³ denotes a di- (alkyl) phenyl radical, the alkyl group having 1 to 6 carbon atoms. Examples of hydroxybenzoates are the following:

(2 ', 4'-Di-t-butylphenyi) -3,5-di-t-butyl-

4-hydroxybenzoate
Methyl-S-methyl-S-isopropyl-

4-hydroxybenzoate

Ethyl 3,5-diisopropyl-4-hydroxybenzoate
Propyl 3,5-di-sec-butyl-4-hydroxybenzoate
Isobutyl 3,5-di-tert-amyl-4-hydroxybenzoate
Decyl SS-di-tert-octyl ^ -hydroxybenzoate
Dod'-cyclo 3-methyl-5-isoamyl-4-hydroxybenzoate
Octadecyl S ^ -diisopropyM-hydroxybenzoate
Hexadecyl SS-di-tert-butyM-hydroxybenzoate
Phenyl 3,5-diisopropyl 4-hydroxybenzoate
p-Isopropylphenyl-S-methyl-S-tert-amyl-

4-hydroxybenzoate

The additives used can be added to the substrates in various concentrations. The nickel phosphonate can be in a concentration of from about 0.001 to 10% by weight of the organic material, more preferably in an amount from about 0.05 to 2% by weight can be used. The ultraviolet light absorber (Benzophenone or benzotriazole) can be used in a concentration of about 0.01 to 10% unc! preferably from about 0.05 to 3% can be used. The light stabilizer (p-hydroxybenzoate) can be used in one concentration from about 0.01 to 5%, preferably from 0.05 to 2%, can be used. However, for special application the additives in both higher and lower concentrations than those given above be used.

The following examples are intended to explain the present invention further without, however, illustrating it restrict.

example 1
Open air investigations

(a) Sample preparation
Oriented multifilaments of 15 denier

The additives are dissolved in distilled methylene chloride and mixed with polypropylene in a Hobart mixer mixed. For every 100 parts of polypropylene, 0.15 parts of calcium stearate and 4.00 parts of titanium dioxide are added as 50% dispersion and 0.10 parts of octadecyl - /? - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate added in dry form to the polymer mixture. To make moisture removal easier, all were Mixtures dried in vacuo shortly before extrusion

The samples were made as follows:

1. Compounding and Pelletizing
2.54 cm extruder L / D = 20/1 at 40 rpm

This term means that the diameter of the screw of the extruder is 2.54 cm and the ratio of Long to diameter (L / D) of the screw is 20 to 1, and that the screw is 40 revolutions per Minute (RPM) is operated.

Melt temperature 232 ^C C.

2. multifilament
234 cm extruder-L / D-24/1 at 20rpm

Spinneret - 10 holes - diameter of the holes 0.508 mm.
Melt temperature 260 ° C.

Air cooling was effected by making the

Threads which was equipped with a fan in a cooling tower with the dimensions 15.24 cm 1,89m χ χ 12.70 cm, the I, 84m ³ / min moving air into spun.

3. Filament pick-up

The cooled multifilament was on godet rolls ίο at a filament speed of l'J7.4 m / min wound up.

4. Orientation

Godet temperature 125 ° C

Orientation ratio 3: 1

(Stretching the fiber in proportion to
the original length)

(b) test procedure for wit? resistance to aging

Dyed knitted multifilar; duck were 45 ° sloping south in Florida beginning November 1st, exposed to the weather The tensile strength tests were used after each time the sample was exposed to the elements Instron Model TM.

The test results presented below show the percent retention of the original tensile strength a fiber after exposure to the stated number of Kilolangleys (KJy). A Langley is a measure of the energy absorbed by the fiber. It is known that some Fibers increase their orientation after the first exposure. For this reason, the percentage increases Retention of tensile strength again after the initial drop.

Polypropylene filaments containing the following additives were made as described above:

0.20% nickel bis [(O-n-butyl-34-di-t-butyl-4-hydroxybenzyl) phosphonate]

0.25% 2,4-di-t-butylphenyl-3,5-di-t-butyl
4-hydroxybenzoate

0.55% 2- (2'-Hydroxy-3 \ 5'-di-t-butyiphenyl) -7-chlorobenzotriazole

The test results were as follows:

20 KIy. - 69%
40 KIy. - 82%
50 KIy. - 84%
60KIy. - 71%
70 KIy. - 82%
80 KIy. - 82%
90 KIy. - 64%
100 KIy. - 58%

Similar results were obtained when using 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole in the above example by

2- (2'-Hydroxy-5'-methylphenyl) benzotriazole

2- (2'-Hydroxy-5'-ethoxy-phenyl) -benztriazole

2- (2'-Hydroxy-5'-phenyl-phenyl> -

5-chlorobenzotriazole
2-hydroxy-4-methoxybenzophenone
2-Hydroxj -4-n-octoxybenzophenone

replaced.

In Examples 2 to 5, results similar to those in Example 1 were obtained.

Example 2

Polyethylene is stabilized by the following «: composition:

0.05% nickel-bis-fO-octadecyl ^ -hydroxy-3,5-di-t-butylbenzylphosphonate)

0.05% 2,4-dihydroxybenzophenone

0.05% methyl 3-methyl-5-isopropyl-4-hydroxybenzoate.

This gives a good stabilization of the same when in the above example, the nickel compound by

Nickel bis (O-butyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate) is replaced.

Example 3

Polybutene is stabilized by the following composition:

2.0% nickel bis [(O-n-butyl-3,5-dimethyl-4-hydroxybenzy I) - phosphonate]

0.2% 2- (2'-hydroxy-3 ', 5'-dimethylphenyl) -5 methylbenzotriazole

0.1% methyl 3,5-di-t-butyl-4-hydroxybenzoate.

Example 4

Polypropylene is stabilized by the following additives:

0.5% 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -

5-chlorobenzotriazole
0.5% nickel bis [(on-butyl-3,5-di-t-butyl-

4-hydroxy benzyl) phosphonate] 0.5% 2.4-di-t-butylphenyl-3.5-di-t-btityl-

4-hydroxybenzoate.

Example 5 Nylon bearings are mixed with:

0.25% nickel bis [(O-n-butyl-3.5-di-t-hutyl-4-hydroxybenzyl) phosphonate]

0.5% pentamethylene-1,5-di- (3,5-di-t-octyl-4-hydroxybenzoate)

0.1% 2,2 ', 4,4'-tetrahydroxybenzophenone.

B 2 i s ρ i (■

Oriented multifilaments. > n were 16.2 denier

according to example l (a) hergestel 'with additionally /.u the

^r , additives 0.10 parts of 2,6-di. ^ ri.-butyl-4-methylpiienol per 100 parts of polypropylene were added. They were inclined 45 ° in a southerly direction, exposed to weathering in Florida as described in Example 1 (b).

The stabilized polypropylene filaments contain

in the following additives:

0.125% 2- (2 'hydroxy-3', 5'-di-tert-butylphenyl)

5-chlorobenzotriazole 0.125% nickel bis - [(O n-butyI-3,5-di-tert-butyl-

4-hydroxybenzyl) phosphonate]

'' 0.25% 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-

4-hydroxybenzoate

The test results were as follows:

20 KIy. - 94%

^: "40 KIy. - 77%

50 KIy. - 59%

60 KIy. - 59%

70 KIy. - 34%

B e i s ρ i e

Polypropylene filaments were made and searched as in Example 6 and contain the following Additives:

"'0.125% 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -

5-chlorobene <: triazole 0.25% nickel bis - [(O-n-butyl-3,5-di-tert-butyl-

4-hydroxybenzyl) phosphonate] 0.125% 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-

^II 4-hydroxybenzoate.

The test results were as follows:

20 KIy. - 82% _{J (} . 30 KIy. - 77%

40 KIy. - 78% 50 KIy. - 62% 60 KIy. - 53% 70 KIy. - 36%

Claims (1)

Claim: Synergistic stabilizer combination to stabilize organic material against oxidative or thermal decomposition by light and heat, consisting of a) a nickel hydroxybenzyl phosphonate of the general formula CH ₂ -PO OA ³ Ni wherein A ¹ denotes an alkyl group with 1 to 6 carbon atoms, A ² denotes hydrogen or an alkyl group with 1 to 6 carbon atoms, and A ³ denotes an alkyl group with 1 to 18 carbon atoms, b) (1) a benzophenone of the general formula OH CO JO