DE2042808C3 - Stabilizer system made from nickel hydroxybenzyl phosphonates, UV absorbers and benzoates - Google Patents

Description

Ni

OA ³

wherein A ^{1 is} an alkyl radical having 1 to δ carbon atoms, A ^{2 is} hydrogen or an alkyl radical having 1 to 6 carbon atoms, and A ^{3 is} an alkyl radical having 1 to 18 carbon atoms.

the general

OH

b) (1) a benzophenone
formula

CO

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 'is hydrogen, halogen or an alkyl radical with I to 6 carbon atoms, R ^{4 is} hydrogen, chlorine, an alkyl radical with I to 6 carbon atoms, a cycloalkyl or phenylalkyl radical with 7 to 12 carbon atoms, R' is an alkyl radical with I to 12 carbon atoms, cycloalkyl or Phenylalkyl radical with 7 to 12 carbon atoms means such that the sum of the atomic weights of the ^{atoms contained in the final R 1} , R ¹ and R " ¹ is at least 107;

as 1 ^: ltravioiettlichlcil>si> rber and

c) a p-hydroxybenzoate of the general formula

COOE ²

where E denotes an alkyl group with 1 to 6 carbon atoms or a cycloalkyl group, E ¹ denotes hydrogen, an alkyl group with 1 to 6 carbon atoms or a cycloalkyl group, and E ² denotes an alkyl group with 1 to 20 carbon atoms, the phenyl group, an alkyl-substituted Ph »Nyl radical, the alkyl group having 1 to 6 carbon atoms. Benzyl or alkyl substituted benzyl groups, the alkyl group! to 6 carbon atoms, such that no more than two alkyl substituents are present on the phenyl or benzyl groups.

The present invention relates to a synergistic stabilizer combination for stabilizing organic substances Material against oxidative or thermal decomposition by light and heat according to the patent claim.

From BE-PS 6 22 977 are synergistic stabilizer combinations known from heat light stabilizers and a UV absorber for organic material, z. 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 polypropybn of a 0.1 mm thick film in the Xenotest 1200, 815 It took hours to bring the carbonyl extinction to 3 o'clock.

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

0.1% / J- (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.
0.2'5% 2'-hydroxy-3 ', 5'-di-t-butyl-5-chloro-

benzotriazole,
0.?5 ⁰ /n(2'.4'=Di=t=biityl)-4.hydroxy

J.Vdi-t-butyl-bisuoate

stabilizes polypropylene in the same test as in the prior art for 2480 hours until carbonyl absorption reaches the value 0.3. This improvement was not / u expected and proves the technical Progress.

The stabilizer combination according to the invention is

JO

useful for stabilizing organic materials, which are normally oxidative or thermal Are subject to decomposition. Materials that can thus be stabilized include synthetic, organic polymeric substances such as vinyl s resins formed by the polymerisation of Vinyl halides or through the interpolymerization of vinyl halides with unsaturated polymerizable Connections, e.g. B. vinyl esters, "^ -unsaturated aldehydes and unsaturated hydrocarbons in Substances such as butadienes and styrene; Poly-a-olefins, such as Polyethylene, polypropylene, polybutylene and polyisoprene, including copolymers of poly-a-olefins, Polyurethanes such as those obtained from polyols and organic polyisocyanates; Polyamides such as polyhexamethylene adipamide and polycaprolactam; Polyester, such as polymethylene or Polyethylene terephthalate; Polycarbonates; Polyacetals; Polystyrene; Polyethylene oxide; and copolymers, like the high-impact polystyrene-containing copolymers of butadiene and styrene and those formed by the interpolymerization of Acrylonitrile, butadiene and / or styrene. Other materials stabilized according to the present invention include aliphatic esterate lubricants e.g. B. di (2-ethylhexyl) 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, fuel oils, drying oils, cutting fluids, Waxes or resins, fatty acids and soaps.

The stabilizers used in the present invention can be incorporated into the substrates e.g. B. be incorporated as follows: dissolving the stabilizer in any organic solvent with a low boiling point and then adding the solution to the substrate or dry blending 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 screw conveyor.

A ¹ is preferably tert-butyl or tert-amyl and 4-, A 2 is preferably t-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. 5;

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. to

Examples of metal phosphonates are

Nickcl-bis- (O-butyl-3,5-di-t-butyl-

4-hydroxybenzylphosphonate)
Nickel-bis-10-octadecylO-methyl-

4-hydroxy-5-t-butylben / ylphosphonate)
Nickel-bis-iO-octadecyl ^ -hydroxy-

3,5-dit-butylbenzylphosphona!) Nickel-bis-CO-octadecyl-a.S-di-t-butyl-

4-hydroxybenzylphosphonate) Nickel-bis- (O-ethyl-3,5-dimethyl-

4-hydroxybenzylphosphonate) NiekeI-bis- (O-tetracosyl-3,5-diethyl-

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

4-HydroKybenzylphosphonat) Nickel-bis- (O-methyI-3,5 dihexyl-

4-hydroxybenzylphosphonate) nickel-bis-fO-octyl-S.ö-di-isopropyl-

4-hydroxybenzylphosphonate) Nickel-bis-iO-dodecyl-S-butyl-S-isopropyl-

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

4-hydroxybenzyl phosphonate).

In a preferred embodiment, R ^{1 is} hydrogen and R ^{3 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 ~ ^Ί 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 a «-phenylethyl group; and R ⁵ denotes an alkyl radical having 1 to 12 carbon atoms, a cyclohexyl, benzyl or α-phenylethyl group. Examples of benzotriazoles used according to the invention are:

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

2- (2'-Hydroxy-5'-amyiphenyl) -benztriazole 2- (2'-Hydroxy-5'-1 crt.-butylphenyl) -benztriazole 2- (2'-Hydroxy-3 ', 5'-dimethylphenyl) -benztriazole 2- (2'-Hydroxy-3', 5'-dimethylphenyl) -5-methylbenzotriazole

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

2- (2'-Hydroxy-5'-amylphenyl) benzotriazole 2- (2'-Hydroxy-5'-tert-butylphenyl) benzotriazole 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 ', 5'-dichlorophenyl) -benzotriazole 2- (2'-Hydroxy-5'-phenyl-phenyl) -benztriazole.

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 ² 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-butylphenyl) -3,5-di-l-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 ^ .S-di-tert-octyM-hydroxybenzoate
Dodecyl S-methyl-S-isoamyM-hydroxybenzoate
Octadecyl SS diisopropyl ^ hydroxybenzoate
Hexadecyl SS-di-tert-butyl ^ -hydroxybenzoate
Phenyl 3,5-diisopropyl-4-hydroxybenzoate
p-Isopropylphenyl-S-methyl-S-tert-amyl-

4-hydroxybenzoate t.

The additives used can be added to the substrates in various concentrations. The nickel phosphonate can be used in a concentration of about 0.001 to 10% by weight of the organic material, more preferably in an amount of about 0.05 to 2% by weight. The ultraviolet drug absorber (benzophenone or benzotriazole) can be in a concentration of about 0.01 to 10% and 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 part octadecyl / 9- (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:

I. 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 Length 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 2) 2 ° C

2. Multifilamcnl
2.54 cm F. extruder -1./D = 24/1 at 20 rpm

.Spin nozzle - 10 holes - diameter of the holes O. ^r ) O8 mm.

'temperature of the melt 26 (1 (".

Air cooling was effected by making the

Threads in a cooling tower measuring 1.89 m × 15.24 cm × 12.70 cm, which was provided with a fan that moved 1.84 m ³ / min of air, stretched.

3. Filament pick-up

The cooled multifilament was on godet rolls in with a filament speed of 157.4 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 method for resistance to weathering

Dyed knitted multifiiar. Duck were inclined 45 ° in a south direction in Florida, starting with November 1st, exposed to the elements. The tensile strength tests were carried out after each interval, in which the sample was exposed to the elements, on the Instron Model ™.

The test results presented below show the percent retention of the original tensile strength a fiber after exposure to the stated number of Kilolangleys (KIy). 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-3,5-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 "/ n
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 ⁱ -carbethoxyphenyl) benzotriazole

2- (2'-Hydroxy-5'phenyl-phen> l)

5-chlorobenztriazole
2-hydroxy-4-methoxybenzophynone
2-Hydroxy-4-n-octoxybenzophynone

replaced.

In Examples 2 to 5, similar results were obtained as in Heisnicl 1 or / irlt

Example 2

Polyethylene is stabilized by the following composition:

0.05% nickel bis (O-octadecyl-2-hydroxy-3,5-di-t-butylbenzylphosphonate)

0.05% 2,4-dihydroxybenzophenone

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

An equally good stabilization is obtained if, in the above example, the nickel compound is through

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-hydroxybenzyl) phosphonate]

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

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-hydroxybenzyl) phosphonate] 0.5% 2,4-di-t-butylphenyl-3,5-di-t-butyl-

4-hydroxybenzoai.

Example 5 nylon pellets are mixed with:

0.25% nickel bis [(O-n-butyl-3,5-di-t-butyl-4-hydroxybenzyl) phosphonate]

U, 57o Kentametnyien-i, 3-di- (J, 3-di-t-octyi-4-hydroxybenzoate)

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

Example 6

Oriented multifilaments of 16.2 denier were produced according to Example 1 (a), with additional Additives 0.10 parts of 2,6-di-tert-butyl-4-methylphenol per 100 parts of polypropylene were added. she were inclined 45 ° in a southerly direction, exposed to weathering in Florida as described in Example 1 (b).

The stabilized polypropylene filaments contain the following additives:

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

5-chlorobenzotriazole 0.125% nickel bis - [(O-n-butyl-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%

Example 7

Polypropylene filaments were made as in Example 6 and investigates and contains the following additives:

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

5-chlorobenzotriazole 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

4-hydroxybenzoate.

The test results were as follows:

20 KIy. - 82% 30 KIy. - 77% 40 KIy. - 73% you K.iy. - ozvb 60 KIy. - 53% 70 KIy. - 36%

Claims (1)

Claim: Synthetic stabilizer combination for stabilization of organic material against oxidative or thermal decomposition by light and heat, consisting of a) a nickel hydroxybenzyl phosphonate of the general formula