DE2257997A1 - PIPERIDINOLESTER - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. E. Assmann Dr. R. Koenl.gsb.erg.er - DIpK-Phys. R, timber builder - Dr. F. Zumstein jun.

PATENT LAWYERS

TELEPHONE: COLLECTIVE NO. 225341

TELEX 529979

TELEGRAMS: ZUMPAT

CHECK ACCOUNT: MUNICH 91139

BANK ACCOUNT: BANKHAUS H. AUFHÄUSER

8 MUNICH 2, BRÄUHAUSSTRASSE 4 / III

CASE: 3-7861 / MA 1495

CIBA-GEIGY AG, CH-4-0Q2 Basel / Switzerland

"Pip eridinoie s t he"

The invention relates to piperidine derivatives, and more particularly alkyl-substituted p-hydroxyaryl esters or alkyl-substituted ones p-Hydroxyaralkyl ester of 2,2 ~ dimethylpiperidin-4-ol, the stabilizers for polymers, in particular for polypropylene, are those stabilized with these substances Compositions.

In German Patent No. 1 929 928 are compounds the following general formula

.- 2

309824 / 1U1

η ¹

described, in which TL, 'and Rp', which are identical or different and represent, for example, methyl groups, n ^{1 is} an integer from 1 to 3 and ftz'i when n · = 1 is, inter alia, an acyl group belonging to certain classes is derived from monocarboxylic acids, of these acids only aryl, chlorine-substituted aryl and aralkyl carboxylic acids are described.

The invention now relates to a new class of esters derived from aryl and aralkyl carboxylic acids, the on the aryl radical with both hydroxy and alkyl groups are substituted.

The invention therefore relates to compounds of the following general terms Formula I.

Il

(A) _n - CO

CD

309824/11

■ worm

A is a group of the formulas -CHp-, -CHpCHp- or -CHp-CH-,

it. land Rp, which can be the same or different, straight-chain or branched alkyl groups with 1 Ms 6 carbon atoms, I-methylcyclohexyl groups or α, α-dimethylbenzyl groups, ,

R, and R ,, which can be the same or different, Alkyl groups with 1 to 12, preferably 1 to 6 carbon atoms or together with the carbon atoms to which they are attached form a saturated alicyclic ring having 5 to 8 carbon atoms or a group of the following Formula:

and η mean zero or 1 ·.

Examples of the groups R ^ and Rp are methyl, ethyl, n-propyl, isopropyl, sec-butyl, tert-butyl ", tert '.- pentyl (1,1-dimethylpropyl) and tert-hexyl (1,1-dimethylbutyl) groups. Preferably one or both Groups R ^ and Rp represent tert-butyl groups, although it is clear that the tert-butyl group is a bulky group, so that

'30982 kl 1 141

it is unlikely that two such groups will be attached to adjacent carbon atoms of the phenyl radical
are"

Examples of "the groups R, and IL are methyl, ethyl, Isopropyl, η-butyl, n-hexyl, n-octyl or n-dodecyl groups. However, the groups R 1 and R 1 preferably represent each represent a methyl group.

Preferred compounds of the general formula I are
Compounds in which the group A is a -CH ₂ CH ₂ -GrUpPe and η is 1, while further preferred compounds are those in which η is zero.

Further preferred compounds of the general formula I are the compounds of the general formulas II and III

tert-butyl

(II)

tert-butyl

-CH,

(III)

309824/1

In formulas II and III, the group J & p is preferred a tert-butyl group, which is in the ortho position the hydroxyl group is bonded or a methyl group which is in the ortho position or in the me'ta position to the hydroxyl group is bound to represent.

The invention also relates to a first method for Preparation of the compounds of the general formula I, which consists in the fact that a piperidinol of the general Formula IV

R, R>

with an acid halide of the general formula V

(V)

wherein R ^, Rp, A and η have the meanings given above and Y is a halogen atom, preferably a chlorine atom,

3 0 9 8 2 A / 1 U 1

means, reacts in the counterv / art of a substance which binds hydrohalic acid, e.g. a base such as triethylamine, using an excess of the amine reactant as Can use hydrohalic acid binding compound.

The invention also relates to a second method for Preparation of the compounds of the general formula I, which consists in that a compound of the general Formula IV with an ester of the general formula VI

(VI) R ₂

wherein the group R is an alkyl group with 1 to 6 carbon atoms, preferably a methyl or ethyl group, in the presence of a transesterification catalyst such as an alkali metal amide, z * B. Lithium amide.

The second process of the present invention is suitably carried out in such a way that one of the reactants melts together and the melted Hasse to zuia complete The course of the reaction stirs - which can be established, for example, by collecting the alcohol formed during the reaction and terminating the reaction when,, the theoretical amount of alcohol released is * xr vj

The invention also relates to a third, less preferred process for the preparation of the compounds of the general

309824/1 Ui '

my formula I, which consists of the Piperidino! der-general formula IV with a carboxylic acid of the general Formula VII

(VII)

in which R. _f Rp, A and η have the meanings given above, in the presence of an esterification catalyst, which is preferably a neutral catalyst, for example tetraalkyl titanate, is reacted.

The starting materials of the general formulas V, VI and VII can be prepared according to procedures known per se.

Particularly preferred compounds of the general formula I are the following:

2,2,6,6-tetramethylpiperidinyl-4- (3 ', 5'-dimethyl-4'-hydroxy) benzoate,

2,2,6, ö-tetramethylpiperidinyl - ^ - ß- (3 ', 5 ^f -dimethyl-4 ^f hydroxyphenyl) propionate,

2,2,6,6-tetramethylpiperidinyl 4- (3 ', 5'-diisopropyl-4'-hydroxy) benzoate, .

2,2,6,6-tetramethylpieridinyl-4-ß- (3 ', 5'-di-isopropyl-4'-hydroxyphenyl) propionate,

309824 / 1U1

2,2,6, ö-tetramethylpiperidinyl ^ - (3'-t-butyl-5'-methyl-4'-hydroxy) benzoate,

2,2,6,6-tetramethylpiperidinyl-4-ß- (3 -t-butyl-5'-methyl-4'-hydroxyphenyl) propionate,

2,2,6,6-tetramethylpiperidinyl-4-ß- (3'-t-butyl-6'-methyl ~ 4 ^! - hydroxyphenyl) propionate,

2,2,6,6-tetramethylpiperidinyl 4- (3 ', 5 '-di-t-butyl-4'-hydroxy) -benzoate,

2,2,6,6-tetramethylpiperidinyl-4- (3 ·, 5'-di-t-butyl-4 ¹ -hydroxyphenyl) acetate,

2,2,6,6-tetramethylp ip eridinyl-4-ß- (3 ', 5'-di-t-butyl-4 · - hydroxyphenyl) propionate,

1-Aza-4- [3 ', 5 ^l ~ di-t-butyl-4 ^l -hydroxybenzoyloxy] -2,2-dimethylspiro [5.5] undecane,

1-Aza-4 - [- S- (3 ¹ , 5'-di-t-butyl-4'-hydroxyphenyl) propionoxy] -2,2-dimethylspiro [5.5] undecane,

1,9-diaza-4- [3 ^! , 5'-di-t-butyl-4'-hydroxybenzoyloxy] -2,2,8,8,10,10-octamethylspiro [5.5] undecane,

2,2,6,6-tetramethylpiperidinyl-4- [3 ', 5'-bis- (α, α-dimethylbenzyl) -4'-hydroxybenzoate],

2,2,6,6-Tetramethylpiperidinyl-4- [3 ', 5'-bis (1 "-methylcyclohexyl) -4'-hydroxyphenyl] propionate.

The invention also relates to compositions that contain a organic material and a compound of the general formula I given above in a stabilizing amount.

It was found that the compounds of the general formula I give polyolefins an exceptionally high hatred of stability to the decomposition that normally occurs through exposure to ultraviolet radiation or heat

3 0 9 8 2 4/1 U 1

is caused. Furthermore, this improved stability is achieved without affecting the coloring properties of the treated Polyolefins are impaired, - The inventive In particular, stabilizers impart low and high density polyethylene, polypropylene and polystyrene as well as polymers of 1-butene, 1-pentene, 3-methylbutene-1, Hexene-1, 4-methylpentene-1, 4-methylhexene-1 and 4,4-dimethyl-pentene-1 and mixed and terpolymers of olefins, in particular of ethylene or propylene, a Effective stabilization against exposure to light and / or heat.

Other, organic materials that react when exposed to light Are sensitive to decomposition and their properties are improved by the incorporation of a compound of the general formula I. can be include natural and synthetic polymeric materials, e.g. natural and synthetic rubbers, where "the latter e.g. homo-, Mixed and ter-polymers; from acrylonitrile, butadiene and Include styrene. .

Special synthetic polymers are polyvinyl chloride, "polyvinylidene chloride and vinyl chloride copolymers, Polyvinyl acetate as well as condensation polymers made up of ether groups, ester groups (those of carboxylic acids, Sulfonic acids or carboxylic acids are derived), amide groups or urethane groups are built up. These polymers can e.g. form the basis for media for covering surfaces, such as paints and varnishes, which are based on based on an oil or a resin such as an alkyd resin or a polyamide resin; are constructed.

The amount in which the compound of general formula is incorporated into the organic material I, in order to achieve maximum protection against the decomposition by light, 'iduv & nkf nrn't c | e _n £ {^ einschäften of the to be treated

3 098 24/1 U 1-

the organic material, the energy content of the light radiation and the exposure time. For most purposes it is however, the compounds of general formula I are sufficient in an amount ranging from 0.01 to 5% by weight, more preferably in an amount in the range from 0.1 to 2 percent by weight, based on the weight of the untreated organic material to be used.

The compounds of general formula I can be incorporated using any known procedure of additives in polymers are introduced into the polymeric material. For example, the connections of the general formula I and the polymer in an internal mixer, mixed v / earth. Alternatively, the compounds of general formula I can be in the form of a solution or a Slurry in a suitable solvent or dispersant, e.g. an inert organic solvent such as methanol, ethanol or acetone to the powdery one Polymer are added, whereupon the mass is intimately mixed in a mixer and then the solvent Will get removed. Another method is that the compounds of general formula I during the preparation of the polymer is added to the polymer, for example in the latex stage of polymer formation, so that a pre-stabilized polymer material is obtained.

The compositions according to the invention can optionally one or more other additives, especially those in polymer formulations used, contain, such as antioxidants based on phenols or amines, UV absorbers and light stabilizers, phosphite stabilizers, Peroxide decomposers, polyamide stabilizers, basic co-stabilizers, polyvinyl chloride stabilizers, coim-forming agents, Plasticizers, lubricants, emulsifiers, antistatic Agents, flame retardants, pigments, soot, asbestos, glass fibers, Kaolin and talc.

3 0 9 8 2 4 / I U 1

The invention therefore relates to binary »; tertiary and compositions with even more ingredients _for the. contain a stabilizer of the general formula I together with one or more functional polymer additives.

Examples of suitable antioxidants are the sterically hindered phenols, such as those given in the following groups:

(1) Phenolic compounds of the general formula

₂ ) _{V /} A,

wherein Q is a group of the formula

: -0H

A is a group of formulas

-u- CR (COOR ") ₂ or

CQOR "

C (CII ₂ ) _W. ■ - Q COOR "

R is a hydrogen atom or a low molecular weight alkyl group,

R ^{1 is} a low molecular weight alkyl group,

R "is an alkyl group having 6 to 24 carbon atoms and

3098? A / Ί Ί A 1

w is an integer from zero to 4.

Examples of compounds of the above general formula are di-n-octadecyl-a- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, di-n-octadecyl-a- (3-tert-butyl -4-hydroxy-5-methyl-benzyl) malonate, which is described in Dutch patent specification No. 6,711,199 and di-n-octadecyl-a, a ^l -bis- (3-tert-butyl- 4-hydroxy-5-methylbenzyl) malonate, which is described in Dutch patent specification No. 6,803,498.

(2) Phenolic compounds of the general formula

Q-R

wherein Q and R have the meanings given above.

Examples of compounds of this type are 2 f 6-di-tert-butyl-p-cresol,

2-methyl-4,6-di-tert-butylphenol and the like

as

2,6-di-octadecyl-p-cresol.

(3) Phenolic compounds of the general formula

QC _w H _2w -Q

wherein Q and w have the meanings given above.

Connections of this kind are:

309824/11 A 1

2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol.) ,. 4,4'-Butylidene-bis- (2,6-di-tert-butylpheno!), '4 _f 41 _ (2-butylidene) -hi s- (2-tert-butyl-5-methylphenol),

2,2 ■ · -Methylene-bis- [6-. (2rtert ..- methyl · cyclohexyl) -4'-] -methylphenol ,, ■ .. -.-. ■■■ - ■ - 2,2'-methylene-bis- (3-tert-butyl-5-ethyiphenol), ■ 4,4'-methylene-bis (3,5-di-tert. ~ butylphenol), 4,4 ^f -plethylene-bis- (3 ~ tert, -butyl-5-methylphenol), 2,2 · -methylene-bis- (3-tert-butyl-5-methylphenol> etc.

(4) Phenolic compounds of the general formula

R-O-Q

wherein R and Q have the meanings given above. '- ^: - - - ■■■■■■. · ■ ·. - · "■ -., ■

Examples of connections of this type are:. . 2,5-di-tert-butylhydroquinone,. ,,

2,6-di ~ tert-butylhydroquinone, _2> 5-di-tert-butyl-4-hydroxyanisole.

30 9 8 2Λ /1.1 Λ 1

(5) Phenolic compounds of the general formula

QSQ
wherein Q has the meaning given above.

Examples of compounds of this type are; 4,4'-thio-bis (2-tert-butyl-5-methylphenol), 4,4'-thio-bis- (2 ~ tert-butyl-6-methylphenol), 2,2 »-thio-bis- (6-tert. ~ Butyl-4-methylphenol), 4,4'-thio-bis (2-methyl-5-tert-butylphenol).

(6) Phenolic compounds of the general formula

) _W C-OR "

wherein Q, w and R ″ have the meanings given above.

Examples of connections of this type are the following:

Octadecyl (3,5-dimethyl-4-hydroxybenzylthio) acetate and

Dodecyl (3,5-di-tert-butyl-4-hydroxybenzylthio) propionate.

309824 / 1U1

(7) Phenolic compounds of the general formula

where T is a hydrogen atom and R, w and Q have the meanings given above.

Examples of compounds of this type are the following:

1,1,3-tris (3,5-dimethyl-4-hydroxyphenyl) propane,.

1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) r butane,

1,1,5,5-tetrakis (3'-tert-butyl-4-hydroxy-6-methylphenyl) -n -pentane. "

(8) Phenolic. Compounds of the general formula

CH,
V. >
O
I. CH ₂ B ¹ - QH ₂ B ² QCH ₂ - \ ■ \ CH ₃ CH ₂ B ³

12 3

wherein B, B and B ^v hydrogen atoms or methyl groups

13 2

or in which, when B and B are Q, B is a Represents hydrogen atom or a methyl group and

2 13

when B denotes Q, B ■ and B hydrogen atoms or Methyl groups and Q have the meanings given above owns.

309824/114 1

Examples of connections of this type are:

1,4-di- (3,5-di "tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetram ethylbenzene,

1,3,5-Tri ~ (3,5-di-tert-butyl-4 ~ hydroxybenzyl) ~ 2,4,6 ■■

(9) Phonolic compounds of the general formula

S-D

(Q) - NH

NN
N

wherein Z is NHQ, -S-D or -0-Q, v / orin Q is the has the meaning given above and D is an alkyl group having 6 to 12 carbon atoms or a group of the formula

represents

v / orin R "and w have the meanings given above.

Examples of connections of this type are:

2,4-dis (n-octylthio) -6- (3,5-di-tert-butyl-4-hydroxy anilino) -1,3,5-triazine, '

6- (4-IIydiOxy-3-methyl-5-tert-butylanilirio) -2,4-bis- (n-octylthio) -1,3,5-triazine,

6- (4-Hydroxy-3, 5-dimethylanilino) -2,4-bis- (n ~ octylthio) -1,3, ! 3-triazine,

6- (4-Hydroxy-3, ^t Jd.i-tcrt.-butylanilino) -4- (4-hydi ^> oxy-3, 5-di-tert _# -butylphonoxy) -2- (n-octylthiü) -1 , 3,! J-tria:

3 0 iUi ■ ■; '-j ι /, ι

2,4-bis- (4-hydroxy.3,5-di-tert-butyl aniline) -6- (n-octylthio) -1 _J 3,5-triazine.

The above plienolic triazine stabilizers are described in more detail in U.S. Patent- "Hr, 3,255" W. .

(10) Phenolic compounds of the general formula

Z '

Q-O

in which Z 'represents a group of the formula -0-Q, -SD or -S- (C Hn J-SD, in which Q, D and \ i have the meanings given above.

Examples of connections of this type are:

2,3-Bi s- (3,5-di-1ert-butyl-4-hydrο xyp heno xy) - ~ 6- (n-octylthio ) - 1, 3,5-triazine,

2,4,6-Tri s ~ (4-hydroxy-3,5-di-1ert-butylphenoxy) -1,3,5-triazine,

6- (4-hydroxy-3, 5-di-tert-butylphenoxy) -2,4-bis ( n-octylthio ethyl thio) -1,3 ,, 5-1 ri az in,

6- (4-Hydroxy-3-methylphenoxy) -2,4-bis (n-octylthio) 1,3,5-triazine,

6- (4-Hydroxy-3-tert-butylphenoxy) -2,4-bis (n-oetylthioethylthio)> r1,3,5-triazine, ■

6- (4 ~ hydroxy-3-raethyl- 5-1 tert-butylphenoxy) ° 2-, 4-bis- (n-octylthio) -1,3,5-triazine,

30882 4/1141

2, Ί-bis (4-hydroxy-3-methy 1-5-tert-butylphenoxy) -6- (n-octylthioJ-l ^ rS-triazine,

2,4,6-TrIs - (^ - hydroxy-3-methyl-5-tert.-butylphenoxy) -

6- ( ^/ l-Hydroxy-3,5-di-tert-butylphenoxy) -2, ⁱ 4-bis- (noctylthiopropylthio) -l, 3> 5-triazine,

6- ( ¹ i-Hydroxy-3,5-di-tert-buty Iphenoxy) -2,4-bis- (ndodecylthioethylthio) - !, 3,5-triazine,

2, ⁱ l-bis ( ⁱ i-hydroxy-3i5 ~ di ~ tert-buty Iphenoxy) - <6-butylthio-1,3,5-triazine,

2,1-bis- ( ⁱ l-hydroxy-3,5-di ~ tert -butylphenoxy) -6- (n-octadecylthio) -1, 3,5-triazine,

2 _> ⁱ l-bis (4-hydroxy-3,5 ~ di-tert-buty Iphenoxy) -6- (n-dodecylthio) -1, 3,5 ~ triazine,

2, M-bis- ( ⁱ -hydroxy-3, i? -Di "tert-buty Iphenoxy) -6- (n-octylthiopropylthio) -1, 3,5-triazine,

2, ⁱ 4-bis- ( ⁱ J-hydroxy-3,5-di-tert-buty Iphenoxy) -6- (n-octylthioethylthio) -1, 3,5-triazine,

2, ¹ t-Bis - (^ - hydroxy-3,5-di-tert-butylphenoxy) -6- (n-dodecylthioethylthio) -1, 3 »5-triazine.

The triazine phenolic stabilizers identified above are described in greater detail in U.S. Patent No. 3,255,191.

30982A / 1U1

(11), Phenol is before compounds, of the general formula

where ρ is an integer from 2 to 4 ,. R "'a quadruple Group "such as an aliphatic hydrocarbon with 1 to 30 carbon atoms, an aliphatic Mono- or dithioether with 1 to 30 carbon atoms and / or a mono- or dietary aliphatic residue with 1 to 30 carbon atoms and ζ is an integer from zero to 6 mean,

Examples of connections of this type are:

Subclass I '■

n-Octadecyl-3- (3,5-di-tert-butyl- ^ l-bj'droxyphenyl) -. propionate, '·. · ■

n-Octadecyl-2- (3,5 ~ di-tert-butyl - ^ - hydroxyphenyl), - acetate,

n-Octadecyl-3,5-di-tert-butyl-1-hydroxybenzoate, n-hexyl-3j5-di-tert-butyl-4-hydroxyphenylbenzoate, n-dodecyl-3,5-di-tert-butyl - ^ - hydroxyphenyl benzoate ₃

Neo-dodecyl-3- (3,5-di-tert-butyl- ¹ »-hydroxyphenyl) -propioKat,. ».

Dodecy 1-ß- (3, ij-di-tert-butyl- ¹ ) -hydroxyphenyl) -propioriate,

t.-butylphcnyl) -iso-

butyrate, ■

Octadc.cyl-o- (lj-hydrüxy-3 _J i; -di-tert. -Buty! Phenyl) -i r; obut.yrrit., .. ■

Octadf3cy.li- (li-i ₁ ydroxy-3,5-di-t.ert.-butylphenyl) - i VlIi) I.

. 3 π 'i P.' h / 1 1 /. i

Subclass II

2- (n-Octylthio) ethyl-3,5-di-tert-butyl - ^ - hydroxybenzoate,

2- (n-Octylthio) ethyl-3,5-di-tert-butyl- ^ i-hydroxyphenyl acetate,

2- (n-Octadecylthio) ethyl-3,5-di-tert-butyl-4-hydroxyphenyl acetate,

2- (n-Oetadecylthio) -ethyl-3,5-di-tert-butyl - ^ - hydroxybenzoate,

2- (2-Hydroxyäthylthio) -äthyl-3,5-di-tert. ~ Butyl-4-hydroxybenzoate,

2 _> 2'-thiodiethanol bis (3,5-di-tert-butyl-4-hydroxyphenyl) acetate,

Diethy lglycol-bis- (3,5-di-tert-buty-1-li-hydroxyphenyl) propionate,

2- (n-Octadecylthio) ethyl 3- (3,5-di-tert-butyl-hydroxyphenyl) propionate,

2,2'-thiodiethanol-bis-3- (3 > 5-di-tert-butyl-4-hydroxyphenyl ) propionate,

Stearamido-N, N-bis- [ethylene-3- (3,5-di-tert-butcyl-hydroxyphenyl) propionate ],

n-Butylimino-N, N-bis- [ethylene-3- (3,5-di-tert-butyl- ¹ ! - hydroxyphenyl) propionate],

2- (2-Stearoyloxyäthylthio) -äthyl-3,5-di-tert- ⁱ | -but.yl-M-hydroxybenzoate,;

2- (2-hydroxyethylthio) ethyl 7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) heptanoate,

2- (2-Stearoyloxyätltiylthio) -ätliyl-7- (3-diethyl-5-part ^> t-butyl-1-hydroxyphenyD-heptanoate.

3 0 H S '/ ϊ ι .-, ι

IJhteyfclasse, III ■

1,2-propylene glycol bis- ^ 3- (3 * 5 ^Ä di-tert -butyl ⁴ -4 ■ * -. HydioxypheriyD -propionat %

Ethylene glycol bis [3- (3 ^^, S-di ^ fcert »-batyl - ^ - hyaroxy * ■ phenyl) -pfopionät],

NeGpentylglykol-bis- [3- (3> 5-di-tert- ^Ä butyl ^{i! I} - ⁱ l-, hydroxyphenyl) -propiöriäfe],

Ethylene glycol bis (3 j 5-di-tert.-butyl- ^ hydroxyphenyl acetate) j

Glyeerin-in- ⁱ octadecanoat-2 3,3 ^ bIS- "(3, S-di ^ -tert. ^A butyl-4 ^ hyaroxyphenylaeetat,

Pentaethylthritol-teferakis * [3 * (-3-, S ^ di-tert. -Buty1-4-hydroxypheny1) -propionafc],

III, i-trimethyl oil-ethane-tris-3- (3,5-dl-tert -b.utyi'-4-hydroxypheny1) propenate

Sorbitol-hexa - [3- (3,5-di-tert »-fe-utyl-4-li'diöxyphenyi) pröpionat],

i j2,3-Bufcahtriöl-tris-f 3 - "(3, S-di ^ tert -butyl ^Äi i-hydroxyphehyl) -propionät ~ \, _f..

2-Hydroxyethyl-7 ⁱ - (3-ynethyl'-5-'tert> buiyl- ⁱ l-hydroxyphenyl) heptanoate,

hydroxyphehyD ^ heptanoate,

l, 6-n-Hexandiöl-bis (3 ^f, .5'-dipheny1) ^ -t propionate] j

The phenolic ester stabilizers given above of subclasses I, II and III are cut in the " U.S. Patent No. 3,330,859 "

309824/1141

(12) Phenolic compounds of the general formula

Q- (CH ₉ -) - P - OR »

c- X ι

OR "

wherein R "and Q have the meanings given above and χ is 1 or 2.

Examples of connections of this type are:

■ Di-n-octadecyl-3, .5-di-tert. -butyl-'J-hydroxybenzylphosphonate,

Di ~ n-octadecyl-3-tert-butyl-4-hydroxy-5-methylbenzylphosphonate,

Di-n-octadecyl 1- (3,5-di-tert-buty1-4-hydroxyphenyl) ethane phosphonate,

Di-n-tetradecyl-3 »5-di-tert.-butyl-M-hydroxybenzylphosphonate,

Di-n-hexadecyl-3 »5-di-tert-butyl-4-hydroxybenzylphosphonate,

Di-n-docosy1-3,5-di-tert-butyl - ^ - hydroxybentylphosphonate,

Di-n-octadecy1-3,5-di-tert-butyl-A-hydroxybenzylphosphonate.

The di- (higher molecular) alkylphenolphosphonates given above are more detailed in U.S. Patent No. 3,281,505.

3 0 9 8 2 4/1 U

(13) Phenolic compounds of the general formula

(CH ₂ ) _W Q

• where w and Q have the meanings given above. , .'- .. ·: '.

Examples of connections "of this type are:

Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,

Tris (3-tert-butyi-4-hydroxy-5-methylbenzyl) isocyanurate. .

The above-mentioned hydroxyphenylalkenyl isocyanurates are, more precisely in Up Patent No. 3,531,483 described. .

The phenolic hydrogen stabilizers listed above are known and many are commercially available,

Though all of the above. Antioxidants in combination with the invention are screened ate ultraviolet stabilizers verv / ends can ground v /, the sterically hindered phenols of the above groups 1, 8, 9, 10, 11 _r 12 and 13, the preferred are .Antioxidantien. The most preferred sterically hindered phenols are those of groups 1, 9, 11, 12 and 13 «

Further examples of antioxidants are the compounds of the aminoaryl series, e.g. aniline and naphthylamine derivatives and their heterocyclic derivatives, such as the compounds given below:

Phenyl-1-naphthylamine, Phenyl-2-naphthylamine, N, N'-diphenyl-p-phenylenediamine, NjN'-di-sec-butyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, Mono- and di-octyliminodibenzyl and polymerized 2,2,4-trimethyl-1,2-dihydroquinoline.

Ultraviolet absorbers and light stabilizers include:

(a) 2- (2'-Hydroxyphenyl) -benzotriazoles, e.g. 5'-methyl-, 3 ^l , 5'-di-tert-butyl-, 5'-tert-butyl-, 5-chloro-3 ' , 5'-di-tert.-butyl-, 5-chloro-3 ^I -tert.-butyl-5 ^l methyl-, 3'-sec-butyl-5'-tert.-butyl-, 3 '- [ a-methylbenzyl] -5 '-methyl-, 3' - [α-methylbenzyl] -5 ', -methyl-5-chloro-, 4'-octoxy-, 3', 5'-di-tert-amyl- , 3'-methyl-5 ^l -carbomethoxyethyl and 5-chloro-3 ·, 5'-di-tert-amyl derivatives. <

(b) 2,4-bis (2 ^l -hydroxyphenyl) -6-alkyl-S-triazines, for example the 6-ethyl or 6-undecyl derivatives.

(c) 2-Hydroxybenzophenones, for example the 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4,2 ', 4'-trihydroxy or 2'-hydroxy-4 , 4 ^l -diraethoxy derivatives.

(d) 1,3-Big (2'-hydroxybenzoyl) -benzolß _l, for example 1,3-bis (2'-hydroxy-4'-hexyloxybenzoyl) benzene,

1,3-bis- (2 ^l -hydroxy-4'-octoxybenzoyl) -benzene, 1,3-bis- (2'-hydroxy-4'-dodecyloxybenzoyl) -benzene.

(e) Aryl esters from optionally substituted benzoic acids such as e.g. Phenyl salicylate, Octylphenylsalicylat, DibehZOy! Resorcin, Bis-t ^^ tert ^ -butylbenzöyD-resOrcini Ben ζ oy Ir es or c in and 3,5 - ⁴ Di -1 ert * -but y 1- 4 -hydro xy -to enz ο e acid ~ 2,4-di * -tert-butylpheny! ester and -c as well as -2-r

(f) Acrylates, for example «- or is'O-octylesfe or buty! ester and N-iB-Ca indoline.

(g) Niekel compounds, such as Niekel complexes of

(4-tert, »- octylphenoi), ζ / B. the 1: 1 and 1: 2 complexes, which may have other ligands, such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine; Niekel complexes of bis-C 1-4 tert.; - OGtylp: henyl ·) -sulfOn, such as the 2: 1 complex, which may have other ligands, such as 2-ethylcaproic acid .; Nickel dibutyl dithio-carbamates, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid-πiono-alkyl esters, such as the methyl, ethyl or butyl esters; the nickel complex of 2-Hydroxy- k- methy1-pheny1-undecylketonοxim and Ni ekeI-3,5 * "di-tert-butyl-4-hydroxybenzoate, as well as

(h | oxalic acid diamides, e.g..

¹ I ₃ ^ ¹ -dioctyloxyoxanilide, 2,2'-dioctyloxy-5 ₃ 5 '-di-tert . -buty1-oxanilide, 2,2 ¹ -Di-dadecyiöxy-S , Ψ * -di-t ert *. -

2-Ä "thöxy-2 ^t-ethyl oxanilide,

Hybrids of ο- and p-methoxy and ethoxy dl » substituted oxanilides and the compound of the formula: '.,

CH _x CH,

3 y 3

N- (CH ₂ ) ~ - NHCOCONlK CII ₂ ) j

_x CH *

3 3

Phosphite stabilizers include triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, trinonyl phenyl phosphite, trilauryl phosphite, trioctadecyl phosphite, 3,9 ~ di-isodecyloxy- * 2,4 _> 8,10-tetraoxa-3 »9-diphosphaspiro and -3 , 5-di-tert-butylphenyl) * phosphite.

Include peroxide-decomposing compounds for polyolefins ß-Thiodipropionsäuren, for example the lauryl _t stearyl, myristyl or tridecyl esters, salts of Mercaptobena · iniidazolen as the zinc salt, as well as DiphenyltMohärastoff.

Suitable polyamide stabilizers include Kiipfersalze In Combination with iodine & an and / or other phosphorus compounds and salts of divalent manganese.

Basic co-stabilizers are e.g. polyvinylpyrrolidone, Melamine, benzoguanamine, triallyl cyanurate, dicyandiamide, Urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth salts of more highly saturated or unsaturated fatty acids such as calcium stearate.

Polyvinyl chloride stabilizers include organotin compounds, organo lead compounds, and Ba / Cd salts ¥ öä fatty acids.

30982 4 / IUl

Examples of nucleating agents are 4 ~ tert-butylbenzoic acid, Adipic acid and diphenylacetic acid.

As the compounds of the general formula Ϊ be optionally further additives employed advantageously in an amount in the range of 0.01 to 5 wt -.% _F used based on the weight of the untreated Polymerisätmaterials.

In the form of binary combinations with one or more of the above-mentioned antioxidants or in the form of tertiary combinations with such antioxidants and the above The specified UV absorbers represent the compounds of general formula I effective stabilizer combinations for Polyolefin formulations. '

The following examples are intended to explain the invention further without, however, restricting it «,

Example 1 '-. .

A mixture of 15.70 parts by weight of 2,2,6,6-tetramethylpiperidin-4-ol, 29.20 parts by weight of methyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl ) propionate and 1.00 parts by weight of lithium amide were stirred 5 hours in the melt at 150 ⁰ C. The methanol formed during the reaction was removed using a modified Dean-Stark apparatus. The cooled reaction mass was then column chromatographed on an alumina column using petroleum ether as the solvent to give 2,2,6,6-tetramethylpiperidinyl-4-β : propionate in the form of a white solid having a melting point of 77-78 ⁰ C and received the following analytical values - (3 iyphenyl ^t, 5'-di-tert-butyl-4 ^I ~ hydro)

3 0 9 8 7 UI ι 1

Analysis C ₀ , -H, -, NO,: ^J 2o 43 3

78 1 H 38 22nd 5 7997 C. 97 1 ο, 37 N 74, O, 3 , 35 74, 3 , 15

"ber .: found .:

Example 2

A mixture of 9.50 parts by weight of 2,2,6,6-tetramethylpiperidine-4-oil and 9.50 parts by weight of 3,5-di-tert-butyl-4-hydroxybenzoyl chloride in 150 parts by weight of dry benzene heated under reflux for 6 hours. The solution was then allowed to cool and the precipitate formed was filtered off. Separation of the benzene by distillation under reduced pressure gave a yellow oil which slowly solidified. A crystalline solid precipitated out by the addition of ether, which was filtered off, washed with ether and dried, whereby 2,2,6,6-tetramethylpiperidinyl-4- (3 '»5'-di-tert.-butyl-4 ^f hydroxybenzoate) in the form of a white solid with a melting point of 180 to 182 ⁰ C and the following analytical values:

Analysis C ₂ g

74 C. H ° 3 3 N ber .: 74 , 02 10, 84 3 , 60 found: , 28 9, , 71

3 0 9 R 2 h / 1 1 ύ i

- '29

B e Is pi e 1 3 and %

38 parts by weight of ^ oil ^^ apylBn were: with U, <376 parts by weight n-Öetädecyl ^ ß ^ C ^ '^ hydr ^^ -

Propionate three minutes in Biner Kaei; facility. homogenized. Bans were given 0 _; , 1B GeW ^ TellB of the product e's from example 1 or wn example .2 and continued the homogenization for a further seven -nuts-,

The homogenized mixture was then removed from the kneading device and pressed ^{in a press at 20O 0} G to a thickness of 2 to 3 minutes. 9 parts by weight of the polypropylene mixture were then introduced into a press. whose press plates were protected with a 0.1 mm thick aluminum foil 'ge ^ -'. The sample was then surrounded by four square steel strips with a thickness of 0.3HIm, which act as spacers between the aluminum foils. The press was closed-then 2 ^minutes: sen, with no pressure was applied. The pressure was then increased to a maximum of 12 tons in the course of 2 minutes, whereupon this pressure was held at a temperature of 260 ° C. for a further Z minutes. Then the application of pressure was interrupted and the (0.3 mm thick) material was immediately cooled under running water.

2.2 parts by weight of this material made a square cut up and put back into the press. The same pressure was applied as indicated above, however, a 0.1 mm thick steel rim was used as a spacer between the aluminum foils. The press was closed and no pressure was applied for 2 "minutes. Pressure then increased over 2 minutes increased to 5 tons, the temperature of the press being 260 ° C. This pressure was then maintained for 2 minutes * obtain. . ■

309824/1

2: 25.7397

The "sandwich" of the 0.1 mm thick polypropylene film and the aluminum foil was then removed and annealed for 1 hour in an immediately maintained at 150 ⁰ C air rotary kiln ge ~. The "sandwich" was then quenched in cold running water, whereupon the aluminum foils were peeled from the inner polypropylene foil and the edge spacers removed.

A section measuring 44 ζ 100 ram was made of removed from the heat-treated 0.1 mm thick polypropylene film and in an exposure device (fademeter) »the 28 daylight and UV light lamps arranged in a circle existed, exposed. The daylight lamps passed from 61 cm (2 feet) long 20 watt fluorescent lamps, 4ie had a peak emission of 3000 5t-uniton. The UV light lamps were also 61 cm (2 feet) in length, had an output of 20 Viat.t and delivered a peak emission of 3500 Α units. the The sample was rotated concentrically within the circle of the annularly arranged lamps so that the The radiation emitted by the lamps is uniform over the; to test sample was distributed.

The exposed sample was examined periodically and the time (T) at which the sample reached 50 % of the initial elongation at break was determined.

Similar tests were carried out on polypropylene samples, which do not have a stabilizer or a known stabilizer ((2,2,6,6-tetramethylniperid.inyl-4.) benzoate. ,, described in the German patent Hr. 1 929 928) contained. The results obtained are summarized in Table I below.

30 98? I * I 1 I U ί

The results given in Table I show that the connections according to the invention to the structurally next related connections, in particular in German Patent No. 1,929,928 are clearly superior to light and heat stabilizers for polypropylene. -

309824/1 1 U 1 -

TABLE I. example

Additive

none

2,2,6,6-tetramethylpiperidinyl

4-benzoate

2,2,6,6-tetramethylpiperidinyl-4-3 ' , 5'-di-t-butyl-4-hydroxybenzoate

2,2,6, ö-Tetramethylpiperidinyl- ^ iß- (3 » , 5'-di-t-butyl-J "'- hydroxyphenyl) propionate

Time until
Becoming brittle

in the heat aging test

(Hours.)

11
18th

Time until 50 % of the original elongation at break is reached

(Hours.)

125 330

437 655

2257M7

At . _: ö _: - &., ie, 1 .... 5 ■ "·

töOQ Gewi ^ parts not ^ stabilized polypropylene powder applies in the Trociceiie Mt \ ÖeWv ~ parts n-Oetä y ^ · 3HS '* ^: - & L-tert * ^ butyiph ^ nyl ■) -p

€ es P ^ oxM &fees;'voä Beispl & L ί vöi ^ iisfelit ^ Me mixture viÄe € iann böi Eyl fy to 22Ö ^Ö C extriiäiert ^ what

% ur ^ e * The siaMliüierte Forüiude s © preserved spun in xier Schiaelze and under * ä Conditions rebkti

Aandstiicit:

Mecklenburgi . ■ "" 145

Ti% er deö MuI ti filament ©: 130/1 ^ 7 ßenier

Tensile strength i. "■, S g / öenier»

The obtained MEaLtif iiaiaent v / was mounted under ^ erde of Weißefii iCartön as a base on uen iPröfeenhärter of an exposure device (Xenotest ^ 50, quartz lamps tktfbH »). In Belichtungszeitintervaileil "of 200 hours five Pas -were test, examined and it was their retained Zugfestiglieit bestiiMiti would die. Values obtained graphically the exposure time gegön applied and #e BeliehtungSZeit (T)> ^ AEIE to eleventh ^ O joigeh Ver * 1 ütst #ER original tensile strength leads-e _ä, was removed from the curve * This ¥ ertwird as the time to 'angenofiiffien to decomposition.

The values obtained are given in the following tables II, which also have the values of 'a.MergleichsunterBia ^ chmng {in which no Li ent stabilizer was used) and show for a comparison experiment defa a commercially available light stabilizer has expired became. .

TABLE II example

CaJ O CD

Additive

none

2 * · (2'-Hydroxy-3 »* 5 'butylphenyl) -5 ~ <benzotriazole time (T) to
at a loss of 50 %
the tensile strength

(Hours.)

530

Pactor

T (additive)

T (control)

1.2

2,2,6,6-Tetremethylpiperidinyl- ^ -ß- (3 ^f »5 ^f -äi-t-butyl-4'-hydroxyphenyl) * propionate 1500

3 * 5

The values in Table II clearly show the better light stabilizer effect, which is inventive connection compared to the effects, which result in the control and comparison tests is achieved. . "" ■ .-

Claims (3)

PATE N TANSP. RETURN: (l. Piperidine derivatives of the general Forrael (A) _n - CO (D A is a group of the following formulas -, -CH ₂ CII ₂ - or -CH ₂ -CII- R ^ and R ₂ »which are identical or different; can be straight-chain or branched alkyl groups with 1 to 6 carbon atoms, 1-Ilethylcyclohexyl groups or a, a ~ dimethylben ^ yl groups, R ^ and R /, which can coin the same or different, Alkyl groups with 1 to 12 carbon atoms or together with the carbon atom to which they are bound »one 3 0 98- 4 /! saturated al icyeli ropes tight with 5 to 8 cabbage casteff atoms or the group egg- F and η zero or 1 mean ,, ^: '. . 2. Connections; according to; Claim "1, characterized in that one of the groups R ₁ , and Ro &&^& Ρ- both groups mean a tert-butyl group. -. ' 3. Compounds according to claim 1 or 2, characterized in that R ₃ . and R-λ similar or, and are alkyl groups with \ to 6 carbon atom ens to ff s th, · - k. Yerbindungen according to φη Aiaspiliehea 1- to 3 _f characterized _f that A is a ^ group of and η .1; mean,. - ■,: ..... ■ - · __.- ■ 5. Compounds according to ¹ djen Arisppäoheri, I to 5, thereby ge indicates that η means mull. 3 Q 9 8 2 4/114 7 6. Compounds of the general formula tert-butyl CB, CIL v / orin the group R _{2 has} the meaning given in claim 1. Compounds of the general formula tert-butyl CH ₂ CH ₂ CO ₂ wherein the group R _{2 has} the meaning given in claim 1. 8. Compositions containing an organic material and a small amount of a compound as a stabilizer of claim 1. 30 9.82 A / 1 U 1 9. Compositions according to claim 8, characterized in that the organic material-a polymer
is. . 10. Compositions according to claim 9, characterized in that that the polymer is a polyolefin. 11. Compositions according to claim 8, characterized in that the organic material is polyethylene,
Is polypropylene or polystyrene. 30 98 2 4 / 1ΗΊ 3 0 9 R / /./n /, ι