Piperidine derivatives their preparation and their use as stabilisers for polymeric materials

New piperidine derivatives, their preparation and their use as stabilisers for polymeric materials

CIBA-GEIG7 AG

C/ ?8886

40888-2'

The present invention relates to new piperidine derivatives, and in particular to new piperidine derivatives substituted at the 1- and 4- positions and having value as stabilisers for polymeric materials.

In German Patent Specification No. 1,929,928 there are described compounds having the general formula:

<img file="IL40888A_D0001.tif" />

<img file="IL40888A_D0002.tif" />

wherein R^' and R2' are the same or different and each is an alkyl group, or, together with the carbon atom to which they.are bound, they form a saturated alicyclic group or a group having the formula:

0Η_ς CH₃

<img file="IL40888A_D0003.tif" />

ch₃ ch₃ n' is a whole number from 1 to 3 inclusive; and when n' is 1, R₃ is an acyl group derived from an aliphatic, alicyclic or heterocyclic mono-carboxylic acid, an N-substituted carba- 2 -

<img file="IL40888A_D0004.tif" />

<img file="IL40888A_D0005.tif" />

40888-2 moyl group derived from an N-substituted carbamic acid, an N-substituted thiocarbamoyl group derived from an N-substituted thiocarbamic acid, a monovalent group obtained by removing an hydroxyl group from an oxo-acid, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or a group having the formula:

<img file="IL40888A_D0006.tif" />

wherein R' and R₉' have their previous significance; when n' is 2, R₂ is a diacyl group derived from an aliphatic, alicyclic, aromatic or heterocyclic dicarboxylic acid, a dicarbamoyl group derived from dicarbamid acid, a bis-thiocarbamoyl group derived from bis-thiocarbamic acid, a carbonyl group, a divalent group obtained by removing two hydroxyl groups from an oxo-acid, an alkylene group, an arylene group, or an arylenedialkylene group; and when n' is

3, ^R3 is a triacyl group, derived from an aliphatic, alicyclic, aromatic or heterocyclic tricarboxylic acid, a tri carbamoyl group derived from tricarbamic acid, a tris-thio carbamoyl group derived from tris-thiocarbamic acid, a trivalent group obtained by removing three hydroxyl groups from an oxo-acid, an alkanetriyl group, arenetriyl group or an arenetriyl trialkylene group.

<img file="IL40888A_D0007.tif" />

*) «4ksSSSt.t ^: 40888-2

We have now found that certain piperidine derivatives substituted in the 1- and 4- positions are effective stabilisers for polymers, especially against photo- and thermal degradation.

According to the present invention, there is provided a compound having the formula

<img file="IL40888A_D0008.tif" />

or a salt thereof, wherein n is 1, 2 or 3, is an alkyl residue having from 1 to 12 carbon atoms or a substituted alkyl residue having the formula or -CH₂-X₂ wherein

X. is -CN, -OH, -OCH0, -0-C-R₃ or -0־C-NH-R₄, ^J I ^J R .

X2 is phenyl, -CH״CH_2> -CH ־^pH₂ .-0 or -C-ORj, 0 r₃ is alkyl having from 1 to 20 carbon atoms, alkenyl having from 2 to 4 carbon atom/’, aryl having 6 or 7

<img file="IL40888A_D0009.tif" />

carbon . atoms,

R4 is alkyl having from 1 to 12 carbon atoms,

Rg is alkyl having from 1 to 20 carbon atoms, or

R-L is a group -CO-Y or -CO-NH-Z, wherein

Y is alkyl having 1 to 4 carbon atoms, alkenyl having 2 or 3 carbon atoms, and

Z' is alkyl having 1 to 12 carbon atoms, aryl or substituted aryl having 6 to 10 carbon atoms, and when n is-1, R₂ is a monovalent residue and is -CH2־CH₂־CN or benzyl or an acyl group -C-Rg, where

Rg is benzyl, vinyl, propenyl, cyclohexyl a group

<img file="IL40888A_D0010.tif" />

tert.C₄H₉ . tert.C₄H₉ or Rg is Rg' and Rg¹ is alkyl having from 1 to 20 carbon atoms or an aromatic group having from 6 to 10 carbon atoms or an aromatic group substituted with alkyl having from 1 to 4 carbon atoms, or

R₂ is a carbamoyl residue -C-NH-R? wherein ί) .

R? is a monovalent residue and is an alkyl residue having from 1 to 20 carbon atoms, an alkenyl residue having 3 or 4 carbon atoms, an alicyclic residue having from 5 to 12 carbon atoms or an aromatic residue having from 6 to 12 carbon atoms, or

R₂ is a monovalent residue obtained by removing one hydroxyl group from a phosphorus containing acid, when n is 2, R₂ is a divalent residue and is one of the groups

-C-C-, -C-R_o-C- or -C-NH-R_q-NH-C-, wherein

4i f J &lt;J A ^K8 is an alkylene residue having up to 18 carbon atoms, a phenylene residue or the group

-(CH₂)2S(Ct^)2”י

Rg is an alkylene residue having up to 20 carbon atoms, a divalent alicyclic residue having from 5 to 15 carbon atoms or a divalent aromatic residue having from 6 to 15 carbon atoms, or

R₂ is a divalent residue obtained by removing two hydroxyl groups from a phosphorus containing acid, or when n is 3, R2 is a trivalent residue derived from phosphoric, phosphorous or boric acid, provided that when R₂ represents -COR^¹, -CO-, -CO-CO-,

-CO-R0-CO- or a trivalent group derived from phosphoric, 0 phosphorous or boric acid, the number of carbon atoms of

40888/3 alkyl group designated, by is limited to 5 to 12, and provided that only one of and R₂ can represent an unsaturated acyl group.

^R!׳ ^r4 ^{or z} may be an alkyl residue having from 1 to 12 carbon atoms, examples of this substituent are methyl, ethyl, n-propyl, n-butyl, sec-butyl, t-butyl, n-hexyl, n-octyl, 2ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl. If, howeve'r, R₂ is an acyl group -CO-R^¹, -CO-, -COCO-,

-CO-Rg-CO- or a trivalent group derived from H״P0,, Η,ΡΟ, □ Η Ο Ο or Η₃ΒΟ₃ the number of carbon atoms of Rjl as alkyl group is restricted to 5 to 12.

R3 or R^ may be an alkyl residue having from 1 to 20 carbon atoms, examples of this substituent are methyl, ethyl, n-propyl, n-butyl, sec-butyl, t-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, ntridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

When Y is an alkenyl residue having 2 or 3 carbon atoms it may be a vinyl or propenyl group. R_{3 as} alkenyl may be allyl or methallyl or vinyl.

When r₃ is an aryl residue having 6 or 7 C-atoms, it may be phenyl or tolyl, z as aryl may be phenyl or phenyl substituted with alkyl having 1 to 4 carbon atoms.

When n is 1 and R₂ is an acyl group -COR , R _may be 0 b ^R6' and Rg' may be an alkyl residue having from 1 to 20 carbon atoms as for example a methyl, ethyl, propyl, butyl, hexyl, n-octyl_f 2-ethylhexyl, n-decyl, n-undecyl, n-tridecyl, n-tetradecyl, n-hexydecyl, n-heptadecyl and eicosyl residue.

Rg' may be an unsubstituted aromatic group having from 6 to 10 carbon atoms such as a phenyl or naphthyl, or may be an aromatic group, substituted by alkyl having 1 to 4 carbon atoms such as tolyl or p-tert-butylphenyl.

When n is 1, R2 may also be a carbamoyl residue -C-NH-R?

A wherein R? is an alkyl residue having from 1 to 20, preferably 1 to 8, carbon atoms, an alkenyl residue having 3 or 4 carbon atoms, a cycloalkyl residue having from 5 to 12 carbon atoms, preferably cyclohexyl, or an unsubstituted or substituted. aryl residue having from 6 to 12 carbon atoms, preferably 6 to 10 C-atoms. Examples of suitable carbamoyl residues R₂ within this group are N-methylcarbamoyl, N-ethyl-carbamoyl, N-n-propylcarbamoyl, N-isopropylcarbamoyl, N-n-buty!carbamoyl, N-n-pentylcarbamoyl, N-n-octylcarbamoyl, N-n-decyldarbamoyl, N-n-dodecylcarbamoyl, N-n-octadecyl, N-n-eicosylcarbamoyl, N-cyclopentylcarbamoyl, N-cyclohexylcarbamoyl, N-methylcyclohexylcarbamoyl, N-cyclododecylcarbamoyl, N-phenylcarbamoyl, N-(o-, m- and p-tolyl)carbamoyl, N-(2,4- and 2,6-xylyl)carbamoyl, N-(a- and β-naphthyl)carbamoyl.

When n is 2, R״ may be a diacyl residue -C-R_o-C- and is an alkylene residue having from 1 to 18, preferably

2־40888

,׳־־ . י . י י י . י: י to 6, carbon atoms such as methylene, ethylene, trimethylene, tetramethylene or hexamethylene residue. 1 ' ! R״ may be a dicarbamoyl residue -C-NH-Rg-NH-C- wherein.

. 1 δ

Rg may be an alkylene residue having up to 20 carbon atoms, j for example methylene, ethylene, trimethylene, tetramethylene, ף . hexamethylene, octamethylene, dodecamethylene or octadecaj methylene or Rg may be a cycloalkylidene residue, for ׳ example a 1,4- or 1,3-cyclohexylidene or a methylene-4,4'dicyclohexylidene residue, or Rg may be an arylidene residue having from 6 to 15 carbon atoms, as for example a 1,4- or

1,3-phenylene, 2,4-toluylene, 1,4-naphthylene or diphenyl| methane-4,4*-diyl residue.

I ' .

Examples of compounds of the present invention are:

; Examples where n = 1

4-(2'-Cyanoethoxy)-1,2,2,6,6ךpentamethylpiperidine

1-(2¹-Hydroxy®thyl)-4“benzyloxy-2,2,6,6-tetramethyli piperidine

2)-1 ן'-Cyanoethyl)-4-benzyloxy-2,2,6,6-tetramethy!piperidine

1-(2¹-Cyanoethyl)-4-(2¹-cyanoethoxy)-2,2,6,6-tetramethyl.ί piperidine

I 1-(2¹,3'-Epoxypropyl)-4-benzyloxy-2,2,6,6-tetramethyl| piperidine

1-C2¹ - (Methylcarbamoyloxy)ethyl]-4-benzyloxy-2,2,6,6-tetramethylpiperidine

1-[2¹ -(Phenylcarbamoyloxy)ethyl]-4-(2¹-cyanoethoxy)-2,2,6,6ί tetramethylpiperidine

<img file="IL40888A_D0011.tif" />

1.2.2.6.6- Pentamethylpiperidinyl-4-cyclohexanecarboxylate

1.2.2.6.6- Pentamethylpiperidinyl-4-phenylacetate l-n-Octyl-2,2,6,6-tetramethylpiperidinyl-4-benzpate l-n-Dodecyl-2,2,6,6-tetramethyIpiperidinyl-4-n-octanoate l-n-Dodecyl-2,2,6,6-tetramethylpiperidinyl-4-p-chlorobenzoate

־ ׳ \ \

l-Allyl-2,2,6,6-tetramethylpiperidinyl-4-n-octanoate l-Allyl-2,2,6,6-tetramethylpiperidinyl-4-cyclohexanecarboxylate l-Allyl-2,2,6,6-tetramethylpiperidinyl-4-benzoate l-Benzyl-2,2,6,6-tetramethylpiperidinyl-4-n-octanoate l-Benzyl-2,2,6,6-tetramethylpiperidinyl-4-(2¹-ethylhexanoate) l-Benzyl-2,2,6,6-tetramethylpiperidinyl-4-stearate l-Benzyl-2,2,6,6-tetramethylpiperidinyl-4-benzoate

1-(2'-Hydroxyethyl)-2,2,6,6־tetramethylpiperidinyl-4acetate

1-(2'-Hydroxyethyl)-2,2,6,6-tetramethylpiperidinyl-4laurate

1-(2’-Hydroxyethyl)-2,2,6,6״tetramethylpiperidinyl-4stearate

1-(2'-Hydroxyethyl)-2,2,6,6-tetramethylpiperidinyl-4benzoate

1-(2'-Cyanoethyl)-2,2,6,6-tetramethylpiperidinyl-4-benzoate

1-(2',3'-Epoxypropyl)-2,2,6,6-tetramethylpiperidinyl-4-acetate

1-(2'-Acetoxyethyl)-2,2,6,6-tetramethylpiperidinyl-4-laurate

1-Γ2 י -(Methylcarbamoyloxy)ethyl] -2,2,6,6-tetramethylpiperidinyl-4-benzoate

1-[2'-(Phenylcarbamoyloxy)ethyl]-2,2,6,6-tetramethylpiperidinyl-4-isobutyrate l-Ethoxycarbonylmethyl-2,2,6,6-tetramethylpiperidinyl-4-pmethoxybenzoate

4-Methylcarbamoyloxy-l,2,2,6,6-pentamethyIpiperidine 4-Isopropylcarbamoyloxy-l,2,2,6,6-pentamethylpiperidine 4-t-Butylcarbamoyloxy-l,2,2,6,6-pentamethyIpiperidine 4-n-Hexylcarbamoyloxy-l,2,2,6,6-pentamethylpiperidine 4-[2'-Ethylhexylcarbamoyloxy]-1,2,2,6,6-pentamethylpiperidine

4-n-Dodecylcarbamoyloxy-l,2,2,6,6-pentamethylpiperidine 4-n-0ctadecylcarbamoyloxy-l,2,2,6,6-pentamethylpiperidine 4-Cyclohexylcarbamoyloxy-1,2,2,6,6-pentamethylpiperidine

4- [3' -Methylcyclohexylcarbamoyloxy] -1',2,2,6,6-pentamethylpiperidine

4-[4'-t-Butylcyclohexylcarbamoyloxy]-1,2,2,6,6-pentamethylpiperidine

4-CyclohexyImethylcarbamoyloxy-1,2,2,6,6-pentamethylpiperidine .

4-Phenylcarbamoyloxy-l,2,2,6,6-pentamethylpiperidine

4-m-Tolylcarbamoyloxy-1,2,2,6,6-pentamethyIpiperidine 4-p-Tolylcarbamoyloxy-1,2,2,6,6-pentamethyIpiperidine 4-p-Chlorophenylcarbamoyloxy-l,2,2,6,6-pentamethylpiperidine 4-p-t-Butylphenylcarbamoyloxy-1,2,2,6,6-pentamethylpiperidine 4-a-Naphthylcarbamoyloxy-l!2,2,6,6-pentamethylpiperidine

4-Cyclohexylcarbamoyloxy־l-ethYl-2,2,6,6-tetramethylpiperi׳dine . . ’

40888-2

4-Methylcarbamoyloxy-l-n-propyl-2,2,6,6-tetramethy!piperidine 4-Methylcarbamoyloxy-l-secbutyl-2,2,6,6-tetramethy!piperidine 4-n-Octadecylcarbamoyloxy-l-n-butyl-2,2,6,6-tetramethvlpiperidine ^J .

4-Methylcarbamoyloxy-l-n-octyl-2,2,6,6-tetramethylpiperidine

4-Phenylcarbamoyloxy-l-allyl-2,2,6,6-tetramethy!piperidine 4-Phenylcarbamoyloxy-l-benzyl-2,2,6,6-tetramethylpiperidine 4-Methylcarbamoyloxy-l- (.2' -hydr.oxyethyl) -2,2,6,6-tetra״ methylpiperidine

4-Methylcarbamoyloxy-l-(2',3'-epoxypropyl)-2,2,6,6-tetramethylpiperidine ’

4-n-Hexylcarbamoyloxy-l-[2'-(methylcarbamoyloxy)ethyl]-

4,2,6,6-tetramethylpiperidine

Examples where n = 2.

Bis(l-n-octyl-2,2,6,6-tetramethyl-4-piperidinyl)sebacate

Bis-(l-n-dodecyl-2,2,6,6-tetramethyl-4-piperidinyl)adipate

Bis(l-allyl-2,2,6,6-tetramethyl-4-piperidinyl)adipate Bis(l-benzyl-2,2,6,6-tetramethyl-4-piperidinyl)sebacate adipatP' ^hydroxyethy1^ 6 י ⁶י ²» ²־-tetramethyl-4-piperidinylJ Bis[1-(2¹-cyanoethyl)-2,2,6,6-tetramethyl-4-piperidinyl] SeDHCSte

Bis [1-(2¹,3’ azelate

-epoxypropyl) -2,2,6,6-tetramethyl-4-pipe.ridinyl.]

Bis tl-(2'-methoxyethyl)-2,2,6,6-tetramethyl-4-piperidinyl] pimelate

Bis tl(2¹-acetoxyethyl)-2,2,6,6-tetramethyl-4-piperidinyl] glutarate

Bis CL- (2¹-methylcarbamoyloxyethyl)-2,2,6,6-tetramethyl-4piperidinyl]malonate

Ethane-1',2'-bis [4-carbamoyloxy-l,2,2,6,6-pentamethylpiperidine]

Hexane-1',6'-bls [4-carbamoyloxy-l,2,2,6,6-pentamethylpiperidine]

2',4',4’-Trimethylhexane-l',6'-bis[4-carbamoyloxy-l,2,2,6,6pentamethylpiperidine]

Cyclohexane-1¹,3¹-bis [4-carbamoyloxy-l,2,2,6,6-pentamethylpiperidine]

Benzene-1',4¹-bis [4-carbamoyloxy-l,2,2,6,6-pentamethylpiperidine]

4'-bis[4-carbamoyloxy-l,2,2,6,6-pentamethylNaphthalene-1',5'-bis [4-carbamoyloxy-l,2,2,6,6-pentamethylpiperidine]

Diphenylmethane-4¹,4-bis[4-carbamoyloxy-l,2,2,6,6-pentamethylpiperidine]

Toluene-2',4'-bis [4-carbamoyloxy-l-n-propyl-2,2,6,6-tetramethylpiperidine]

Hexane-1¹,6¹-bis[4-carbamoyloxy-l-n-butyl-2,2,6,6-tetramethylpiperidine]

Hexane-1',6'-bis[4-carbamoyloxy-l-n-octyl-2,2,6,6-tetramethylpiperidine!

Cyclohexane-1¹,4¹-bis[4-carbamoyloxy-l-allyl-2,2,6,6-tetramethylpiperidinel

2',4',4'.Trimethylhexane-1¹,6'-bis [4-carbamoyloxy-l-allyl-

2,2,6,6-tetramethy!piperidine]

Toluene-2

Toluene-24 , י'-bis L4-carbamoyloxy-l-benzyl-2,2,6,6-tetramethylpiperidine]

Toluene-2,4-bis r4-carbamoyloxy-l-(2¹-hydroxyethyl)-2,2,6,6tetramethylpiperidine]

Diphenylmethane-4',4-bis [4-cafbamoyloxy-l-(2'-cyanoethyl)-

2,2,6,6-tetramethylpiperidine]

Toluene-2,4-bis [A-carbamoyloxy-l-(2-acetoxyethyl)-2,2,6,6tetramethylpiperidine]

Hexane-1,6-bis Γ4-carbamoyloxy-1-(2¹-methylcarbamoyloxyethyl)-2,2,6,6-tetramethy!piperidine]

Examples where n = 3.

Tris(l-allyl-2,2,6,6-tetramethyl-4-piperidinyl)phosphate phos h ־ t²' ^-cyanoet:hyl)־6 ’ ⁶י ²י ²־tetr.amethyl-4-piperidinyl Tris(l-hexyl-2,2,6,6-pentamethyl-4-piperidinyl)borate

The invention also includes salts of the compounds of Formula I, for instance salts of inorganic acids such as phosphates, carbonates, sulphates and chlorides and salts of organic acids such as acetates, stearates, maleates, citrates, tartrates] oxalates, benzoates and substituted carbamic acids.

40888/3

R₂ can be represented by a mono- or divalent group obtained by removing one or two groups from a phosphorus containing acid, such as phosphoric, phosphorous, phosphonic or phosphinic acids and their esters. Examples of compo.unds with such groups for R₂ are the following compounds.

l,2,2,6,6-Pentamethylpiperidinyl-4 phenyl phosphonate l,2,2,6,6-Pentamethylpiperidinyl-4 dimethyl phosphite l,2,2,6,6-Pentamethylpiperidinyl-4 diphenyl phosphate Bis(1,2,2,6,6-pentamethyl-4-piperidinyl phosphonate Bis(l,2,2,6,6-pentamethyl-4-piperidinyl) phenyl phosphate.

A preferred sub-group of compounds of formula I are those compounds having the formula

<img file="IL40888A_D0012.tif" />

and their salts, wherein n is 1 or 2 and is an alkyl group having from 1 to 12 carbon atoms, allyl or benzyl, and when n is 1, R^q is cyclohexyl, vinyl., propenyl ^;

־

40888-2 benzyl or R_lo Is R_lo' and R_lo' is alkyl having from 1 to 20 carbon atoms or an aromatic group having from 6 to 10 carbon atoms and when n is 2, R^q is -CH2CH2־S-CH2CH2־ or R^q is R^q and

R_lo is an alkylene group having 1 to 18 carbon atoms or is a phenylene group. However, if R_lo is R_lo&lt; or R_1Q the number of. carbon atoms of alkyl groups designated by R! is limited to 5 to 12,

A further preferred sub-group of compounds of formula I are those having the formula:

<img file="IL40888A_D0013.tif" />

<img file="IL40888A_D0014.tif" />

lb and their salts, wherein n is 1 or 2 and

R! .is an alkyl residue having from 1 to 12 carbon atoms, a benzyl or allyl residue, and when n is 1, R^ is a monovalent residue and is an aliphatic residue having from 1 to 20 carbon atoms, an alicyclic residue having from 5 to 12 carbon atoms or an aromatic residue having from 6 to 12, or when n is 2, R^ is a divalent residue and is an alkylene residue having up to 20 carbon atoms, an alicyclic residue having 5 to 15 carbon atoms or an aromatic residue having

־ 16 40888/3 from 6 to 15 carbon atoms.

Preferably is an alkyl residue having from 1 to 12 carbon atoms or an allyl residue and R^^ is an alkyl residue having from 1 to 8 carbon atoms, a cyclohexyl residue, an aryl residue having from 6 to 10 carbon atoms or a hexamethylene, toluylene or diphenylmethane-4,4¹-diyl residue.

The compounds of formula I may be prepared by methods known ffom other classes of compounds. For instance in

2,2,6,6-tetramethyl-4-hydroxypiperidine the hydrogen atom ¹at the nitrogen may be substituted by the residue R^ by known processes of alkylation, hydroxyalkylation or cyanoalkylation. The obtained N-substituted piperidinols may be transferred to the end products by etherification, esterification, or by reaction with isocyanates in a second reaction step.

Alternatively, 2,2,6,6-tetramethyl-4-hydroxypiperidine may first be substituted at the hydroxyl group and afterwards at the nitrogen atom. A number of different preparation methods are described in more detail in the following Examples.

The compounds of formula I have been found to impart to polyolefines an exceptionally high degree of stability towards deterioration normally induced by the effects of ultra-violet radiation or exposure to heat. Moreover, this improved stability is achieved without affecting

40888-2 the colour properties of the treated polyolefine. The stabiJisers of the invention provide effective light and/or heat stabilisation, especially for low- and high-density polyethylene and polypropylene and polystyrene as well as polymers of butene-1, pentene-1, 3-methyl-butene-l, hexene-1, 4-methylp.entene-l, 4-methylhexene-l and 4,4-dimethyl-pentene-l, and also co- and ter-polymers of olefines, particularly of ethylene or propylene. . '

Other organic materials susceptible to degrad/ation by the effects of light and the properties of which are improved by the incorporation therein of a compound of formula I include natural and synthetic ,polymeric materials, for . instance natural and synthetic rubbers, the latter including, for example, homo-, co- and ter-polymers of acrylonitrile, butadiene and styrene.

' Specific synthetic polymers include polyvinyl chloride, polyvinylidene‘chloride and vinyl chloride co-polymers, polyvinyl.acetate as well as condensation polymers derived from ether, ester (derived from carboxylic sulphonic or carbonic acids), amide or urethane groupings. These polymers can, for instance, form the basis of surface coating

<td colspan="4"> media such as paints and lacquers having an oil or resin,</td>

<td> for instance an alkyd or</td><td colspan="3"> polyamide resin base. , ‘ ־ 18 -</td>

<td> ׳ . . 1 י '¹Ά'^, &lt; •</td><td></td><td> :^; ΙΑ' .Ί</td><td> f</td>

<td> .י.. A ׳ . '1 it ' ,- ; ,״ || ׳ ... :' . ' ׳-. :A A . . ' | י . f . ' ' . 1. . 1:</td><td> ׳׳, ׳ Ai׳ p ׳־.j. </td><td> ־'׳!A ׳ .. ί ׳ aAaa :.*; '/;/ ' י 1׳ ύ: [I י ? ׳ ׳: .׳ £ : . AA י.״ &amp; ! V-1V“¹'. Iי. .'.־ : ?A,i!1' .: φ י</td><td> • ;</td>

<td> י</td><td></td><td> • iji.</td><td></td>

--««-*־«^*«־־*»1,15 ־'.׳«.*י«.««

4.0888-2

The amount of the compound of formula I which is incorporated into the organic material in order to achieve maximal protection against degradation by light varies according to the properties of the organic material

I. ' ' treated and according to the severity of the light radiation and to the length of exposure. However, for most purposes it is sufficient to use an amount of the compound of formula I . within the range of from 0.01% to 5/» by weight, more preferably within the range of from 0.1/־ to 27» by weight based on the weight of untreated organic material.

The compounds may be incorporated into the polymeric material by any of the known techniques for compounding additives with a polymer. For example,, the compound and the. polymer may be compounded in an internal mixer. Alternatively, the compound may be added as a solution or slurry in a suitable solvent or dispersant, for instance an inert organic solvent such as methanol,, ethanol or acetone to powdered polymer and the whole mixed intimately in a mixer, and the solvent subsequently removed'. As a further alternative the compound may be added to the polymer during the preparation of the .latter,, for instance'at the latex stage of polymer production, to provide pre-stabilised polymer material.

״ 19 - .

<img file="IL40888A_D0015.tif" />

Optionally, the composition of the invention may contain one or more further additives, especially those used in polymer formulations, such as antioxidants of.the phenol or amine type, U.V. absorbers and light protectants, phosphite stabilisers, peroxide decomposers, polyamide stabilisers, basic co-stabilisers, polyvinyl chloride stabilisers, nucleation agents, plasticizers, lubricants, emulsifiers, anti-£(:atic agents, flame-protectants, pigments, carbon black, asbestos, glass fibres, kaolin and talc.

The present invention therefore includes binary, tertiary and multi-component compositions containing the stabiliser of formula I together with one or more functional additives for polymers.

In binary combinations with one or more antioxidants listed above or in.tertiary combinations with such antioxidants and U.V. absorbers listed above, the compounds of formula I provide very effective stabiliser packages in polyolefine formulations.

Some Examples will now be given. Parts and percentages are by weight unless otherwise stated.

Examples 1 to 7

A mixture of 11,86 parts of l-allyl-2,2,6,6-tetramethylpiperidin-4-01, 7,7 parts of cyclohexane carboxylic acid and 1.0 parts of tetra-n-butyl titanate in 100 parts . of xylene was heated under reflux for 60 hours. Removal of the xylene by distillation under reduced pressure gave an oily solid which was heated under reflux conditions with 0.5 pdrts of sodium carbonate and 0.5 parts of carbon in 25 parts of water for 1 hour.

Removal of the water by distillation under reduced pressure gave a black residue which was repeatedly extracted with ether. The combined ether extracts were dried and the ether removed by distillation under reduced pressure to give a yellow oil which was distilled under reduced pressure to give 5.0 parts of bis(l-allyl-2,2,6,6-tetramethyl-4-piperidinyl) cyclohexane carboxylate as a colourless oil having a boiling point of 130°C at 0.05 mm Hg and the following elemental analysis by weight:

<td></td><td> Found Required (for C^H^IM^)</td>

<td> Carbon</td><td> 74.86% 74.22%</td>

<td> Hydrogen</td><td> 10.65% 10.82%</td>

<td> Nitrogen</td><td> 4.26% 4.56%</td>

<td> Table I gives a list</td><td> of esters prepared using the proce-</td>

dure of Example 1.

־ 21

Table 1

<td rowspan="3"> Example No.</td><td rowspan="3"> . V</td><td rowspan="3"> ־״</td><td rowspan="3"> m.p, or b.p. °C nm</td><td rowspan="3"> Molecular Formula</td><td colspan="8"> ________________________ . . Analysis</td>

<td colspan="4"> ׳Required (&lt;l . ♦«</td><td colspan="4"> Found (/)j</td>

<td> c</td><td> H</td><td> i N/</td><td></td><td> C</td><td> H</td><td> N</td><td></td>

<td> 2</td><td> 0%</td><td> CH (CH-) CH-l- J 2 JI CH CH 2 J</td><td> 18j5־’C at 0.1 mm Hg</td><td> C.H NO 24 J9 2</td><td> 77.16</td><td> 10.52</td><td> 3-75</td><td></td><td> 77.43</td><td> 10.39</td><td> 3.54</td><td></td>

<td> 3</td><td> Ch</td><td> CH (CH I J- 3 Z16</td><td> 55-fi-C</td><td> CH NO 34 59 2</td><td> 79.47</td><td> 11.57</td><td> 2.73</td><td></td><td> 79-32</td><td> 11.59</td><td> 2.45</td><td></td>

<td> it</td><td> ΤΛγ</td><td> ch_j(c«₂)₆1</td><td> 19o°c at 0.05 nim Hg</td><td> C H NO ' 29 57 2</td><td> 77.10</td><td> 12.72</td><td> J.10</td><td></td><td> 77.20</td><td> 13.02</td><td> 3.08</td><td></td>

<td> 5</td><td> T2'11־</td><td> 0</td><td> 56°c</td><td> C _ftH NO Cl 28 46 2</td><td> 72.60</td><td> 9.9Ο</td><td> 3.02</td><td> ־01 7:66</td><td> 71.98</td><td> 10.19</td><td> J.01</td><td> Cl־ 7.35</td>

<td> 6</td><td> ף</td><td> 0 II CH ־CH-C- 2</td><td> 65°C at 0Λ mm Hg</td><td> C H NO 13 23 2</td><td> 69.29</td><td> 10.29</td><td> 6.22.</td><td></td><td> 69.64</td><td> 10.30</td><td> 6.15</td><td></td>

<td> 1</td><td>^c״</td><td> Η H SI r^H A / ^K . ^H Z\ CO- ’ Η H</td><td> 180°C at 0,5 mm Hg</td><td> C H NO 17 JI 2</td><td> 72.77</td><td> 11.10</td><td> &gt;1.98</td><td></td><td> 72.84</td><td> 11,04</td><td> 4.77</td><td></td>

co

נס

2־40888

Example 8 .

A solution of 17.10 parts of 1,2,2,6,6-pentamethylpiperidin-4-01 in 50 parts of dry benzene was stirred at 15 - 20°C whilst adding 5.0 parts of acryloyl chloride dropwise over 15 minutes. The mixture was stirred for a further 12 hours at room temperature after which the 1,2,2,6,6-pentamethylpiperidin-4-01 hydrochloride formed during the reaction was filtered off. The benzene was removed by distillation under reduced pressure to give a yellow oil, which was distilled under reduced pressure to give Ws(l,2,2,6,6-pentamethyl-4-piperidinyl)acrylate as a colourless oil having a boiling point of 218-20*0 at 0.4 m o . Hg and the following elemental analysis by weight:

<td></td><td> Found</td><td> Required (for</td>

<td> Carbon</td><td> 69.8% .</td><td> 69.4% /7</td>

<td> Hydrogen</td><td> 10.0%</td><td> 10,2%</td>

<td> Nitrogen</td><td> ... 6.1%</td><td> 6.2% ...</td>

Example 9

In analogous manner (l,2,2,6,6-pentamethyl-4-piperidinyl) 4-hydroxy-3,5-di-tert-butylbenzoate was prepared from 17.10 parts of pentamethylpiperidinol and 13,5 parts of 4-hydroxy-3,5-di-tert.butyl-benzoyl chloride.

40888-2

<td colspan="3"> The ester melts at 142°C and showed the following ana-</td>

<td> lytical data:,</td><td> Found</td><td> Calculated (for θ25^Η41^Νθ3^</td>

<td> Carbon</td><td> ״74.87</td><td> 74.4%</td>

<td> Hydrogen</td><td> 10.0%</td><td> 10.2%</td>

<td> Nitrogen</td><td> 3.4%</td><td> 3.5%.</td>

Example 10

A mixture of 17.10 parts of 1,2,2,6,6-pentamethylpiperidin-4-01, 14.60 parts of methyl-/3-(3,5-di-t-butyl4-hydroxyphenyl)propionate and 1.0 part of lithium amide was heated together to 130°C. Water pump vacuum was then applied to the reaction mixture whilst maintaining the temperature at 125-135°C for 3 hours.

The temperature of the reaction mixture was then raised to 160°C and high vacuum (0.5-1 mm Hg) was applied for 1 hour. The reaction mixture was cooled, dissolved in chloroform and filtered. Removal of the chloroform by distillation under reduced pressure gave a brown oil which, when triturated with ether, gave a white solid which was collected by filtration, washed well with ether, and dried to give 16.0 parts of l,2,2,6,6-pentamethylpiperidinyl-4-3-(3^l,5' di-t-butyl-4'-hydroxyphenyl)propionate as its bicarbonate . salt having a melting point of 210°-ll°C and the following

י. . ן Ί ל

I . . j-i

¹ י. . :

. elemental analysis by weight:

<td></td><td> Found</td><td> Required (for ^28^Η47^Νθ6^</td>

<td> ] Carbon</td><td> . ־68.907</td><td> ,. ־68.107</td>

<td> ׳ Hydrogen.</td><td> . ־9.567</td><td> ־9.607</td>

<td> ί . . . 1 Nitrogen</td><td> ־2.917</td><td> ־2.847</td>

Example 10a .

15.0 parts of the product from Example 10 were dissolved in water and neutralised with sodium hydroxide, solution. The aqueous solution was extracted with ether, the combined ether extracts were dried over anhydrous magnesium sulphate. The ether was removed by distillation under reduced pressure to give a white solid which was recrystallised from ethanol . .to give 9.30 parts of l,2,2,6,6-pentamethylpiperidinyl-4-0(3',5'־di-t-butyl-4'-hydroxyphenyl)propionate having a melting point of 124°-5?C and the following elemental analysis by weight:.

<td> •</td><td colspan="4"> Carbon _z Hydrogen Nitrogen</td><td> Found ־75.007 10.50 3.50</td><td> Calculated ־75.307 10.20 .3.30</td><td> (for C₂₇^H₄₅B°₃). </td>

<td> .</td><td></td><td></td><td></td><td></td><td> -&gt;t- .</td><td></td><td> , . </td>

<td> t</td><td> - [’ l. A</td><td> Ε !</td><td> . ׳</td><td> ז , .</td><td> ' AA</td><td></td><td> • f.':,. ־. .l. ii.¹ 1.1 ׳ י ;{'״־</td>

<td></td><td> ! .f.</td><td> ׳1 ' ־ ’W! ί</td><td></td><td></td><td> ft . my;, . '׳,־‘!A</td><td></td><td> ׳ 7; ΐή;Γ-^:.,׳ ;</td>

<td></td><td> A A,.</td><td></td><td> A'.»!</td><td> &lt; ί</td><td>^,'A f ' </td><td> w .׳. ׳</td><td> .« fer v.יי׳ ״</td>

<td></td><td> J ' _י , j </td><td> )י!' '&lt;׳׳.« ׳ . ׳ ׳? tf’A ׳ ft ί i ; ¾1 1</td><td></td><td> __</td><td> ־,;H i? ,. ¹; : ו :־)׳ _t׳ י. י</td><td> ׳</td><td> ft׳.' ' ’ A A A 1:' . ' ׳ S:if ' . '.ί »..A׳ ii7. : ׳ ,.:1 . ' ί ( 'λיי : י .?’*'׳</td>

⁴i L. b U U י ־

Examples 11 to 24

A mixture of 16.4 parts of 1,2,2,6,6-pentamethylpiperidin-4-01, 6.27 parts of methyl isocyanate and 0.5 parts of 1,4-diazabicyclo [2,2,2] octane was refluxed in. 150 parts of dry benzene for 24 hours. Removal of the benzene solvent by distillation under reduced pressure yielded an oily solid which was poured on to 200 parts of water and allowed to stand for 24 hours. The solid formed was collected by filtration, dried and crystallised from n-hexane to give 14.2 parts of 4-methylcarbamoyloxy-

1,2,2,6,6-pentamethylpiperidine having a melting point of 96-7°C and the following elemental analysis by weight:

Table 2 gives a list of carbamates prepared . using the procedure of Example 11.

<td></td><td> Found</td><td> Required</td><td> (for 52^24^2!׳θ2^</td>

<td> Carbon</td><td> 63.28%</td><td> 63.12%</td><td></td>

<td> Hydrogen</td><td> 10.70%</td><td> 10.59%</td><td></td>

<td> Nitrogen</td><td> ' 12.09%</td><td> 12.27%</td><td></td>

<img file="IL40888A_D0016.tif" />

<img file="IL40888A_D0017.tif" />

Table 2

N &lt; I

I

<td rowspan="3"> Ex- '־י ample</td><td rowspan="3"> ־׳ R 1</td><td rowspan="3"> R 2.</td><td rowspan="3"> m.p, or, b.p. °C mm</td><td rowspan="3"> Molecular Formula</td><td colspan="6"> Analysis___________________ ׳</td>

<td colspan="3"> Rpnuirpd (il</td><td colspan="3"> ________Found (#1__________________</td>

<td> C</td><td> H</td><td> /«</td><td> C</td><td> H</td><td> N.</td>

<td> 12</td><td> CH 3׳</td><td>_י t CH (CH ) NHC3 25</td><td> 6j°C</td><td> C Η N 0 1? )4 2 2</td><td> 68.41</td><td> 11.48</td><td> 9.39</td><td> 68.17</td><td> 11.J2</td><td> 9.16</td>

<td> 13</td><td> CH' 3</td><td> CH (CH ), J- 5 2 17</td><td> 56-7’C</td><td> C HJO 29 5θ 2 2</td><td> 74.62</td><td> 12.52</td><td> 6.00</td><td> 79.58</td><td> 12.34</td><td> 5.96 '</td>

<td> 14</td><td> ף</td><td> CH =CH‘CH Nh!- 2 2</td><td> 62’C</td><td> C ,H J 0 14 26 2 2</td><td> 66.11</td><td> 10.50</td><td> 11.01</td><td> 66.40</td><td> 10.27</td><td> 10.92</td>

<td> 15</td><td> CH 3</td><td> HH H M</td><td> 184-6 °C 2 mm Hg</td><td> C H NO 17 J2 2 2</td><td> 68.88</td><td> 10.88</td><td> 9.»5</td><td> 68.98</td><td> 10.84</td><td> 9.15</td>

<td> 16</td><td></td><td> 0-J</td><td> 109-10’C</td><td> C Η J 0_A17 26 2 2</td><td> 70-31</td><td> 9.02</td><td> 9.85</td><td> 70.61</td><td> 8.80</td><td> 9-53</td>

<td> 17</td><td>^C”5</td><td></td><td> 106-7’c</td><td> C _ftH _ftN 0 18 28 2 2</td><td> 71.02</td><td> '9-27</td><td> 9.20</td><td> ' 71.42</td><td> 9.41</td><td> 9.02</td>

<td> 18</td><td> CH 3</td><td> C1-Q-J-</td><td> 121°C</td><td> 'AW¹</td><td> 62.86</td><td> 7-70</td><td> 8.68</td><td> 62.92</td><td> 7-75</td><td> 8.87</td>

<td> 1?</td><td> c״</td><td> NH-CO05</td><td> 129°C</td><td></td><td> 74.08</td><td> 8.29</td><td> 8.2J</td><td> 7».J7</td><td> 8.0?</td><td> 8.41</td>

We 2 (cont)

<td colspan="11"></td>

<td rowspan="3"> Example</td><td rowspan="3"></td><td rowspan="3"> V .</td><td rowspan="3"> M. or b.p. ’C nm</td><td rowspan="3"> Molecular Formula</td><td colspan="6"> ________________Analysis .</td>

<td colspan="3"> Required ({&amp;)</td><td colspan="3"> Found ()5)</td>

<td> c </td><td> H</td><td> N</td><td> c</td><td> H</td><td> N</td>

<td> 20</td><td> CH 3</td><td> 0 ⁰ -m(ch1.nhI 26</td><td> 101-4״C r</td><td> WA</td><td> 65.84</td><td> 10.66</td><td> 10.97</td><td> 65.86</td><td> 10.40</td><td> 10.64</td>

<td> 21</td><td> CH 3</td><td> ן 0 H C 3</td><td> 163-5’C ׳</td><td> WA</td><td> 67.41</td><td> 9.36</td><td> 10.81!</td><td> 67.21</td><td> 9.52</td><td> 10.83</td>

<td> 22 1</td><td> “3</td><td> -OCHN-^H^NHCO</td><td> . 18rc</td><td> C H 1,0 י ‘ 52 35</td><td> 70.91</td><td> 8.84</td><td> 9.15</td><td> 70.64</td><td> 8.79</td><td> 9.24</td>

<td> 23</td><td> CH . 3</td><td> NH-CO0 .OCNH</td><td> 165’C at. 0.05 B Kg</td><td> WA</td><td> ws</td><td> 10.6)</td><td> 8.69</td><td> 70.64</td><td> 10.80</td><td> 9.04</td>

<td> 2Ί</td><td> CH ־CH. CH - 2 2</td><td> H ״ Δ_Ζη xV^H! h׳VA nhc-</td><td> 165’c at ' 0.05 B Hg '</td><td> WA</td><td> ?o.?6</td><td> 10.63</td><td> 8.69</td><td> 70.64</td><td> 10.80</td><td rowspan="2"> 9.04</td>

<td colspan="5"></td><td colspan="3"></td><td colspan="2"> _____1—-</td>

40888-2

Examples 25 to 31

A mixture of 28.3 parts of 2,2,6,6-tetramethyl-4piperidinyl-n-octanoate and 8.55 parts of benzyl bromide was stirred and heated at 105°C for 72 hours. Ether was added to the cooled reaction mixture and the 2,2,6,6-tetramethyl-4-piperidinyl־n-octanoate hydrobromide formed during the reaction was filtered off. The ether solvent was removed by distillation under reduced pressure and the (L residue distilled under rediced pressure to give 16.40 parts of l-benzyl-2,2,6,6-tetramethyl-4-piperidinyl-noctanoate having a boiling point of 180°C at 0,1 mm of Hg and the following elemental analysis by weight:

Found Required (for ^C24^H39^N02^ Carbon 77.46% 77.16%.

Hydrogen 10.5010.52

Nitrogen 3.863.75

Table 3 gives a list of esters prepared using the procedure of Example 25.

Table )

<td rowspan="10"> ׳ ' 1 1 1</td><td colspan="11"></td>

<td rowspan="3"> Example</td><td rowspan="3"> ’1</td><td rowspan="3"> . V</td><td rowspan="3"> m.p. or . b.p. °C mm</td><td rowspan="3"> Molecular Formula</td><td colspan="6"> •_________________Analysis</td>

<td colspan="3"> Required (¢)</td><td colspan="3"> — —— Found (¢).</td>

<td> C</td><td> H</td><td> N ,</td><td> . C</td><td> H</td><td> N</td>

<td> 26</td><td> (H</td><td></td><td> 98-9’C</td><td> C. H.,N 0. 42 6U 2 4</td><td> 76.32</td><td> 9.?6</td><td> .4.24</td><td> 76.04</td><td> 9.49</td><td> 4.04</td>

<td> 27</td><td> 0 Ο-L - 25 2</td><td> 0 CH 0 ׳ 3</td><td> 1912־^CC at 0.1 nun Hg</td><td> C H NO 2131 5</td><td> 66.82</td><td> 8.28</td><td> 3.71</td><td> 66.81</td><td> 8.52</td><td> 3.84 .</td>

<td> 28</td><td> CH =CH CH - 2 2</td><td> 0 TA⁸־</td><td> 142-4⁰¢ at 0.2 ran Hg</td><td> C H NO 20 J? 2</td><td> 74.25</td><td> 11.53</td><td> Ί.33</td><td> 74.06</td><td> 11.)6</td><td> 4.)2</td>

<td> 29</td><td> CH =CHCH - 2 2</td><td> a¹</td><td> !50’C at 0.05 DIB Hg</td><td> C H NO 19 27 2</td><td> 75-71</td><td> 9.03</td><td> 4.65</td><td> 75.58</td><td> 9.25</td><td> 4.45</td>

<td> 30</td><td> CH =CHCH - 2 2</td><td> L.J co</td><td> 25O°C at 05״ mm Hg</td><td> WA</td><td> 72.81</td><td> ,10.78</td><td> ».99</td><td> 73.07</td><td> 10.60</td><td> »77</td>

<td> 31</td><td> Λ cyarcH-</td><td> Η HH H η Η H</td><td> 139-42⁰¢ at 0.2 ran Hg</td><td>^C19^H33^NO3</td><td> 70.55</td><td> 10.28</td><td></td><td> 70.37</td><td> 10.)8</td><td> 4.39</td>

to

U Ο ύ u

Example 32

a. A mixture of 2.83 parts of 2,2,6,6-pentamethyl-4piperidinyl-n-octanoate and 1.50 parts by volume of. liquid ethylene oxide was charged into a 50 ml autoclave previously cooled to -50°C. A pressure of 100 atmospheres of nitrogen was applied and the autoclave heated at 200°C, with stirring, for three hours. Fractional distillation of the cooled reaction mixture yielded 2.30 parts of 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinyl-n-octanoate having a.boiling point of 186-7°C at 0.25 mm of Hg and the following elemental analysis by weight:

<td></td><td> Found</td><td> Required (for C_1QH0^״_Q)</td>

<td> Carbon</td><td> . 69.93%</td><td> 69.68%</td>

<td> Hydrogen</td><td> 11.09</td><td> • 11.39</td>

<td> Nitrogen</td><td> 4.37</td><td> 4.28 .</td>

b, A mixture of 11.32 parts of 2,2,6,6-tetramethyl-4piperidinyl-n-octanoate and 2.50 parts of 2-bromoethanol was stirred at 100°C for 65 hours. Petroleum ether (bp 40-60°C) was added to the colled reaction mixture and the 2,2,6,6-tetramethyl-piperidinyl-4-noctanoate hydrobromide formed during the reaction was filtered off. The petroleum ether solvent,was removed by distillation under reduced pressure and the residue,

- AT׳־40888-2 distilled to yield 1-(2'-hydroxyethyl)-2,2,6,6-tetra. methyl-4-piperidinyl-n-octanoate having a boiling point of 176°C at 0.2 mm of Hg. This sample was identical to that prepared under Example 32. ί

Example 33

A mixture of 3.27 parts of the product from Example 32a, 0.60 parts of acetic acid and 0.1 parts of tetra-n-butyl titanate in 40 parts of xylene was heated under reflux conditions for 24 hours. The xylene solvent was removed by distillation under reduced pressure and the residue fractionally distilled to give 1-(2¹-acetoxyethyl)-2,2,6,6tetramethyl-4-piperidinyl-n-octanoate having a boiling point of 190-2°C at 1 1m Hg and the following elemental analysis by weight:

Found Required (for ^c₂₁H3₉N°₄) Carbon 68.17% 68.25%

Hydrogen 10.65 10.64

Nitrogen 3.36 3.79

Example 34

A mixture of 3.27 parts of the product from Example 32a, 0.63 parts of methyl isocyanate and 0.1 parts of 1,4-diazabicyclo 2,2,2 octane in 30 parts of dry benzene was heated

40888-2 j ijr ' 1“ under reflux conditions for 24 hours. The benzene solvent was removed by distillation under reduced pressure and the{ residue crystallised from aqueous ethyl alcohol to give'ן

1~(2 -methylcarbamoyloxyethyl)-2,2,6,6-tetramethyl-4piperidinyl-n-octanoate having a melting point of 61-3°C .:

and the following elemental analysis by weight:i

<td></td><td> Found</td><td> Re£uired (for</td>

<td> Carbon</td><td> 65.72%</td><td> 65.59%</td>

<td> Hydrogen</td><td> 10.37</td><td> 10.48 '</td>

<td> Nitrogen</td><td> 7.11</td><td> 7.28</td>

Example 35

A mixture of 15.70 parts of 2,2,6,6-tetramethylpiperidin-4-01, 22.80 parts of methyl isocyanate and 0.5 parts of

1,4-diazabicyclo[2,2,2]octane in 100 parts of dry benzene was heated-under reflux conditions for 24 hours. The benzene solvent was removed by distillation under reduced pressure and 150 parts of water added to the residue which was stood overnight at room temperature. The solid.formed was collected by filtration and dried to yield 19.60 parts of a white crystalline solid having a melting point of

167-8°C. This solid was shown to contain 80% of 4-methyl- . carbamoy^L-methylcarbamoyl-2,2,6,6-tetramethy!piperidine from microanalysis and nuclear magnetic resonance spectra.

<img file="IL40888A_D0018.tif" />

.J־40888 '

Example 36 j ^: .... . ׳,״............1 .

2,65 ־*. parts ,of acrylonitrile was added dropwise with ^{: ;}׳ stirring to a solution of 8.55 parts of 1,2,2,6,6-penta- ׳ j . methylpiperidin-4-01 and 0.30 parts of 40 7־ potassium . hydroxide solution in 80 parts, of benzene. Stirring wasί continued at room temperature for 16 hours after which timeί the solution was. washed with water, dried and the benzene ^! , solvent removed by distillation under. reduced pressure. '‘

Fractional distillation of the residue, under reduced pressure gave 1.70 parts of 4-(2׳-_Cyanoethoxy)-1,2,2,6,6-penta- ן methylpiperidine having a boiling point of 105-6°C at 0.1 mm of Hg and the following elemental analysis by weight: י

<td></td><td> Found</td><td> Required (for C.-H״,N0״)</td>

<td> Carbon</td><td> ־7 69.27</td><td> 69.60 7,</td>

<td> Hydrogen</td><td> . ' 10.69 70</td><td> ־7 10.78</td>

<td> Nitrogen _z .</td><td> ־7 12.40.</td><td> 12;49 %. ^r. ^,; . '</td>

. . .ו ' ' . ¹ ן י'.^,..' ' ’ ׳ ־' . ’ . I

b. To 51 parts of 1,2,2,6,6-pent&lt;methylptp_eridin-4-01 a solution of metallic sodium in two parts of tert.butanol was added. 52.5 parts of acrylonitrile was dropped in with rapid ־' '! stirring. After standing for two days at room temperature I the mixture was heated to 80“C for two hours and distilled | under reduced pressure yielding 4-(2'-cyano־thoxy) 1,2,2,6,6- י ,... .׳...ו . ..

<img file="IL40888A_D0019.tif" />

- je- -

<img file="IL40888A_D0020.tif" />

40888-2 pentamethylpiperidine with a boiling point of 172-4°C at 17 mm Hg. This sample was identical to that prepared under Example 36a.

Example 37

...A mixture of 4-benzyloxy-2,2,6,6-tetramethy!piperidine and 1.67 parts of ethyl a-bromoacetate in 30 parts of ethyl alcohol was heated under reflux conditions for 115 hours.

The ethyl alcohol solvent was removed by distillation under reduced pressure and the residue fractionally distilled to give 4-benzyloxy-l-ethoxy-carbonylmethyl-2,2,6,6-tetramethylpiperidine having a boiling point of 145-6°C at 0.2 mm of Hg and the following elemental analysis by weight:

Found Required (for ^C2O^H31^NO3> Carbon 71.62% 72.04%

Hydrogen 8,909.37

1.

Nitrogen 3.944,20

Example 38

101 parts of l-n-hexyl-2,2,6,6-tetramethylpiperidin-4-01 and

8.7 parts of boric acid were added to 500 parts of dry toluene and the solution stirred and heated at reflux with water separation using a Dean and Stark apparatus for 72 hours.

The solution was then filtered and the solvent removed by

40888-2 evaporation in vacuo to yield an amber liquid. Unreacted alcohol was removed by distillation under reduced pressure loeaving 83.1 parts of tris(l-n-hexyl-2,2,6,6-tetramethylpiperidinyl-4)borate as a pale yellow gum of boiling point 230°C/0.2 mm. This material gave the following elemental, analysis by weight:

<td> ׳־</td><td> Required (for θ3θ^60^3θ3^^</td><td> Found</td>

<td> Carbon</td><td> 73.837»</td><td> 73.567»</td>

<td> Hydrogen</td><td> 12.397»</td><td> 12.077»</td>

<td> Nitrogen</td><td> 5.74%</td><td> 5.46%</td>

Example 39

A mixture of 9.87 parts of 4-allyloxy-2,2,6,6-tetramethylpiperidine and 3.03 parts of allyl bromide was heated at 90°C for 96 hours. Ether was added to the cooled reaction mixture and the 4-allyloxy-2,2,6,6tetramethylpiperidine hydrobromide formed during the reaction was filtered off. The ether solvent was removed by distillation under reduced pressure and the residue purified by chromatography to give 4-allyloxy-lallyl-2,2,6,6-tetramethylpiperidine.

Examples 40 52 ־

Testing in polypropylene film parts of polypropylene yere hpmpgepised with

- -52 -

<img file="IL40888A_D0021.tif" />

י 40888-2

0.076 parts of n-octadecyl-0(4'-hydroxy-3',5'-t-butylphenyl) propionate in a kneading machine over a period of 3 minutes

- at 200°C. 0.19 parts of the additives listed in Table 4 was then added and homogenisation continued for another 7 minutes.

....This composition was compression moulded into films of 0.1 mm thickness at 260°C for 6 minutes and the films so obtained were then quenched in cold water.

Λ section measuring 44 x 100 mm was separated from the 0.1 mm annealed polypropylene foil and exposed to light irradiation in a fademeter device consisting of a circular bank of 28 alternate sunlight and blacklight lamps. The sunlight lamps were 2 feet long, 20-watt fluorescent lamps characterised by a peak emission of 3,100 Angstrom units; the blacklight lamps were 2 feet long, 20-watt ultraviolet lamps characterised by a peak emission of 3,500 Angstrom units. The sample was rotated f' ' . .

concentrically about the bank of lamps so that the radiaί ׳ tion therefrom was uniformly distributed over the section '׳under test.

׳ , ; The exposed sample was examined periodically and portions of it tested for the percent/elongation at break, u.

¹ the time at which the sample reached 50 % of the initial r. * ׳ ^J ,,. . '.

. ? elongation at break was noted.

. . * 1 . . . . . ' . .y j . . ’ * .,’.. » , ., .

- .sr-

2־40888

Similar tests were carried out on polypropylene samples containing, respectively, no stabiliser and known, stabilisers, and also stabilisers falling within the scope of German Patent SpecificationNa. 1.929,928. The results obtained are set out in the following table:

<img file="IL40888A_D0022.tif" />

<img file="IL40888A_D0023.tif" />

<img file="IL40888A_D0024.tif" />

Table 4

<td rowspan="2"> Example</td><td rowspan="2"> Light Stabiliser</td><td> Factor Time to 5070 of initial elongation at break (additive)</td>

<td> Time to 5070 of initial elongation at break (control)</td>

<td> .i</td><td> none</td><td> 1.0</td>

<td></td><td> 2-(2¹-hydroxy-3', 5 ’-di-t-butylphenyl) -5chlorobenzotriazole</td><td> 3.2</td>

<td></td><td> 4-phenylcarbamoyloxy-2,2,6,6-tetramethyl piperidine</td><td> 1.8</td>

<td> M</td><td> 1,6-bis E4’-carbamoyloxy-2¹,2¹,6¹,6¹-tetramethylpiperidine] hexane</td><td> . 2.4</td>

<td></td><td> 2,2,6,6-tetramethylpiperidinyl-4-benzoate</td><td> 2.6 .</td>

<td> *</td><td> bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate</td><td> 4.7</td>

<td> 40</td><td> 1,2,2,6,6-pentaethylpiper idinyl-4phenylacetate</td><td>²״5 . ,</td>

<td> 41</td><td> bis(l-benzyl-2,2,6,6-tetramethyl-4piperidinyl)sebacate</td><td> 5.0</td>

<td> 42</td><td> l-ethoxycarbonylmethyl-2,2,6,6-tetra- methylpiperidinyl-4-(p-methoxy-benzoate)</td><td> 5.1</td>

<td> 43</td><td> l-benzyl-2,2,6,6-tetramethylpiperdinyl-4(2¹ethylhexanoate)</td><td> . 5.2</td>

<td> 44</td><td> 1-(n-dodecyl)-2,2,6,6-tetramethyIpiperidinyl. 4-octanoate</td><td> 5.2</td>

<td> 45</td><td> 1(2¹-hydroxyethyl)-2,2,6,6-tetramethylpiperi dinyl-4-octanoate</td><td> 5.8</td>

Table 4 (cont.)

<td rowspan="2"> Example</td><td rowspan="2"> Light Stabiliser</td><td> : Factor Time to 50% of initial elongation at break (additive)</td>

<td> Time to 50% of initial elongation at break (control)</td>

<td> 46 47 . 48 49 50</td><td> 4-(2'-cyanoethoxy)-1,2,2,6,6-pentamethylpiperidine Tris(l־n-hexyl-2,2,6,6-tetramethyl-4-piperidinyl)־ borate 2,4-bis(4’-carbamoyloxy-1¹,2', 2', 6', 6¹ - ': pentamethylpiperidine)toluene ׳ 4-p-tolylcarbamoyloxy-l,2,2,6,6-pentamethylpiperidine 4-allylcarbamoyloxy-l,2,2,6,6-pentamethylpiperidine .</td><td> 6.0 5.2 5.2 5.2 5.5 '</td>

<td> 51 </td><td> 4-phenylcarbamoyloxy-l,2,2,6,6-pentamethylpiperidine</td><td>⁵¹⁶</td>

<td> 52</td><td> 4-methylcarbamoyloxy-l,2,2,6,6-pentamethylpiperidine</td><td> 5.8</td>

40888-2

Examples 53 to 55

The procedure described in Examples 40-52 was repeated except that 0.25% by weight of the light stabiliser under test was used, and, instead of polyporpylene, a lowdensity polyethylene was employed as substrate.

The pressing was conducted at 180°C and the pressings were compression-moulded into 1 mm thick plaques at 150’C.

The plaques were stored at 20°C and were periodically examined visually for the first sign of exudation.

The results obtained are summarised in the following Table which also includes data relating to comparative experiments (known light stabilisers added).

Table 5

<td> Example</td><td> Light stabiliser added</td><td> Dime to exudation (days)</td>

<td> -</td><td> 2,2,6,6-tetramethylpiperidinyl-4-stearate bis(2,2,6,6-tetramethyl-4piperidinyl)sebacate 4-stearylcarbamoyloxy-2,2,6,6 tetramethylpiperidine</td><td> 15 . 20 ¹³</td>

<td> 53 54 55</td><td> l-benzyl-2,2,6,6-tetramethylpiperidinyl-4-stearate bis(l-benzyl-2,2,6,6-tetramethyl-4-piperidinyl)sebacate 4-stearylcarbamoyloxy1,2,2,6,6-pentamethylpiperidine</td><td> 50 50 . 50־</td>

<td colspan="3"> • ^: ? ' - . ' - 57 - -hi- .</td>

<td> ׳ 7</td><td> •. . . . χχ . \ יי׳ י</td><td> X7 ' י</td>

<td></td><td> .'&gt;! ' ¾ .¹,] .י ; ־, .י .י</td><td> י ק; י י?</td>

<td></td><td> / ׳ , . ׳</td><td> ׳; .:;׳י0 ¹</td>

<td></td><td> ־ .׳ . * . , . 7:.!; i י י : ί j .</td><td> Μ '׳. ז.^,^,!‘. » . ¹ .־'' ΐτ '! j</td>

2־40888 r

ין . .

' . י >

Examples 56 - 58

The procedure described in Examples 53 - 55 was repeated except that the compression moulding was carried out at 200°C and the substrate used was high-density polyethylene.

.....The results obtained are set out in the following Table, which also contains data relating to comparative experiments (using a known light stabiliser).

Table 6

<td> Example</td><td> Light Stabiliser j</td><td> Time to exudation (days)</td>

<td> -</td><td> 2,2,6,6-tetramethylpiperidinyl4-stearate</td><td> 40</td>

<td> 56</td><td> l-benzyl-2,2,6,6-tetramethylpiperidiny1-4-stearate</td><td> &gt;75</td>

<td> 57</td><td> 4-stearylcarbamoyloxy1,2,2,6,6-tetramethylpiperidine</td><td> &gt;75</td>

<td> 58</td><td> 1-(n-dodecyl)-2,2,6,6-tetramethylpiperidinyl-4octanoate</td><td> 775</td>

-.:5a׳—42 -

2־40888

Examples 59 to 63 .

100 parts of crystal polystyrene pellets were dry blended with 0.25 parts of l-benzyl-2,2,6,6-tetramethylpiperdinyl-4-(2*-ethylhexanoate), and the dry blend was homogenised by extension. The stabilised pellets so obtained were injection moulded to form plaques 2 mm thick.

These plaques were exposed for 3000 hours in a ״Xenotest , 150 exposure unit, and any yellowing of the plaques was measured by determining the yellowness factor by means of the following equation:

yellowness factor

1^2218°^ ־). _{x 100}^r(56O) wherein the AT values represent the transmission loss of the sample at wavelengths of 420 mm and 680 mm respectively, after exposure in the Xenotest unit, and Τ^θθ^ represents the transmission value of an unexposed sample at a wavelength of 560 mm.

The results obtained, as well as the results relating to a control experiment and other compositions of this invention are recorded in the following Table.

40888-2

<td colspan="3"> Table 7</td>

<td> Example 1</td><td> Light stabiliser</td><td> yellowing factor. after 3000 hours</td>

<td> -</td><td> none</td><td> 35.0</td>

<td> 59</td><td> l-benzyl-2,2,6,6-tetramethylpiperidinyl-4-(2¹-ethylhexanoate)</td><td> 9.8</td>

<td> 60</td><td> l-dodecyl-2,2,6,6-tetramethylpiperidinyl-4-(noctanoate)</td><td> 8.5</td>

<td> 61</td><td> 4- (2'-cyanoethoxy)-1,2,2,6,6pentamethylpiperidine</td><td> 8.0</td>

<td> 62</td><td> 4-stearylcarbamoyloxy- 1,2,2,6,6-pentamethylpiperidine</td><td> 7.5</td>

<td> 63</td><td> bis-(l-benzyl-2,2,6,6-tetramethyl-4-piperidinyl)sebacate</td><td> 7.0</td>

<td> Examples &lt;</td><td colspan="2"> 1. )4 - 66</td>

parts by weight of a polyester-based film-forming polyurethane were dissolved in 75 parts by weight of a 1:1 mixture, (by volume) of dimethylformamide and acetone, and 1 7־ by weight of 4(2'-cyanoethoxy)^1,2,2,6,6-pentamethylpiperidine was added.

<td> The</td><td colspan="2"> clear and homogeneous solution was drawn out on a</td>

<td colspan="3"> glass plate to a £11™ of 400-500 p thickness, ״hlch vas then</td>

<td> '. dried as</td><td> follows:</td><td></td>

<td> . .:׳יי &lt;</td><td></td><td></td>

<td></td><td> . . - j6e -</td><td></td>

<td></td><td></td><td> י י^, ,/ 9 ' dx</td>

<td> 1.</td><td> c‘ ¹ &gt;׳׳׳ ₍.</td><td>^,. :׳w.</td>

<td> H .' ,;/:'.־ ׳; 1' ,׳ ,.,</td><td> -'M ^J J ' 'J/׳:״: ' a, PL</td><td> י יי.^,:׳ ־'׳.¹:.0 ׳ : V .</td>

<td> i ״ . Η/' 1</td><td> : . ¹ 1 .' J . ., . i .1 1 ׳! . !</td><td> X0 '., ־ 11.: ' . 'y:׳?^:</td>

2=40888 . . ־ ן

. . י י י י י . .׳׳'״׳׳׳

. י . ; י י ,¹ ] ’ at 50°C for 4 minutes .

at 140°C for 6 minutes.

. ׳ ' ; ' ' . ׳ 1 ; The final thickness of the ilm was 80. - 100^u.

. The dried film samples were removed from the glass ! . plate, mounted on white cardboard and exposed in a | Xenotest 450 exposure unit, one half.of the exposed ! . sample being covered to facilitate subsequent visual | estimation of yellowing due to exposure. The sample ί was controlled and rated visually at intervals of ΐ 100 hours.

I The data obtained are set out in the following Table which also includes data relating to a control experiment (no added light stabiliser) and to other. experiments using 1 stabilisers of this invention.

Table 8

<td> Example</td><td> Light Stabiliser</td><td> Time to onset of yellowing (hours)</td>

<td> —</td><td> none</td><td> 100</td>

<td> 64</td><td> 4- (2'-cyanoethoxy)1,2,2,6,6-pentamethylpiperidine</td><td> 200</td>

<td> 65</td><td> l-dodecyl-2,2,6,6-pentamethylpiperidinyl-4octanoate</td><td> 400</td>

<td>⁶⁶</td><td> 4-phenylcarbamoyloxy-l-npropyl-2,2,6,6-tetramethylpiperidine</td><td> 400</td>

_דΓ-

<img file="IL40888A_D0025.tif" />

Examples 67 69 י

1000 parts by weight of unstabilised polypropylene powder were thoroughly dry-blended with 1 part by weight of n־octadecyl-P־i(4'-hydroxy-3’,5’-di-t-butylphenyl) propionate and 2 parts by weight of 1,2,2,6,6-pentamethyl4-piperidinyl-(3',5^I-di-t-butyl-4'-hydroxy)benzoate. The dry-blend was extruded at cylinder temperatures of from 180° to 220°C, and the resulting strand was granulated. The stabilised formulation so obtained was melt-spun and stretched under the following conditions.

Extruder temperatures

Melt temperature at the dye

Spinning speed

Stretching Ratio

Titer of multifilament . Tensile Strength

230/265/275 C

27O°C

400 m/minute

1:5

130/137 denier g/denier.

The multifilament obtained was mounted on a sample holder of a Xenotest 150 apparatus (Quarzlampen GmbH) using white cardboard as backing. In intervals of 200 hours of exposure time, 5 fibre samples are measured for their retained tensile strength. The data obtained are plotted against exposure time and the exposure time (T) to give 50% loss of original tensile strength is derived from the graph. This value is taken as the failure time.

Table 9

<td> Example</td><td> Light Stabiliser</td><td> Time (T) to 50% retained tensile strength . /</td><td> Factor, T stabiliser T control .</td>

<td> w</td><td> none</td><td> 430 .</td><td> . 1.0 . .</td>

<td></td><td> Z-^'-hydroxy-S'jS'-di-tbutylphenyl)-5־chlorobenzotriazole</td><td> 530 '</td><td> 1.2</td>

<td> 67</td><td> l,2,2,6,6-Pentamethyl-4piperidinyl-(]^,,5¹-di־tbutyl-4¹-hydroxybenzoate)</td><td> 1400</td><td> 3.3</td>

<td> 68</td><td> l,2,2,6,6-Pentamethyl-4piperidinyl-p-O'jS'-dit-butyl-4¹-hydroxyphenyl) propionate</td><td> 1600</td><td> 3.7</td>

<td> 69</td><td> Bis(l-benzyl-2,2,6,6־penta- methyl״4־piperidinyl)sebacate</td><td> 2100</td><td> 4.9</td>

I . 40888-2 ״ j.

, . ' . ’ 7 ' י

I ' י ' י י ' ' ' ' י י ' -י ' ' i Examples 70 - 75׳ י ! ' . ..’.ί

I The procedure described in Examples 40 to 52 was repeated except that the annealed polypropylene specimens j were exposed to light irradiation in a Xenotest 450 exi posure unit rather than in the fademeter device.:

׳ י ' . ־׳״' The results obtained are summarised in the following!

. .I

I Table which also includes data relating to a control ex-ן j periment (no added light stabiliser) and a comparative'.

! *יJ

I experiment (a known light stabiliser added).!

Table 10

<td> Example</td><td> Light Stabiliser</td><td> Time to Failure (hours)</td>

<td> *</td><td> none (control)</td><td> 800</td>

<td> -</td><td> 2-(2¹-hydroxy-3',5'-di-t-butylphenyl) -5-chlorobenzotriazole</td><td> 1630</td>

<td> 70</td><td> bis(l-benzyl-2,2,6,6-pentamethyl-4piperidinyl)sebacate</td><td> 8000</td>

<td> 71 72</td><td> 1,2,2,6,6-pentamethylpiperidinyl-40-(3^5¹ -di-t-butyl-4' -hydroxyphenyl) 1,2,2,6,6-pentamethylpiperidinyl-4(3¹,5' -di-t-butyl-4¹ -hydroxy, benzoate)</td><td> 10000 &gt;8600</td>

<td> 73</td><td> 4-phenylcarbamoyloxy-l,2,2,6,6pentamethyl piperidine</td><td> &gt;7000</td>

<td> 74</td><td> 4-methylcarbamoyloxy-l,2,2,6,6pentamethylpiperidine</td><td> 6000</td>

<td> ‘ 75</td><td> 1,2,2,6,6-pentamethylpiperidinyl-. 4-cyclohexane-carboxylate</td><td> &gt;6000</td>

- ־64 . Λ8 ~

<img file="IL40888A_D0026.tif" />

40888-2 j

... - : ' /.' . i

Examples 76 to 80

100 parts by weight of polyamide-6. pellets containing

1.8 parts by weight of Ti0₂ were dry-blended with 0.5 parts of 4-benzyloxy-l,2,2,6,6-pentamethyl piperidine.

The resulting mixture was melt-spun directly into monofilaments of 20 denier.!

The monofilaments were mounted on white cardboard| without tension and were exposed to light radiation ini a Xenotest 450 exposure unit.;

After 500, 1000, 1500 and 2000 hours of exposure timeן respectively, 5 fibre samples of each formulation and time interval were tested for tensile strength. The arithmetic mean percentage values of residual tensile strength wereן plotted as a function of exposure time. The failure points - j time to 50% loss of original tensile strength - were qb-1 tained from these graphs.1

<img file="IL40888A_D0027.tif" />

Table 11

40888/3'

7~ /

<td> Example ־</td><td> Light Stabiliser</td><td> Time to 50% loss of original tensile .strength (hours)</td>

<td> -</td><td> none (control)</td><td> 475</td>

<td> . 76</td><td> 4-benzyloxy-l,2,2,6,6-pentamethylpiperidine</td><td> 1420</td>

<td> 77</td><td> bis(l-benzyl-2,2,6,6-tetramethyl-4-piperidinyl)sebacate</td><td> 1550</td>

<td> 784</td><td> 1-(2¹-acetoxyethyl)-2,2,6,6־ tetramethylpiperidinyl4־octanoate</td><td> 1300</td>

<td> 79</td><td> 4-phenylcarbamoyloxy-l,2,2,6,6pentamethylpiperidine</td><td> 1450</td>

<td> 80</td><td> 1,6-bis (4'-carbamoyloxy-1',2'2',6',6'־pentamethylpiperidine) hexane</td><td> 1500</td>

40888*4 r ί

Example 81

A mixture of ?0.1 parts of 1-(2'-hydroxyethyl)-

2,2,6,6-tetramethylpiperidine-4-01, 30 ’parts״'of methyl benzoate and 0,20 parts of lithium amide in 100 parts of xylene was heated at 1.37° for 8 hours. The methyl alcohol formed during tl/e reaction being removed by destination. The cooled reaction mixture was filtered to remove the lithium amide and the xylene solvent removed by destination under reduced pressure. The residue was recrystallised from petroleumether to give 35 parts of 1-(2¹-benzoyloxyethyl)-2,2,6,6-tetramethylpiperidinyl4-benzoate having a melting point of 92-94°C.

Example 82

Parts of 1-(2’hydroxyethyl)-2,2,6,6-tetramethyl piperfdinyl-4-octanoate were added to 1000 parts of dry benzene and a stream of dry nitrogen was passed through the solution for 30 minutes, maintaining a׳temperature of 15°C. 8.2 Parts of acryloyl chloride were added dropweise over 30 minutes with vigorous stirring and the reaction mixture allowed to stir at room temperature for 18 hours. The solvent was then evaporated in vacuo and 150 parts of ether added. The .insoluble oily material was separated and,the ether phase dried and evaporated to yield 50 parts of a colourless oil. Chromatography of this

; 4־40888 oil on an alumina column afforded 26,52 parts of l-(2'-acryloyloxyethyl)-2,2,6,6-tetramethyl piperidinyl-4-octAnoate which had a boiling point of 193°C/0^:, 3 mm. This material gave the following elemental analysis:

Required Found for C,2^39^0¢.

Carbon 69.25769.16% . ־

Hydrogen 10.30710.45% ־

Nitrogen 3.67% 3.66% .

Example 83

110.2 parts pf stearic anhydride, 36.18 parts of 1(2 *-hydroxyethyl)-2,2,6,6-tetramethyl piperidin-4-01, 2.0 parts of tetra n-butyl titanate and 250 parts of xylene were charged to a reaction vessel. The mixture was stirred and heated at reflux for 24 hours with water separation jjsing a Dean and Stark apparatus. After cooling the xylene was removed by evaporation in vacuo. The resultant light.brown solid was recrystallised twice from ethanol to yield 112 parts bf 1-(2¹stearoyloxyethyl)-2,2,6,6-tetramethyl piperidiny1-4-stearate which had a melting point of 63°, to 64°C. It gave the following elemental analysis:

- ־468 - ־2־S-

40888-4

Carbon

Hydrogen

Nitrogen

Required for ^C47^H91^N04

־76.927

־12.507

1.91%

Found

76.95%-

- ־12.367

. 1.64%

Example 84

A solution of 20.1 g 1-(2'-hydroxyethyl)-2,2,6,6tetramethyl-4-piperidine in 300 ml toluene was mixed with 42,3 g h-dodecylisocyanate and is stirred 24 hours at 95 to 100°C. Afterwards the solution was diluted with further 300 ml toluene, filtered over alumina and evaporated in vacuo to dryness. There was obtained 51.6 g.1-(2'-dodecylcarbamoyloxyethyl)-4-dodecylcarbamoyloxy-2,2,6,6-tetramethy!piperidine as amorphous resin-like solid. ־

Required׳for , Found ^C37^H73^N3°4

Carbon 71.22% 71.5%

Hydrogen 11.79% 11.67־

Nitrogen 6.737־6.57 . ’ ־ .

40888-4

Example 85

, ־ . ' ־.'־ . י

39.8 g 4-Acetoxy-2,2,6,6-tebramethylpiperidine was. mixed with 35.1 g octadecyl chloroacetate and the mixture was stirred.4־ days under nitrogen at a temperature of 90 to.lOO°C. The mixture then was diluted with 500 ml toluene and filtered from the precipitated acetoxytetramethylpiperidine hydrochlorid. The filtrate was evaporated under reduced pressure. The viscose residue represented the l-octadecyloxycarbonylmethyl-4acetoxy-2,2,6,6-tetramethylpiperidine.

<td></td><td> Calculated for</td><td> Found</td>

<td></td><td>^C31^H59^N°4 .</td><td></td>

<td> Carbon</td><td> ־73.037</td><td> ־73.027</td>

<td> Hydrogen</td><td>¹¹-⁶⁷⁷⁰</td><td> ־11.57</td>

<td> Nitrogen</td><td> ־2.757'</td><td> 2.87□</td>

Example 86 and 87

A solution of 6.4 g oxalic acid dichloride in 20 ml toluene was slowly added to l-allyl-4-hydroxy-2;2,6,6-tetramethylpiperidine dissolved in 200 ml dry toluene.at a temperature of 15 to 20°C. The reaction mixture was stirred 12 hours at room temperature. After filtration of the precipitated allyl-hydroxytetramethylpiperidine.hydrochloride the toluene was destilled off and the solid evaporation residue was recrystallised from ligroin. The obtained bis(l-allyl2,2,6,6־-tetra--70 ־

.4־40888 . . ~f methyl-4-piperidyl)oxalate melted at. 127-129°C.

. . Using in this procedure 19,7 g 4-tert.butylbenzoyl- \ chloride instead of the oxalylchloride there was obtained 1ally14־-tert.butylbenzoyloxy-2,2,6,6-tetramethylpiperidine . It can be destilled in a vacuo of 0.5 mmHg at 169-171°C.

Example 88

24,7 .g l-Benzyl-4-hydroxy-2_l2,6,6-tetramethylpiperidine, 9,7 g dimethyl isophthalate and 0,5 g lithium amide in 200 ml xylene were heated 8 hours.to 145 to 150°C.The methanol formed during the reaction is destilled off simultaneously. The reaction solution is cooled to 15°C, washed with water, dried over sodium sulfate a~nd evaporated. There were obtained 30,2 g bis (l-bcnzyl-2,2,6,6-tetrams thy1-4-piperidyl)i sophtha. . \ late.as a solid residue. After recrystallisation from ligroin the substance melted at 152-153°C. ' ....... ... ....

Examples 89-95

100 Parts of polypropylene powder (Moplen Fibre Grade, Montedison S.A.) were blended with 0.2 parts of octadecyl-/3(3,5-di-tert.butyl-4-hydroxy-phenyl)-propionate as antioxidant and 0,25 parts of a light stabilizer listed in the following table in a Brabender plastograph during 10 minutes at a tempe- ! rature of 200°C. The obtained plastic mixture is pressed to a

4־40888 sheet of 2 to 3 mm thickness. A part of this.sheet is hotpressed in a hydraulic laboratory press during 6 minutes at 260°C to a foil of 0.5 mm thickness, which is quenched in cold, water. By analogous treatment from this foil, a film of 0,1 mm thickness is prepared. Samples of a size of 60 x 44 mm are cut from the film and are exposed to irradiation in the Xenotest 150. .

The exposed samples are '׳examined periodically by measuring the extinction at 5.85 pm in a IR-spectrophotometer. The extinction at this wave-length is.caused by carbonyl groups formed by light deterioration of polypropylene which is accompanied with a decrease of the mechanical strength. When the carbonyl extintion approaches 0.30 a polypropylene film becomes _ brittle .

The following table shows the irradiation time up to this brittleness measured by determining the carbonyl extinction.

/ל

4־40888

Table

Example Light Stabiliser ‘Hours of irradiation until an extinction of 0.30 at 5.85 pm

<td> -</td><td> none .</td><td> 1050</td>

<td> 89</td><td> 4-stearoyloxy-l,2,2,6,6-penta- methylpiperidine-hydrochloride</td><td> 4550</td>

<td> 90</td><td> l-(/J-benzoyloxyethyl)-4benzoyloxy-2,2,6,6-tetramethylpiperidine .</td><td> 8270</td>

<td> 91</td><td> l-(/J-stearoyloxyethyl)-4stearoyloxy-2;2,6,6-tetramethylpiperidine</td><td> . ³¹⁷⁰</td>

<td> 92</td><td> l-allyl-4-p-tert.butyl- benzoyloxy-2,2,6,6-tetra- '׳ . methylpiperidine.</td><td> 2200</td>

<td> 93</td><td> bis-(l-benzyl-2,2,6,6tetramethylpiperidinyl-4)־ isophthalate</td><td> 2200</td>

<td> 94</td><td> bis-(l-allyl-2,2,6,6-tetratnethyl-4-piperidinyl)-oxalate</td><td> 1800</td>

<td> 95</td><td> l-(B-acryloxyet'hyl) -2,2,6,6- tetramethylpiperidinyl-4octanoate</td><td> 1800</td>

40888-4

Examples 96 and 97 . . .

According to the procedure of Example 1 there were prepared the following compounds:

Bis(1,2,2,6,6-pentamethylpiperidinyl)-β,β’-thiodipropionate, boiling at 0.4 mm Hg at 210-220°C.

Analysis

Calculated for C״,H,_oN0״,S: C 64.40% H. 9.98% N 5.78% S 6.60% zb 40 z 4

Found: C 64,26% H 9.89% N 5.51% S 6.59%

1,2,2,6;6-Pentamethylpiperidinyl-4-phenylacetate,boiling at0.2 mm Hg at 120°C. .

Calculated for C._flH₇״N0₉: C 74.70% H 9.40% N 4.84% lo z / z

Found C 74.99% H 9.70% N 4.85% .

Example 98

98.0 Parts of l-n-hexyl-2,2,6,6-tet rametliyl piper id in-4-01, 39.5 parts of dimethyl terephthalate, 3.3 parts of lithium amide and 350 parts of xylene were heated at reflux and the methanol formed separated by means of a refluxratio distillation head. After all the methanol was separated the. solution was cooled and filtered. The solvent was removed by. evaporation in vacuo .and the solid material remaining was crystallised four times from petroleum ether of boiling range 60° to. 80°C. 56.7 Parts of bis(l-n-hexyl-2,2,6,6-tetramethylpiperidinyl-4)terephthalate as a colourless solid of melting point 160.5° to 161.5°C were obtained. This material gave the following elemental analysis:

408884־_z

<td></td><td> Required ^C38^H64^N2°4</td><td> Found</td>

<td> Carbon</td><td> ־74.457</td><td> ־74.757</td>

<td> Hydrogen</td><td> ־10.507</td><td> ־10.667</td>

<td> Nitrogen</td><td> ־4.557</td><td> ־4.357</td>

Examples 99-101 . 21.3 g l-Butyl-4-hydroxy-2,2,6,6-tetramethyipiperiI dine and 12.6 g dodecamethylene-diisocyanate were dissolved in

150 ml dry toluene. After addition of 0,5 g 1,4-diazabicyclo [2.2.2]octane the solution has been stirred 48 hours at a temperature of 90 to 95°C. After dilution with 250 ml toluene, the solution was filtered over silica gel and evaporated to i -

־ '

4־40888 dryness. There were obtained 30.6 g l,12-bis(l-butyl-2,2,6,6tetramethyl-4-carbamoyloxypiperidyl)dodecane as a. ye'llow viscons resin.

<td></td><td> Calculated for . ^C4078^״N4°4</td><td> Found</td>

<td> Carbon</td><td> ־70.757</td><td> ־70.97 f</td>

<td> Hydrogen</td><td> ־11.587</td><td> ־11.47</td>

<td> Nitrogen</td><td> ־8.257</td><td> ־8.07</td>

In analogous manner there were prepared:

p,p'-Bis(l-methyl-2,2,6,6-tetramethyl-4-carbamoyloxypiperidinyl) dicyclohexylmethane (viscous resin)

Calculated for Οή.Η,,Ν,Ο,: C 69.497־ H 10.667־ N 9.267־ Jj 04 44

Found . C 69.777־ H 10.797־ N 9.057־ .

N-[3,3,5-trimethyl-5-(l',2',2',6',6’-pentamethylpiperidinyl4¹-oxycarbonylaminomethyl)-0-(1,2,2,6,6-pentamethylpiperidinyl4)-carbamate (viscous, yellowish resin)

Calculated for Cn₉H_fi״N,0,: C 68.047־ H 10.717־ N 9.927־

Found C 68.257־ H 10.827־ N 9.6,47־ .

Example 102

199.3 Parts of 2,2,6,6-tetramethylpiperidinyl-4־acetate and 124.6 parts of lauryl bromide were heated at. reflux in 1000 parts of dry dimethylformamide for 48 hours. 62.3. Parts of lauryl bromide were added and the solution was heated at.

<img file="IL40888A_D0028.tif" />

׳״ 4־40888 reflux for a further 24 hours. After cooling the reaction mixture was poured into . ice-water and extracted with diethyl ether. Evaporation in vacuo afforded a liquid which was distilled under reduced pressure to yield 49.8 parts״of-l-ndodecyl-2,2,6,6-tetramethylpiperidinyl-4-acetate of .boiling point 156° to 162°C/0.08mm. This macerial, gave the following elemental analysis:

Required Found ^C23^H45^NO3

Carbon 75.12% 75.58%

Hydrogen 12.36% 12.76%

Nitrogen 3.81% .3.83% ,.

Example 103

211.8 Parts of 2,2,6,6־tetramethylpiperidinyl-4-octanoate and

93.5 parts of lauryl bromide were heated at reflux in 1000 parts of dry dimethylfomamide for 48 hours. 46.6 Parts of lauryl bromide were added and the solution was heated at reflux for a further 24 hours. After cooling the reaction mixture

X ־ . . .

was poured into ice-water and extracted with diethyl ether. Evaporation in vacuo afforded a liquid which was distilled under reduced pressure. The fraction of boiling point 226I .

228°/0.1mm was further purified by column chromatography on alumina using toluene/pettoleum ether as eluant. 25 Parts of l-n-dodecyl-2,2,6,6-tetramethylpiperidinyl-4-octanoate were obtained which gave the following elemental analysis:

0/ $&amp;&amp;&amp;&amp;-£ .ϊ

Required Found ^C29^H57^°2

. ׳ \ .

Carbon. 77.07% 76.78%

Hydrogen 12.74% 12.85% ,.

Nitrogen 3.10% , 3.10% .

Example 104

64.1 Parts of l-benzyl-2,2,6,6-tetramethylpiperklin-4-01 were dissolved in 500 parts of dry benzene and 10.98 parts of adipoyl chloride .were added dropwise with stirring,, maintaining a temperature below 20°C. The mixture was stirred at room ternperature for 16 hours after which the solid was filtered off and the filtrate evaporated in vacuo. The residue was crystallised from ethyl acetate to give 23.1 parts of l-benzyl-2,2,6,6tetramethylpiperidinyl-4-adipate which had a melting point of 146° to 147°C. This material gave the following elemental analysis:

Required for Ε״_βΗ_ςςΝ״Ο, r- j

55 2 4 . Found .

z

Carbon 75.46% 75.23% .:

Hydrogen 9.33% 9.26%

Nitrogen 4.63% 4.38% .

Example 105

127 Parts of 2,2,6,6-tetramethylpiperidinyl-4-(4'־chlorobenzoate) and 52.5 parts of laurel bromide in 500 parts of dry dimethylformamide were heated at reflux fo'r 48 hours. 26.2 Parts

888-2 of lauryl bromide were added and the solution was heated at reflux for a further 24 hours. After cooling the reaction mixture was poured into ice-water, the precipitate was filtered off.and washed well with water. Crystallisation twice from ethanol afforded 31 parts of l-n-dodecyl-2,2,6,6-tetramethylpiperidinyl-4-(4'-chlorobenzoate) of melting point 59°-60°C.

,This material gave the following elemental analysis:

Required for ^C28^H46^C1NO2

Carbon

Hydrogen

Nitrogen

72.43%

10.00%

3.01%

Found

72.38%

9.97%

2,75%

Example 106

130.5 Parts of 2,2,6,6-tetramethylpiperidinyl-4-benzoate and

62.5 parts of lauryl bromide in 500 parts of dry dimethyl formamide were stirred at 95° for 4 hours then at 150° for a further 40 hours. After this period 31.5 parts of lauryl bromide were added and the mixture heated at reflux for 20 hours. The solution.was cooled and poured on to excess ice-water. A waxy solid was filtered and washed well with water. Crystallisation twice from ethanol afforded 45 parts of l-n-dodecyl-2,2,6,6-tetramethylpiperidinyl-4-benzoate having a melting point of 56° to 57°C. This material gave the following elemental analysis:

<img file="IL40888A_D0029.tif" />

<td></td><td></td><td></td><td> 40888-2</td>

<td></td><td> . Required for ^C28^H47^NO2</td><td> Found</td><td> . -</td>

<td> Carbon Hydrogen Nitrogen</td><td> 78.32% 10.96% 3.26%</td><td> 78.35% «11.11% 3,06%</td><td> •</td>

Example 107 l-Hexyl-2,2,6,6-tetramethylpiperidin-4-01 .(14.46 parts) was dissolved in toluene (100 parts) and phosphorus trichloride (1.37 parts) in toluene (10 parts) was added below 20°C. The mixture was stirred overnight,. filtered and evaporated to give 7.2 parts of tris(l-hexyl-2,2,6,6־tetramethylpiperidin-4-yl) .

<td> phosphite as a analysis :</td><td> colourless oil</td><td> which had the</td><td> following</td><td> elemental</td>

<td></td><td></td><td> C</td><td> H</td><td> N</td>

<td> CalculaLed for</td><td>^C45^H90^N3°3^P</td><td> 71.85%</td><td> 12,06%</td><td> 5,597«</td>

<td> Found</td><td></td><td> 7176% _</td><td> 12,06%</td><td> 5.37%.</td>

Example 108

When the method of example 107 was followed using 1,2,2,6,6pentamethylpiperidin-4-01 (68.8 parts) diethylchlorophosphite (31.3 parts) and toluene (300 parts) the product was 40׳parts of diethyl l,2,2,6₁6-pentamethylpiperidin-4-yl phosphite, a colourless liquid which had the following elemental analysis:

<td> C</td><td> H</td><td> κ ;.</td><td> P</td>

<td> Calculated for Ο-^Η^θΟ^ΝΡ 57.71%</td><td> 10.38%</td><td> 4.817J</td><td> 10.63%</td>

<td> Found 57.89%</td><td> 10.66%</td><td> 4.66%</td><td> 10.55% .</td>

<td> - wr-</td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td>

A solution of tris(l-hexyl-2,2,6,6-tetramethylpiperidi׳n-4-yl phosphite) (I part). in methylene chloride was stirred for 3 hours with an aqueous solution of potassium permanganate (0.18 parts) containing benzyl tri-n-butyl־ammonium bromide (0.05 parts). .

The organic phase was separated and filtered through a column of silicagel. Evaporation of the eluates gave 0.8 parts of tris(1-hexyl-2,2,6,5-tetramethylpiperidin-4-yl)phosphate as a colourless oil, which had the following elemental analysis:

40888-3

Example 109

<td></td><td> C</td><td> H</td><td> N</td><td> P</td>

<td> Calculated for C, _cH,.״N_o0׳,P 45 90 3 3</td><td> 70.34%</td><td> 11.34%</td><td> 5.47%</td><td> 4.03%</td>

<td> Found</td><td> 70.80%</td><td> 11.75%</td><td> .5.23%</td><td> 4.02% .</td>

Example 110

17.1 Parts of 1,2,2,6,6-pentamethylpiperidin-4-01, 6.9 parts of diethylphosphite and 100 parts of xylene were heated at reflux and the ethanol formed was removed by azeotropic distillation, via a constant reflux ratio head. The reaction was continued until the head temperature reached 136°C. Evaporation of the xylene and recrystallisation of the residue from petroleum ether gave 5.3 parts of bis(l,2,2,6,6-pentamethylpiperidin-4-yl)phosphite, mp. 52-54°C, which had the following elemental analysis: .

Calculated for C^H^N^P: C 6183% H 10.64% N 7.21% P 7.97% Found . . C 61.50% H 10.87% N 7.01% P 7.87%

- .81 40888-2

Example 111 and 112

A mixture of 3.14 g of 2,2,6,6-tetramethylpiperidinol-4 and 3.50 g acetic anhydride is heated at about 100° for one hour. After addition of 20 ml of water the mixture is heated for a further hour. The cooled mixture is. neutralized'with NaHCO^ and extracted with ether. The ethereal solution is dried over magnesium sulfate and the ether removed by distillation under reduced pressure to yield l-acetyl-2_r2,6,6-tetramethylpiperidinyl-4-acetate having a melting point of 33 to 34° and the following elemental analysis:

Required (for C₁₃H₂₃NO₃) 64.73 % C 9;54 % H 5.81 7־ N

Found

9.69 70.H

5.67 % N

In analogous manner from 2,2,6,6-tetramethyl-4-phenylcarbamoyloxypiperidine and acetic anhydride there was obtained 1-acetyl2,2,6,6-tetramethyl-4-phenylcarbamoyloxy-piperidine., a solid substance melting at 195-196°C.

Example 113-116

A mixture of 130.5 g 2,2,6,6-tetramethyl-4-benzoyloxypiperidin and 200 g of acetic anhydride are heated to 8590°־ for 12 hours. The abundant anhydride and the formed acetic acid are removed by vacuum-distillation. The oily residue is dissolved in 400 ml of warm hexane. On cooling the produc^ cristallizes. The cristals are succed off, washed with cold hexane and with water. ' .

After drying in vacuo the obtained l-acetyl-2,2,6,6-tetramethyl 4-benzoyloxypiperidine melts at 95°.

40888-2 in the above procedure 2,2₁6,6-tetra₁־ethyl-4-_caprinoyloxypiperidine, 2,2,6,6-_tetram־thyl-4-־t־aro.yIoxypi_p־ridi־״ or bls(2,2,6,6-tetramethyl-4-pi_Peridinyl)sebacate respectively j, used instead of 2,2,6,6-tetramethyl-4-be0_zoyloxypiperidln, there is obtained

J'*acetyl-2,2_l6,6-tetramethyl-4-caprinoyloxypiperidine, boiling * * at 203 /2.5 mm Ilg, or .

¹^^Cyl-2.2.6.6^־tra_methyl-4-st־ar־yloxyp_ip־rid_in₁־',־elti״_gat jz , or ° bis-(l-acetyl-2,2,6,6-tetran₁ethyl-4-piperidlnyl)-sebaca_Ce '. melting at 67°. ' ’

Examples 117-119

A solution of 18 g of phenyl isocyanate is dropped into a .solution of 39.2 g of'2,2,676-tetrameth^yl-4-benzo^ylox^ypi_peridine in 250 ml of toluene with stirring. The solution is afterwards heated to 80» for 5 hours and to reflex for further ‘ 5 hours. The reaction solution is evaporated in vacuo and the residue is cristallized from hexane. The obtained 1-phenylcarbamoyl-2,2,6,6-tetrameth^yl-4-benzoylox^ypiperidine melts at 80 under decomposition.

If the equivalent amount of bis-(2,2,6,6-tetramethyl,4-piperid!nyl)-sebacate is used instead of the 2,2,6,6-10^^1-4benzoyloxypiperidine in the above procedure there is obtained the bis-(l-ph־nylcarbamoyl-2.,2,6,6-tetramethyl-4-piperidinyl)sebacat, melting at 102° (Dec.).

If the same manner from l-ac_etyl-2,2,6,6-tetramethylpiperidin-401 and phenyl isocyanate there was prepared l-acetyl-2,2,6,6tetrameth^yl-4-phen^ylcarbamoylox^y-pi_Peridine, melting at 196°C.

־ W־־ ׳ ’ V.

40888-2 ’

Examples 120 and 121

\ ׳

A solution of 10 g of acrylic chloride is slowly dropped to a stirred solution of 24.9 g .of 2,2,6,.6-tetramethyl-4-benzoyloxypiperidine and 15 g of triethylamine in 200 ml of benzene.

During the addition the solution is cooled by ice, afterwards the solution is stirred without cooling for about 2 hours and finally it is heated to reflux for a. further 4 hours. After cooling to room temperature the precipitated triethylamine hydrochloride is filtered off and the filtrate is washed with a solution of NaHC0₃ and dried over K₂CO₃. The benzene is .distilled off and .the :residue is cristallized from hexane.

The obtained l-acryl-2,2,6,6-tetramethyl-4-benzoyloxypiperidine melts at 144°.

If in the same procedure 2,2,6,6-tetramethyl-4-phenylcarbamoyloxy-piperidine is reacted with acryloylchloride, there is obtained l-acryl-2,2,6,6-tetramethyl-4-phenylcarbamoyloxy-piperidine as a crystalline solid, melting at 154°C.