DE3229640A1 - COPOLYMERS POLYALKYLPIPERIDINE - Google Patents

Description

Dr. F. Zumstein Sr. --Dr. Ε. · Assmann — Dr. R. Koenigsberger Dipl.-Ing. F. Klingseisen - Dr. F. Zumstein jun.

PATENT LAWYERS

APPROVED REPRESENTATIVES AT THE EUROPEAN PATENT OFFICE REPRESENTATIVES BEFORE THE EUROPEAN PATENT OFFICE

CIBA-GEIGY AG 3-13504 / S / +

Basel, Switzerland)

Copolymers of polyalkylpiperidines

The invention relates to new copolymers made from unsaturated derivatives of polyalkylpiperidines and one or more unsaturated coraonomers, their production and their use as light stabilizers for organic polymers.

It is known that polyalkylpiperidine derivatives are excellent light stabilizers which are used primarily for stabilizing organic polymers. The problem here arises that the stabilizer evaporates during the shaping processing of the polymers or migrates out of the polymer over time. It is also known that this can be largely prevented if a polymeric polyalkylpiperidine derivative is used as the stabilizer. The stabilization of polymers with polymeric stabilizers, however, brings with it the problem of the limited compatibility of polymers with one another. The compatibility is mainly influenced by the chemical structure and the molecular weight of the stabilizer. As is known from various publications, polymeric polyalkylpiperidine derivatives of limited molecular weight are therefore preferred. Depending on the chemical constitution is therefore to molecular weights of about 1000 to 20 ¹ OOO, which is in any case far below the molecular weight of the polymer to be stabilized.

Such a limitation of the molecular weight is in the case of polycondensates relatively simple, it can be done by using an excess of one component or by adding a monofunctional component happen. It is difficult, however, in the case of polymers, the molecular

to limit kular weight in a reproducible manner. In EP-A 496 the addition of regulators, for example mercaptans or aldehydes, is recommended to limit the molecular weight. One Another solution is to use monomers that polymerize slowly and only give polymers of limited molecular weight to lead. A known process for this is the copolymerization of Maleic acid or fumaric acid derivatives with other unsaturated compounds, which mostly run in an alternating manner and form copolymers of limited molecular weight. This principle has already been used for the production of polymeric piperidine light stabilizers used as described in DE-OS 29 20 918. the However, copolymers obtained in this way do not yet meet all practical requirements. They are not enough in certain substrates compatible or soluble, e.g. in paints, in other substrates they show a relatively weak sun protection effect.

Surprisingly, it was found that the effect and the Compatibility of such copolymeric maleic or fumaric acid derivatives of polyalkylpiperidines can be significantly improved if the Piperidine nitrogen substituted by certain substituents.

The invention relates to copolymers from

a) at least one unsaturated polyalkylpiperidine derivative of the formula I.

0 0
ι Il Ι 2
R -XC-CH = CH-CYR (I)

b) at least one comonomer of the formula II

R ³
CH = CR ⁴ (II)

wherein R is one of the groups of the formula III, IV, V, VI, VII or VIII,

el

-y-

₃ / ^ J / V.7

\ - (III) ./ ^ N-CH ₂ -CH- (IV)

\ - (III) ./

3 ^N CH ₂ R ⁶

W _{7 0}

R ⁶ C 1 _{-C 3} H ² B CfI

(V) (VI)

_{3 / R}
R ⁵ - <XX (VII)

"7" Dr ¹ U ΓΊ3

R ^{7 RC} ^ V ^CH 3

/ ^ ₇ OCHo ₇ R

^ wN "^<VIII)

2
R is one of groups III, IV, V, VI, VII or VIII or hydrogen,

C -C alkyl or alkyl interrupted by -0-, C ₃ -C alkenyl, 1 18 jj

C -C -AraIky1 or C -C -cycloalkyl,

10 X and Y are independently 0 or NR,

R is hydrogen or methyl,

R ⁴ hydrogen, C -C ₁ "alkyl, phenyl, Cl, CN, C -C ₁ " alkoxy, CC-

i Io 12 1 "i

Alkanoyloxy, -COOR ¹¹ , -CONH ₂ or -CON (R) (R) means,

RC -C -alkenyl, C -C -alkynyl, -CH -CH (OH) -R, -CH ₂ CN, unsubstituted or substituted by C -C -alkyl, C -C -aralkyl,

C ₂ -C ₁₈ alkanoyl, C ^^ - alkenoyl, -OH, -O (oxyl-oxygen),

-COOC -C -alkyl or -CON (R ¹² ) (R ¹³ ),

6th
R is hydrogen or C -C -alkyl,

7 ^l *

R is hydrogen, C -C alkyl, phenyl, C -C alkoxymethyl, phenoxymethyl or C -C alkyl phenoxymethyl,

R is hydrogen, -C ₁ -C ₁₈ -AlkYl, C ₃ -C ₅ -AHCeUyI, C ₃ -C ₅ -AIkIHyI, C ₂ -C -alkanoyl, C ₃ -C alkenoyl, unsubstituted or substituted by C -C -alkyl C -C aralkyl, -CH CN, -CH-CH (OH) -R or

12 13
-CON (R) (R) means

R is hydrogen, C -C -alkyl, C ₃ -C ₅ -AIkBHyI or C -C -aralkyl,

R ^{10 is} hydrogen, C -C, -alkyl, cyclohexyl, C -C -aralkyl, phenyl i Io / -Li

or is a group of the formula III,

R is hydrogen, C ₁ -C, -alkyl, C -C -hydroxyalkyl, glycidyl or 1 Io Zh

a group of the formula III, IV, V, VI, VII or VIII, or a Group of the formula IX means

R ⁶ CH ^

(IX), CH ₃

14th

wherein R is hydrogen or C -C -alkyl, 12 1 18

RC -C ₁ -alkyl, C -C -cycloalkyl, phenyl, benzyl or a group 11/5 ο

of formula III or IX and

R ^{13 is} hydrogen, C -C, -alkyl, C _c -C ₀ -cycloalkyl or benzyl denotes 1 \ L j ö

or

12 13
R and R together with the N atom to which they are attached form a 5-7 membered heterocyclic ring,

R is hydrogen, methyl or ethyl,

ρ is zero or 1 and

q is one in the case of ρ = zero and zero in the case of ρ = 1

or is 1,
or copolymers of a) at least one maleimide of the formula Ia

O
Il ν 15 11th
/ \ Il \ / B.

-X-

(Ia)

wherein R is a group of the formula III or IX, and b) at least one comonomer of the formula Ha,

CH ₂ = CH-R ¹⁶ (Ha)

wherein R is hydrogen or C -C. -Alkyl is

1 Io

wherein the number average molecular weight of the copolymer is 1,000 to 50,000, in particular 1,000 to 10,000.

If the substituents R ² , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ or R are alkyl, this can be a branched or unbranched alkyl group. Examples of this are - within the defined carbon number - methyl, ethyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-amyl, n-hexyl, 2-ethylbutyl, n-octyl, 2-ethylhexyl, n-decyl, iso-decyl, n-dodecyl, n-tetradecyl, n-pentadecyl or n-octadecyl.

2 5 8 9

If the substituents R, R, R or R are alkenyl, this can be, for example, allyl, methallyl or dimethylallyl. Around

R as alkynyl can be, for example, propargyl, but-2-ynyl or pent-2-ynyl be.

2 5 8 9
R, R, R or R as aralkyl can be, for example, benzyl, phenylethyl, phenylpropyl or naphthylmethyl.

2 12 13
R, R and R as cycloalkyl can be, for example, cyclopentyl, cyclohexyl or cyclooctyl.

R and R as alkanoyl or alkanoyl can e.g. acetyl, propionyl, Butyryl, hexanoyl, lauroyl, acryloyl, methacryloyl or crotonoyl be.

12 13
If R and R together with the nitrogen to which they are attached form a 5-7-membered heterocyclic ring, this can be, for example, a pyrrolidine, piperidine, morpholine or 4-alkylpiperazine ring.

Preference is given to copolymers in which the polyalkylpiperidine groups Are 2,2,6,6-tetramethylpiperidine groups. These are copolymers in which in the groups of formula III, IV, V, VI, VII, VIII and IX of Substituent R is hydrogen.

Copolymers of a compound of the formula I are also preferred and at least one comonomer of the formula II, in which

2 1
R is R or H or C _n -C ₁₀ -AIkVl,

4 1 18

R is hydrogen, C -C alkyl, phenyl, C -C alkoxy, acetoxy or

-COOR is
RC ₃ -C ₅ alkynyl, C ₂ -C alkanoyl, C ₃ -C alkenoyl, benzyl, -CH CN

or -CON (R ¹² XR ¹³ ) is

6th
R is hydrogen,

8th
R is hydrogen, C ^ Cg-alkyl, C ₃ -C ₅ -alkenyl, C ^ Cg-alkanoyl, C ₃ -C-alkenoyl, benzyl or -CH-CN,

9
R is hydrogen, C -C -alkyl, allyl or benzyl, R is hydrogen or C -C -alkyl,

11 ^{X 8}

RC -C -alkyl, C ₂ -C -hydroxyalkyl or a group of the formula III,

IV, V, VI or IX denotes in which R ^{14 is} H or C 1 -C 4 -alkyl,

12 13 1

R and R are C -C alkyl, cyclohexyl or benzyl and R, X, Y, R, R, R and R have the meanings given above, the number average molecular weight of the copolymer from 1000 to 10000 in particular 1000 to 5000.

Copolymers made from are particularly preferred

a) a compound of the formula I in which R is a group of the formula III

2 1
R is R or is C -C alkyl, X and Y are oxygen

5 6

and in formula III R allyl, benzyl or acetyl and R hydrogen

are, and b) a compound of the formula II in which R is hydrogen or methyl and R is hydrogen, C -C -alkyl or -COOR ¹¹ and R ¹¹

1 ο

^C l ~ ^C 4 ~ ^alkyl ° ^{which means a group of the} formula III, in which R is acetyl or benzyl and R is hydrogen, or R is a group of the formula ΐχ

6 14

denotes where R is H and R is H or CH, or from

a) a compound of the formula Ia in which R is a group of the formula

6 14

IX is where R is hydrogen and RH or CH ₃ , and

b) a compound of the formula Ha, in which R is the above Has meaning.

The compounds of the formula I are maleic or fumaric acid derivatives of polyalkylpiperidine alcohols or amines. Some of these are known compounds, such as those described in DE-OS 2 258 752, 2,623,422, 2,349,962 and 2,627,688. Compounds of the formula Ia are described in EP-A 496. So far in the present Invention Compounds of the formula I or Ia are used which are new, they can be used in a manner analogous to the known compounds getting produced.

Examples of monomers of the formula I are:

Bis (1-acetyl-2,2,6,6-tetramethyl-4-piperidyl) maleate Bis (1-benzy1-2,2,6,6-tetramethyl-4-piperidyl) fumarate Bis (1-allyl-2,2,6,6-tetramethyl ~ 4-piperidyl) fumarate Bis (1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate Bis (1-propargyl-2,2,6,6-tetramethyl-4-piperidyl) maleate Bis (1-oxy1-2,2,6,6-tetramethy1-4-piperidyl) maleate ßis (1-hydroxyethyl-2,2) 6,6-tetramethyl-4-piperidyl) fumarate bis [1- (2'-phenoxy-2'-hydroxy) -ethyl-2,2,6,6-tetramethyl- 4-piperidyu] fumarate

Bis (1-cyanomethyl-2,3,6-trimethyl-2,6-diethyl-4-piperidyl) fumarate Mono (1-benzy1-2,2,6,6-tetramethyl-4-piperidyl) maleate Mono (1-acetyl-2,2,6,6-tetramethyl 1-4-piperidyl) monoethyl fumarate N, N'-bis (1-benzyl-2,2,6,6-tetramethyl-4-piperidyl) -fumaric diamide

N.N'-Bisd-benzyl-Z ^ .ö.e-tetramethyl-A-piperidyD-N.N'-dibutylfumaric diamide

213 [2- (2,2, O ₅ 6-tetramethylpiperidino) ethyl] fumarate bis [2- (2,2,6,6-tetramethylpiperidino) propyl] fumarate bis [2- (1,3.8 -triaza-2,4-dioxo-7,7,8,9,9-pentamethyl-spiro [4,5] decyl-3) -ethyl] -fumarate

Bis [2- (1,3,8-triaza-2,4-dioxo-7,7,9,9-tetramethyl-3-dodecyl-spiro- [4,5] decyl-8) -propyl-fumarate

Monoethyl N- (1-butyroyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate monoamide.

Examples of monomers of the formula Ia are:

N- (1,2,2,6,6-pentamethyl-4-piperidyl) maleimide N- (2,2,6,6-Tetramethyl-4-piperidyl) -maleimide N- (1-Benzyl-2,2,6,6-tetramethyl-4-piperidyl) -maleimide N- (1-Acety1-2,2,6,6-tetramethyl-4-piperidyl) maleimide.

As far as the comonomers of the formulas II and Ha are free of piperidine residues, are commercial monomers such as ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-octene, 1-octadecene, styrene, α-methylstyrene, Vinyl chloride, vinyl acetate, vinyl 1-alkyl ethers, alkyl (meth) acrylates, Hydroxyalkyl (meth) acrylates, alkyl crotonates, acrylamide, N-alkyl acrylamides, N-hydroxyalkylacrylamides, methacrylamide or acrylonitrile. Copolymers with ethylene as comonomer in a molar ratio of 1: 1 are particularly preferred.

So much for the comonomers of the formula II derivatives of polyalkylpiperidines are (when R is a group -COOR and R is a group of the formula III, IV, V, VI or IX), then are such compounds e.g. known from DE-OS 2 040 983, 2 258 752 and 2 623 422 or can be produced according to the instructions given there.

Examples of such compounds of the formula II are:

2,2,6, δ-tetramethyl-A-acryloxypiperidine

1-Allyl-2,2,6, δ-tetramethyl-A-acryloxypiperidine 1-Acety1-2,2,6,6-tetramethyl ~ 4-acryloxy-piperidine 1-cyanomethyl-2,2,6,6-tetramethyl-4-acryloxypiperidine 1-Benzyl-2,2,6, o-tetramethyl ^ -methacryloxy-piperidine 1,2,2,6, o-pentamethyl ^ -methacryloxy-piperidine 2,2,6,6-Tetramethyl-4-acrylamido-piperidine 1,2,2,6, δ-pentamethyl-4-acrylamido-piperidine 1,2,2,6,6-pentamethyl-4- (N-butyl) -acrylamido-piperidine 1-Benzyl-2,2,6,6-tetramethyl-4-methacrylamido-piperidine 2,2,6,6-tetramethyl-4- (N-dodecyl) methacrylamido-piperidine.

The inventive copolymers can either by direct Copolymerization of compounds of the formula I or Ia with compounds of formula II or Ha, or by polymer-analogous reaction of prepolymers with (polyalkyl) piperidine derivatives.

The direct copolymerization can be done with or without a solvent, it is preferred to work in an organic solvent or in an aqueous dispersion. The polymerization can be carried out by ionic Catalysts are initiated, working at room temperature or only slightly elevated temperature. It is preferred to initiate the Copolymerization, however, by means of radical catalysts such as peroxy compounds or azo compounds. In this case it works one at an elevated temperature, preferably at 40 ° -15O ° C. Is this If comonomers are gaseous at the polymerization temperature, the copolymerization is advantageously carried out under increased pressure in an autoclave.

The comonomer II or Ha is used in at least an equimolar amount, it is preferably used in excess. Even if an excess of II or Ha is used, predominantly one obtains alternating copolymers, which the two components approximately in

-r-

Molar ratio 1: 1 included. When II is an acrylic or methacrylic acid derivative is, copolymers are obtained with a component ratio which corresponds to the ratio of the monomers used.

In special cases it can be advantageous to have more than one connection of the formula I or Ia, or more than one compound of the formula II or Ha to be copolymerized. Also in these cases predominantly arise alternating copolymers.

The polymerization is generally carried out so that the total amount of the monomeric components together with the initiator in an organic solvent or dispersed in water and the polymerization starts by slow heating. But you can also start the polymerization first with only some of the two components and then the monomer mixture is continuously added dropwise. In general the copolymerizations of I with II and of Ia with Ha are relatively sluggish and require a polymerization time of several hours at elevated temperature until all of the monomers of the formula I or Ia have polymerized into them are. Accordingly, the copolymers obtained in this way have a relatively low molecular weight, which is intentional the invention lies. In general, copolymers are obtained with a number average molecular weight of about 1000 to 20,000 in In some cases the molecular weight can also be higher. However, copolymers with a number average molecular weight are preferred from 1,000 to 10,000, in particular from 1,000 to 5,000.

Examples of organic solvents in which one can copolymerize can perform are hydrocarbons such as toluene or xylene, esters such as ethyl acetate or butyl acetate, or ethers such as dibutyl ether or dioxane. When working in aqueous dispersion, it is expedient to add an emulsifier, for example sodium lauryl sulfate or sodium dodecylbenzenesulfonate. The isolation of the copolymer from solution can, for example, by precipitation by means of a

Ho

- vr-

Nonsolvent or done by evaporation. Is the copolymer Not soluble in the solvent used, it separates out as a dispersion and can be isolated by simple filtration as well as from aqueous dispersions. The inventive Copolymers are usually solid and soften above 60 °, which is desirable for their use as stabilizers.

As already mentioned, however, the copolymers according to the invention can also be produced indirectly by first producing a precopolymer which is then converted into the copolymer according to the invention by a polymer-analogous reaction. For example, a precopolymer I '/ II can be produced by copolymerizing a monomer I ^f with the comonomer II, which is then converted into a copolymer I / II or Ia / II by a polymer-analogous chemical reaction.

Examples of ^{suitable monomers I 1} are maleic anhydride, maleic acid dialkyl ester or fumaric acid dialkyl ester. Precopolymers with maleic anhydride have the structure X

3
R.

Il R

and by reaction with a piperidine derivative of the formula R -XH into the polymer-analogous half-esters or half-amides of the structure XI or XIa

-CH-CH-CH-C (R ³ ) (R ⁴ ) - -CH CH-CH ₂ -C (R ³ ) (R ⁴ )

R -X-CO COOH COOH CO-X-R

(XI) (XIa)

being transformed.

In a second reaction stage, when using excess R -XH get a product of structure XII:

-CH-CH-CH ₂ -C (R ³ ) (R ⁴ ) -R ^ X-CO CO-XR ^{1 (XII)}

Or one uses in the second stage a different one from R -XH

2
Reagent R -YH and then obtain the polymers of structure XHL or XIIIa:

-CH-CH CH ₂ -C (R ³ ) (R ⁴ ) - -CH-CH CH ₂ -C (R ³ ) (R ⁴ ) -

R ¹ ^ X-CO CO-YR ² R ² -Y-C0 CO-XR ¹

(XIII) (XIIIa)

Starting from a maleic anhydride-olefin copolymer of Structure XIV is obtained by reaction with a primary amine of Formula R -NH via the intermediates XIVa an Ia / IIa copolymer of structure XV:

H CH CH ₀ CH

L 15 lift ^(XIVa)

OOH CONHR R ¹⁰

) 2

Copolymers of maleic anhydride of structure X or XIV of relatively low molecular weight are commercially available.

1 2

The reactions of such prepolymers with R -XH, R -YH or R -NH ₉ are preferably carried out in a solvent.

1 The ring opening of the pre-copolymers with 1 mol equivalent R -XH below Formation of half-esters or half-amides of structure XI already occurs at relatively low temperatures, e.g. at 50-100 ° within short time in a quantitative way.

For the second stage of the reaction to XII or XIII or the Iraidbildung to XV you need higher temperatures, about 80-160 °. The second stage can also be carried out under milder conditions if the intermediates of structure XI are first reacted with an equimolar amount of thionyl chloride and then the second ^{molar equivalent of R 1} XXH or R ² -YH is added.

In addition to the pre-copolymers of maleic anhydride with comonomers of the formula II or Ha, it is also possible to use pre-copolymers of maleic or fumaric acid dialkyl esters with these comonomers. Such Copolymers have the structure XVI

COO alkyl

-CH-CH-CH ₂ -C (R ³ ) (R ⁴ ) - ((XVI) COO-alkyl

and are also known compounds, some of which are commercially available.

You can by reaction with 1 mol equivalent of R -XH in the corresponding mixed diesters or ester amides are converted. The copolymers of are obtained by reaction with 2 molar equivalents of R -XH StructureXIl. If the prepolymer of the structure XVI is used first one mole equivalent R -XH and then one of them

send R -YH to products of structure XIII. Used one in the second reaction stage less than 1 mol equiva-

/ β

2
lent R -YH or if the prepolymer is reacted with more than 1 but less than 2 molar equivalents of R -XH, partially converted copolymers are obtained, which are also the subject of the invention and can be used as light stabilizers.

These reactions can be carried out without solvents or in organic

1 2 solvents are carried out. If R -XH or R -YH is an alcohol, the reaction is carried out according to the general procedures for transesterification. It is preferable to work in the presence of Transesterification catalysts and at temperatures of 110-180 °. 1st

1 2
R -XH or R -YH is an amine, the reaction is carried out according to the general procedures for amidation of esters. It is preferable to work with basic catalysts, such as alkali alkoxides, and at temperatures of 120-170 °.

If you have a precopolymer of structure (XVII)

COO alkyl

-CH-CH-CH ₂ -CH (R ¹⁶ ) - (XVII) COO-alkyl

with one mole equivalent of a primary amine R -NH ", so an ester-amide is obtained first, which by heating to temperatures from 130-180 °, e.g. in dimethylformamide, can be converted into an imide copolymer of structure XV.

Finally, the substituents on the piperidine nitrogen, R, R and R, are introduced by reaction with a precopolymer. For this you can use a precopolymer in which R, R or R is hydrogen, and this can be, for example, with an alkyl, alkenyl, alkynyl, aralkyl, alkanoyl or alkenoyl halide realize. An acetyl radical can be introduced by means of acetic anhydride, a cyanomethyl radical by reaction with CH “O / HCN, a Methyl group through CH-0 / HCOOH. Some of these are shown in the examples Conversions of pre-copolymers into copolymers according to the invention described in more detail.

2o

The copolymers according to the invention are effective light stabilizers for organic polymers that are sensitive to light, especially UV light. Examples of such photosensitive Polymers are:

1. Polymers of mono- and diolefins, for example polyethylene (which can optionally be crosslinked), polypropylene, polyisobutylene, Polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene as well as polymers of cycloolefins such as cyclopentene or norbornene.

2. Mixtures of the polymers mentioned under 1), e.g. mixtures of polypropylene with polyethylene or with polyisobutylene.

3. Copolymers of mono- and diolefins with one another or with other vinyl monomers, such as ethylene-propylene copolymers, propylene-butene-1 copolymers, Propylene-isobutylene copolymers, ethylene-butene-1 copolymers, Propylene-butadiene copolymers, isobutylene-isoprene copolymers, Ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, Ethylene-vinyl acetate copolymers or ethylene-acrylic acid copolymers and their salts (ionomers), as well as terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or Ethylidene norbornene.

4. Polystyrene.

5. copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, such as styrene-butadiene, styrene-acrylonitrile, styrene-ethyl methacrylate, styrene-butadiene-ethyl acrylate, styrene-acrylonitrile-methyl acrylate; Mixtures of high impact strength made from styrene copolymers and another polymer such as a polyacrylate, a Diene polymers or an ethylene-propylene-diene terpolymer; as Block copolymers of styrene, such as styrene-butadiene-styrene, styrene-isoprene-styrene, Styrene-ethylene / butylene-styrene or styrene-ethylene / Propylene styrene.

6. Graft copolymers of styrene, such as styrene on polybutadiene, Styrene and acrylonitrile on polybutadiene, styrene and maleic anhydride on polybutadiene, styrene and alkyl acrylates or alkyl methacrylates Polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, Styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, Styrene and acrylonitrile on acrylate-butadiene copolymers, and their mixtures with the copolymers mentioned under 5), such as so-called ABS, MBS, ASA or AES polymers.

7. Halogen-containing polymers such as polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, epichlorohydrin homo- and copolymers, in particular polymers made from halogen-containing vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, Polyvinylidene fluoride; and their copolymers such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl lactate or vinylidene chloride-vinyl acetate.

8. Polymers that differ from α, β-unsaturated acids and their Derive derivatives, such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitriles.

9. Copolymers of the monomers mentioned under 8) with one another or with other unsaturated monomers, such as acrylonitrile-butadiene copolymers, Acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers, or acrylonitrile-alkyl methacrylate-butadiene terpolymers.

10. Polymers that differ from unsaturated alcohols and amines or derive their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate, polyvinyl butyral, Polyallyl phthalate, polyallyl melamine.

11. Homo- and copolymers of cyclic ethers, such as polyalkylene glycols, Polyethylene oxide, polypropylene oxide or their copolymers with

Bisglycidyl ethers.

12. Polyacetals, such as polyoxymethylene, and those polyoxymethylenes which contain comonomers such as ethylene oxide.

13. Polyphenylene oxides and sulfides.

14. Polyurethanes, which differ from polyethers, polyesters and polybutadienes with terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other hand, as well as their precursors (polyisocyanates, polyols, prepolymers).

15. Polyamides and copolyamides, which are different from diamines and dicarboxylic acids and / or derived from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, polyamide 6/10, Polyamide 11, polyamide 12, poly ^^^ - trimethylhexamethylene terephthalamide, Poly-m-phenylene-isophthalamide, as well as their copolymers with Polyethers such as with polyethylene glycol, polypropylene glycol or polytetramethylene glycol.

16. Polyureas, polyimides and polyamide-imides.

17. Polyesters derived from dicarboxylic acids and diols and / or from Derive hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, Poly [2,2-bis (4-hydroxyphenyl) propane] terephthalate, polyhydroxybenzoates, and block polyether esters, which are derived from polyethers with hydroxyl groups, dialcohols and dicarboxylic acids.

18. Polycarbonates.

19. Polysulfones and polyethersulfones.

20. Crosslinked polymers that are derived from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol-formaldehyde, Urea-formaldehyde and melamine-formaldehyde resins.

21. Drying and non-drying alkyd resins.

22. Unsaturated polyester resins that differ from saturated copolyesters and unsaturated dicarboxylic acids with polyhydric alcohols, as well as vinyl compounds as crosslinking agents, as well as their halogen-containing, flame-retardant modifications.

23. Crosslinkable acrylic resins, which differ from substituted acrylic acid esters derived from e.g. epoxy acrylates, urethane acrylates or polyester acrylates.

24.Alkyd resins, polyester resins and acrylate resins with melamine resins, Urea resins, polyisocyanates or epoxy resins are crosslinked.

25. Crosslinked epoxy resins derived from polyepoxides, e.g. of bis-glycidyl ethers or of cycloaliphatic diepoxides.

26.Natural polymers such as cellulose, natural rubber, gelatine, and their polymer homologous chemically modified derivatives, such as Cellulose acetates, propionates and butyrates, or the cellulose ethers, such as methyl cellulose.

The stabilization of polyolefins is of particular importance, Styrene polymers, polyamides, polyurethanes and varnish resins such as alkyd, acrylic and polyester resins.

The copolymeric stabilizers are added to the plastics in a concentration of 0.01 to 5% by weight, calculated on the amount to be stabilized Material, added. Preferably 0.1 to 2% by weight

2 ¥

- vr-

of the compounds, calculated on the material to be stabilized, incorporated into it.

The incorporation can take place during or after the polymerization, for example by mixing the compounds and, if appropriate, further additives into the melt in accordance with those customary in the art Methods, before or during the shaping, or also by applying the dissolved or dispersed compounds to the polymer, if appropriate with subsequent evaporation of the solvent.

The new compounds can also be in the form of a masterbatch, the these compounds, for example, in a concentration of 2.5 to Contains 25 wt .-%, are added to the polymers to be stabilized.

The invention therefore also relates to the addition of 0.01 to 5% by weight of a compound of the formula I stabilized polymers which may optionally also contain other known and customary additives. The plastics stabilized in this way can be used in a wide variety of Form, e.g. as foils, fibers, tapes, profiles or as binders for paints, adhesives or putties.

As further additives, together with those which can be used according to the invention Stabilizers that can be used include, for example:

Antioxidants such as 2,6-dialkyphenols, derivatives of alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidene bisphenols, O-, N- and S-benzyl compounds, hydroxybenzylated malonic esters, hydroxybenzyl aromatics, S-triazine compounds, amides of the β- (3 , 5-di-tert-butyl-4-hydroxyphcnyl) propionic acid, ester of ß- (3,5-di-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid, ester of 3,5-di- tert-butyl-4-hydroxyphenyl ^{acetic acid, acylaminophenols, benzyl phosphonates, aminoaryl derivatives, UV absorbers and light stabilizers, such as 2- (2!} - hydroxyphenyl) benzotriazoles, 2,4-bis- (2'-hydroxyphenyl) -6- alkyl-s-

-pr-

triazines, 2-hydroxybenzophenones, 1,3-bis- (2'-hydroxybenzoyl) -benzenes, Esters of optionally substituted benzoic acids, acrylates, furthermore nickel compounds, sterically hindered amines, oxalic acid diamides, Metal deactivators, phosphites, peroxide-destroying compounds, polyamide stabilizers, basic co-stabilizers, PVC stabilizers, Nucleating agents or other additives such as plasticizers, lubricants, emulsifiers, fillers, soot, asbestos, Kaolin, talc, glass fibers, pigments, optical brighteners, flame retardants, antistatic agents.

Examples of further additives with which together the invention usable stabilizers can be used, can be found in DE-OS 2 427 853 on pages 18-24,

If known stabilizers are used, synergistic Effects occur, which is particularly evident when using UV absorbers, is often the case.

The copolymers according to the invention can also be used in the form of their salts be used. Unless R or R are acyl groups, the piperidine groups of the copolymers according to the invention are used to form Capable of salts with acids, e.g. with hydrochloric acid, phosphoric acid or sulfonic acids. Such copolymers, which have free carboxyl groups,

for example those in which in component I the group -YR

4 is -OH, or those in which m of component II is the group R -COOH can also form salts with strong bases, especially alkali metal salts.

The copolymers according to the invention can also be used in the form of their complexes be used with heavy metal compounds, especially nickel or cobalt compounds. Examples are complexes with Kickel acetate, nickel stearate or nickel acetylacetonate.

The following examples illustrate the preparation of the copolymers according to the invention and their use as light stabilizers. The temperatures listed therein are given in ^0C.

Example 1 : In a 1 liter autoclave (made of Hastelloy B) with a magnetically driven propeller stirrer, 34.5 g (0.06 mol) of bis (1-benzyl-2,2,6,6-tetramethyl-4-piperidyl) are added ) fumarate (melting point 177-178 °), dissolved in 250 ml of butyl acetate and admixed with 1.0 g of azo-isobutyronitrile (AIBN). Ethylene is then injected up to a pressure of 50 bar and the reaction mixture is heated to 88-90 ° for 8 hours with stirring, a final pressure of 75 bar being established at 90 °. The reaction mixture is then evaporated, dissolved in chloroform and filtered through a layer of kieselguhr (Hyflo).

The filtrate is concentrated to about 100 ml and at room temperature under stirred vigorously in about 1 liter of methanol, which is

this separating colorless, fine powder is filtered off and in a high vacuum dried at 50 °. The bis (1-benzyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate-ethylene copolymer thus obtained has a softening point (Tg) of / -w100 ° and has an average molecular weight (M) of 7300 (Copolymer No. 1). η

(C " _o H _r .N Ο.) Calculates N 4.65% jo i> 4 .z 4 η

(602.8) found N 4.4%

Example 2 : Analogously to Example 1, 33.3 g (0.07 mol) of bis (1-allyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate (melting point 121-122 °), 250 ml of butyl acetate and 0.8 g of AIBN were placed in a 1 liter autoclave. 50 bar of ethylene are injected and copolymerized for 7 hours at 88-90 ° with vigorous stirring. Final pressure 84 bar (at 90 °). The bis (l-allyl-2,2,6,6-tetramethyl-4-piperidyl) -fumarate-ethylene copolymer is isolated as in Example 1. The copolymer (No. 2) is obtained as a colorless powder with a softening point of approx . 65 ° and

received an M of 3900,
η

EXAMPLE 3 Analogously to Example 1, 31.1 g (0.065 mol) of bis (1-acetyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate (melting point: 151-152 °; produced by Transesterification of diethyl fumarate with 2 molar equivalents of 1-acetyl-4-hydroxy-2,2,6,6-tetramethylpiperidine of mp.

129-130 °) and 1.0 g of AIBN in 250 ml of butyl acetate, 50 bar ethylene pressed on and heated to 88-90 ° for 6 hours with stirring, a final pressure (at 90 °) of 77 bar being established. Then will the crude copolymer freed from the solvent in a water jet vacuum, the residue dissolved in dichloromethane and washed through a layer of Hyflo filtered clear. After concentration, the filtrate is precipitated in 500 ml of η-hexane at room temperature with vigorous turbination, the precipitate dissolved in a little dichloromethane and completely freed from the solvent in vacuo, whereby the bis (1-acetyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate-ethylene copolymer as white, pulverizable ones

Mass of the softening point 90 ° and an M of 5300 is obtained. (Copolymer No. 3).

Example 4 ; Analogously to Example 1, 10 g (0.04 mol) of N- (1,2,2,6,6-pentamethyl-4-piperidyl) maleimide (melting point: 118-119 °, prepared from maleic anhydride and 4-amino- l, 2,2,6,6-pentamethylpiperidine) and 0.2 g of AIBN in 80 ml of butyl acetate in a 0.3 liter autoclave. 50 bar of ethylene are injected and then copolymerized for 5 hours at 88-90 ° with vigorous stirring. Final pressure at 88 °: 70 bar.

For the isolation of the N- (1,2,6,6-pentamethyl-4-piperidyl) -maleimide-ethylene copolymer the reaction mixture is filtered through Hyflo, washed with dichloromethane, the filtrate is evaporated, again dissolved in a little dichloromethane and poured the copolymer solution into 400 ml of acetonitrile with vigorous turbines. The felled Copolymers (No. 4) is dried in a high vacuum at 50 °; it softens at about 190 ° and has an average molecular weight M of 7,300.

10 g (0.04 mol) of N- (1,2,6,6-pentamethyl-4-piperidyl) maleimide are analogously used and 0.5 g of AIBN in 80 ml of butyl acetate copolymerized with ethylene at 90 ° and isolated analogously to Example 4. The obtained copolymer has a softening point of 150 ° and an average molecular weight of 1900 (copolymer no. 4a).

- does-

Example 5 :

A) Bis- (2,2,6,6-tetramethyl-4 ~ piperidyl) -fumarate-ethylene copolymer:

Analogously to Example 1, 31.6 g (0.08 mol) of bis (2,2,6,6-tetramethyl-4-piperidyl) fumarate are obtained (Mp: 157-158 °) and 0.35 g of AIBN in 250 ml of butyl acetate under a pressure of 40 bar ethylene in a 1 liter autoclave copolymerized and isolated at 75 °. Softening point: approx. 8O ° -82 °.

B) Bis- (l-allyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate-ethylene copolymer by polymer-analogous allylation of A):

A solution of 9.3 g (0.022 mol) of the produced according to A) the copolymer in 50 ml methyl ethyl ketone _w £ _r d _w ith (finely pulverized 6 g of allyl bromide and 7 g of anhydrous potassium carbonate) was added under nitrogen 28 hours at 78- Heated to 80 °. The reaction mixture is then filtered hot and freed from the solvent in vacuo. The residue is dissolved in a little dichloromethane and slowly poured into 300 ml of methanol with vigorous turbines. The precipitate is separated off and dried in a high vacuum at room temperature. The copolymer (No. 5) allylated by a polymer-analogous reaction has a softening point of approx. 90 ° and an M of 11,800. "

(C, _n ! LJ, 0.) Calculates N 5.57 % 30 50 λ 4 η

(502.7) found N 5.3%

Example 6: A solution of 17.3 g (0.03 mol) of bis (1-benzyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate, 12 g (0.12 mol) of ethyl acrylate and 0.6 g of tert-butyl perbenzoate in 50 ml of butyl acetate with stirring in a nitrogen atmosphere at 115-116 ° for 26 hours copolymerized. After this time, no more monomeric starting materials can be detected in the polymerization mixture. Then that will Concentrated reaction mixture and with vigorous turbine at

-pr-

Stirred in AOO ml of methanol at room temperature. The unusual one Bis (1-benzyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate-ethyl acrylate copolymer (No. 6) is separated from the supernatant methanol and dried in a high vacuum at 40 °. Softening point: 88-90 °; M: 3700.

Example 7: A solution of 24 g (0.05 mol) of bis (1-acetyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate, 22.5 g (0, 1 mol) l ^^. O ^ -pentamethyl ^ -piperidyl acrylate and 0.6 g of perbenzoic acid tert-butyl ester as initiator in 100 ml of anhydrous toluene under an argon atmosphere at 110 ° for 30 hours. The toluene is then distilled off in a rotary evaporator, the residue is dissolved in a little methylene chloride, poured into 800 ml of acetonitrile with vigorous turbines and the precipitated bis (1-acetyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate 1 , 2,2,6,6-Pentamethyl-4-piperidyl acrylate-Copolymeri sat separated and dried in a high vacuum at 50 °. It has a softening point of 108-110 ° and an M of 2900 (copolymer no. 7).

Example 8 : Analogously to Example 6, a solution of 14.24 g (0.03 mol) of bis (1-allyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate, 6 g (0.06 Mol) ethyl acrylate and 0.3 g of perbenzoic acid tert-butyl ester as initiator in 130 ml of butyl acetate under nitrogen for 20 hours at 110 °. The copolymer solution is then evaporated in vacuo, the residue is dissolved in methylene chloride, filtered clear and the concentrated filtrate is precipitated by pouring it into 1 liter of methanol with vigorous turbines at -10 °. The precipitate is filtered off and dried in a high vacuum. The bis (l-allyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate-ethyl acrylate copolymer obtained in this way has a softening point of about 135 ° and an average molar weight (M) of 8,000 (Copolymer No. 8).

Example 9 : As in Example 6, a solution of 20.11 g (0.035 mol) of bis (l-benzyl-2,2,6 _} 6-tetramethyl-4-piperidyl) fumarate, 3.93 g (0.035 mol) 1-Octene and 0.2 g of tert-butyl perbenzoate in 200 ml of toluene were heated to reflux under nitrogen for 28 hours.

The copolymer is made by pouring the solution into cold acetonitrile precipitated and purified by redissolving in methylene chloride and precipitating with Acetontril. After drying in vacuo, the bis- (1-

benzyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate-octene copolymer 125 ° and has an M of 2,600 (copolymer no. 9).

Example 10 :

A) Diethyl maleate-ethylene copolymer:

126.2 g (1 mol) of a maleic anhydride-ethylene copolymer (EMA-I103 resin from Monsanto) are placed in 600 ml of absolute ethanol Addition of 0.4 g of p-toluenesulfonic acid heated under reflux for 8 hours. The now completely clear, homogeneous solution is then cooled to 45 ° and added dropwise for 4 hours, with vigorous stirring, 131 g (1.1 mol) of distilled thionyl chloride were added. The mixture is then stirred at 55 ° -57 ° for a further 14 hours. The one cooled to 0 ° The reaction mixture separates into 2 phases after a short time on standing. The lower phase is separated off, at 0 ° three times with 100 ml of ethanol washed and completely freed from the solvent in a high vacuum. The diethyl maleate-ethylene copolymer thus obtained still has 8 χ 10 equivalents of free carboxyl groups per gram, i.e. there are approx. 99.2% of all carboxyl groups are ethyl esters.

B) bis (l-benzyl-2,2,6,6-tetramethyl-4-piperidyl) maleate-ethylene copolymer:

20 g (0.1 mol) of the copolymer obtained according to A) are mixed with 50 g of 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine and 0.4 ml of tetrabutyl orthotitanate in 400 ml of anhydrous xylene in a gentle stream of nitrogen for 24 hours at about 130-135 ° of the transesterification subjected, the split off ethanol continuously from the Reaction mixture is distilled out. Then the xylene completely distilled out and the residue at a pressure of approx.

100 mbar heated to 165-170 ° for a further 8 hours. The copolymer is then redissolved in 150 ml of hot xylene and this solution is poured with vigorous turbination in 1 liter of a methanol-ethanol (1: 1) mixture, whereby the bis (1-benzyl-2,2,6,6-totramethyl-4-piperidyl) -maleate-ethylene copolymer is precipitated as a powder. The precipitate is filtered off and washed with methanol / ethanol 1: 1 and dried in a high vacuum at 60-70 °. Softening point: approx. 120 °;

M 15 300 (Copolymer No. 10).
η

(C "H N 0,) calculated: N 4.65%

jo 54 λ 4 η

(602.8) found: N 4.35%

Example 11 :

A) Dibutyl maleate-ethylene copolymer:

Analogously to Example 10A), 63.1 g (0.5 mol) of a commercial maleic anhydride-ethylene copolymer (EMA-1103 resin, Monsanto) reacted with 300 ml of n-butanol and then with 77.4 g of thionyl chloride (freshly distilled) to give the dibutyl maleate-ethylene copolymer. For purification, after the excess n-butanol has been distilled off, the crude copolymer is washed repeatedly with cold methanol and then completely freed from all volatile components in a high vacuum at 130 ° / 0.01 bar. The resinous Dibutyl maleate-ethylene copolymers have a residual free acid content of 7-10 eq / gram.

B) bis (1-ally1-2,2,6,6-tetramethyl-4-piperidyl) maleate-ethylene copolymer:

Production takes place analogously to Example 10B) by reacting the under HA) produced copolymers with l-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine and ongoing distilling off of the butanol. That

bis- (1-allyl-2,2,6,6-tetramethyl-4-piperidyl) -maleate-ethylene copolymers obtained in this way has a softening point of approx. 100 ° and

a molar weight (M) of approx. 11,500 (copolymer no. 11). η

^(C 3O ^H 5oVVn calculated: N 5.57%

(502.7) found: N 5.1%

Example 12 ; 39 g of a commercial methyl vinyl ether maleic anhydride copolymer of M 16,000 (Gantrez AN - 119 resin,

GAF Corp.) are dissolved in 350 ml of methyl ethyl ketone and stirred at 70 ° (under N) within 4 hours with a solution of 72 g of 4-butylamino-1-benzyl-2,2,6,6-tetraraethylpiperidine droplets added and stirred for a further 8 hours at 70-75 °. The fine-grained precipitate formed during the reaction is filtered off with Washed methyl ethyl ketone and dried at 60 ° in a high vacuum. The maleic acid [1-benzyl-2,2,6,6-tetramethyl-4-piperidyl] monoamide thus obtained - Methyl vinyl ether copolymer softens at 200 ° (copolymer no. 12).

(C ₂₇ H ₄₂ N ₂ O ₄ ) _n calculated: N 6.11 % (458.6) found: N 5.75%

Example 13 : A solution of 38.3 g (0.08 mol) of bis (1-acetyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate (melting point 151-152 °) and 16, 8 g (0.12 mol) of 1-decene in 200 ml of pure toluene are copolymerized with 0.4 g of tert-butyl perbenzoate under nitrogen for 24 hours at 106-108 °. About half of the toluene is then distilled off in vacuo and the concentrated solution is slowly poured into 500 ml of hexane at room temperature with vigorous turbines. The precipitated copolymer is separated off, washed with hexane and completely dried at 60 ° in a high vacuum. The bis (1-acetyl-2,2,6,6-tetramethyl-4-piperidyl) -fumarate-1-decene copolymer obtained in this way has a softening point of approx. 90 ° and an average molecular weight (M) of

3300 (Copolymer No. 13).

(C ,, H _ft -NO) Calc. N 4.53%

(618.6) Found N 4.8 Z.

EXAMPLE 14 Analogously to Example 13, 10 g (0.04 mol) of N- (1,2,2,6,6-pentamethyl-4-piperidyl) maleimide and 8.75 g (0.052 mol) of 1-dodecene are dissolved in 70 ml of pure toluene with the addition of 0.2 g of perbenzoic acid tert-butyl ester copolymerized under argon at 106-107 ° for 24 hours. The toluene is now distilled off in vacuo, the residue is dissolved in a little dichloromethane and slowly poured into 500 ml of acetonitrile at 0-5 ° with vigorous turbines. The precipitated, initially resinous copolymer is separated off, washed with acetonitrile and completely dried in a high vacuum at about 70 °. The N- (1,2,2,6,6-pentamethyl-4-piperidyl) -maleimide-1-dodecene copolymer isolated in this way has a softening point of about 140 ° and an M of 1850 (copolymer no. 14).

Example 15 : 35.1 g (0.1 mol) of a commercial 1: 1 copolymer of 1-octadecene and maleic anhydride (GuIf PA-18) and 17.1 g (0.1 mol) of 4-amino-1,2, 2,6,6-pentamethylpiperidine dissolved in 250 ml of dimethylformamide were heated to about 160 ° for 17 hours with stirring in an N “atmosphere, the water and dimethylformamide formed being slowly distilled off. After the main amount of dimethylformamide has been distilled off, the bath temperature is increased to 175-180 ° for 2 hours and finally held for a further hour at 180 ° in vacuo at 30 torr. The product is then cooled to approx. 80 °, dissolved in 1,2-dichloroethane and this viscous solution is slowly poured into 1 liter of methanol with vigorous turbines, the copolymeric imide precipitating out. It is separated from the supernatant methanol and dried in vacuo and then in a high vacuum at 80 ° / O, O2 Torr. The thus obtained copolymeric imide of structure

^C 16 ^H 33

CH_ · · CH_ 3 \ | I / 3

CH

CH "

has a softening point of approx. 130 ° and an M of 10500 (Copolymer No. 15). It is easily and clearly soluble in η-hexane. That

13 C-NMR spectrum is consistent with the structure indicated.

Example 16 : Analogously to Example 14, 42.1 g (0.12 mol) of the l-octadecene-maleic anhydride copolymer (GuIf PA-18) and 18.8 g (0.12 mol) of 4-amino-2, 2,6,6-tetramethylpiperidine in dimethylformamide is the copolymeric imide of the repeating structural unit

-CH
I.

^C 16 ^H 33

CH

CH CH-

I I

CH

3 \ |

'. CH,

^CH 3 ^/

manufactured. Precipitation in 1.2 liters of methanol gives a practically colorless powder which is dried in a high vacuum at 80 °. It owns a softening point of 120-130 ° and an M of 11000. It is in

Clearly soluble hexane (copolymer no. 16).

Examples 17-28 : Analogously to Example 13, 1: 1 copolymers were prepared from the following pairs of monomers:

Copolymer No. 17 bis (1-benzyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate and 1-octadecene, Softening temperature (T) approx. 64 °, M 2600.

S - Xl

Copolymer No. 18 N, N'-bis (1-benzyl-2,2,6,6-tetramethyl-4-piperidyl) -fumardianiide and 1-octene, softening temperature (T) approx. 140 °, M 2260.

Copolymer No. 19 bis-2- (2,2,6,6-tetramethylpiperidino) ethyl fumarate and 1-octene, softening point (T) 57-65 °, M 1930.

S Tl

Copolymer No. 20 bis (l-allyl-2,2,6,6-tetraraethyl-4-piperidyl) fumarate and butyl vinyl ether, Softening temperature (T) approx. 90 °, M 3000.

S ti

Copolymer No. 21 bis (l-benzyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate and vinyl acetate, Softening temperature (T) approx 142 °, M 3100.

s η

Copolymer # 22

CH ₃ CH C ^ ₃ CH

C ^ ₃ CH NHCO OCNH · '

XX> ^CH 3

»- · C N-CH CH -0OC-CH = CH-COO-CH-Ch -NC · - · '

CH ₃ CH ₃ 0 CH ₃ CH ₃

and 1-decene, softening temperature (T) 110 °, M 3030.

s Γι

Copolymer No. 23 bis (1-acetyl-2,2,6,6-tetraraethyl-4-piperidyl) fumarate and N-vinylpyrrolidone, Softening temperature (T) approx. 170 °, M 4600.

S Xl

Copolymer # 24

f-lTJ PIT

\ 3 / ι

iV \ -CH CH 00C-CH = CH-C00CH ₂ CH_-N ^ ^ ^ j G - \ , T * C NC ₀ H ₁ ,

and 1-octene, softening temperature (T) approx. 98 °, M 4300.

s η

Copolymer No. 25 bis (1-benzyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate and styrene, Softening temperature (T) 140 °, ΪΪ 2250.

s η

Copolymer No. 26 bis (1-benzyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate and 1-octene, Softening temperature (T) approx. 125 °, M 2600.

s η

Copolymer No. 27 bis (1-benzyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate and 1-dodecene, Softening temperature (T ^) approx. 100 °, M 2100.

s η

Copolymer No. 28 bis (1-acety1-2,2,6,6-tetramethyl-4-piperidyl) fumarate and 1-acetyl-2,2,6,6-tetramethyl-4-piperidyl acrylate, Softening point (T) approx. 86 °,

M 1960.
η

Examples 29 and

Analogously to Example 4, 1: 1 copolymers of the following structure were obtained manufactured:

Copolymer # 29

-CH- CH CH-CH-

OiL, CO

T _s approx. 230 'M approx. 16000

ch / V \ h,

Copolymer # 30

"Υ

HpTT

: h — ch-

ι π

OC ^ CO

T approx. 21O ^c s

2200

i / ^CH 3

CH

3 H

Example 31 ; Analogously to Example 12, a half-ester copolymer (No. 31) is made from a commercial maleic anhydride - Octadeaerr- 1: 1 copolymer (Gulf P-18) and 1-acetyl 1-2,2,6,6-tetramethyl-piperidinol-4 structure

manufactured that softens at 190 ° and in most solvents is difficult to dissolve.

Example 32 ; Sunscreen effect in polypropylene film 100 parts of polypropylene powder (Moplen, Fiber grade, from Montedison) are mixed with 0.2 parts of ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester, 0.1 part of calcium stearate and 0.25 parts of a stabilizer of the following Table 1 in a Brabender plastograph homogenized at 200 ⁰ C for 10 minutes. The mass obtained in this way is removed from the kneader as quickly as possible and pressed into a 2-3 mm thick plate in a toggle press. A part of the raw pressed part obtained is cut out and pressed between two high-gloss hard aluminum foils with a manual hydraulic laboratory press for 6 minutes at 260 ° to form a 0.1 mm thick foil

immediately quenched in cold water. This becomes now Sections punched out and exposed in the Xenotest 1200. In regular At intervals, these test specimens are removed from the exposure apparatus and checked for their carbonyl content in an IR spectrophotometer checked. The increase in carbony lext inkt ion at 5,85 ^ i during the Exposure is a measure of the photooxidative degradation of the polymer (see L. Balaban et al., J. Polymer Sei, Part C; 22, 1059-1071 (1969) and experience has shown that the mechanical properties decrease of the polymer connected. The measure of the protective effect is the time it takes to achieve a carbon extinction of approx. 0.3, at which the Comparison film is brittle. In the case of an unstabilized sample, this is approximately 900 hours.

stabilizer Exposure test Copolymer no. in hours 1 3220 2 4900 3 3600 4th 4200 5 3730 6th 3720 8th 3000 13th 4800 14th > * 5500 17th ■ -.- 4300 19th > 5000 20th .1.-45OO 21 3870 22nd "> 3000 23 ^ - 2900 24 '; * 4400 25th 4360 26th . ': -5500 27 5770 28 -> 2350

Claims (8)

Claims 1.jCopolymer made of a) at least one unsaturated polyalkylpiperidine derivative of the formula I 0 0 1 Il Il 2 R-X-C-CH = CH-C-Y-R (I) b) at least one comonomer of the formula II R ³
I a CH ₂ = CR (II) wherein R is one of the groups of the formula III, IV, V, VI, VII or VIII, ₃ / i »CH _{3 /} H ₂ R ^{6 (III)} \ VcH ₂ -CH- (IV) H o ι 0 N ι ₉ Γ (V) (VI) ^ "X ⁰ V 7 R ⁶ C I / _χ / 0 — CHo Jk
-CH-CH-N;. X (VIII) 2
R is one of groups III, IV, V, VI, VII or VIII or hydrogen, C -C alkyl or alkyl interrupted by -0-, C -C alkenyl, i Io J J Is C -C aralkyl or C -C cycloalkyl, 10 X and Y are independently 0 or NR, R is hydrogen or methyl, Λ
R hydrogen, CC ₁ -alkyl, phenyl, Cl, CN, CC ₁₀ -AlkOXy, CC- 1 Io ._ ¹ II- ¹ - ⁰ ^ - ¹ Alkanoyloxy, -COOR ¹¹ , -CONH ₉ or -CON (R) (R), RC ₃ ~ C ₅ -alkenyl, C ₃ -C ₅ -AIkIUyI, -CH ₂ -CH (OH) -R, -CH ₂ CN, unsubstituted or C -C -alkyl substituted C -C -aralkyl, ^C 2 ~ ^C 18 ~ ^{AlkanOyl> c} ₃ " ^c ₅ - ^Alken ° y ' ⁱ -y -OH, -0 · (Oxyl-Oxygen), -COOC -C -alkyl or -CON (R ¹² ) (R ¹³ ), 6th
R is hydrogen or C -C _r -alkyl, 7 ^XJ R hydrogen, C ₁ -C ₃ -AIlCyI, phenyl, C -C -alkoxy-methyl, phenoxy- methyl or C -C alkyl phenoxymethyl, 8 ^l R is hydrogen, C ^ C ^ -alkyl, C ₃ -C ₅ -alkenyl, C ₃ -C -alkynyl, C ₃ -C- Alkanoyl, C ₃ -C ^ alkenoyl, unsubstituted or C -C -alkyl substituted C -C -aralkyl, -CH CN, -CH ₀ -CH (OH) -R ⁷ or 12 13
-CON (R) (R) means R is hydrogen, C ^ -C ^ -alkyl, C ₃ -C ₅ -AIlCeHyI or CC -aralkyl,
R ° hydrogen, C ₃ -C alkyl, cyclohexyl, C -C aralkyl, phenyl or a group of the formula III, R is hydrogen, C ₁ -C ₁ -alkyl, C -C -hydroxyalkyl, glycidyl or denotes a group of the formula III, IV, V, VI, VII or VIII, or a group of the formula IX, 14th
wherein R is hydrogen or C -C -alkyl, RC -C ₁ -alkyl, C -C -cycloalkyl, phenyl, benzyl or a group 1 I ^ 5 ο of formula III or IX and
R is hydrogen, C -C -alkyl, C ₅ -Cg-Cycloallcyl or benzyl or 12 13
R and R together with the N atom to which they are attached form one 5-7 membered heterocyclic ring, R is hydrogen, methyl or ethyl,
ρ is zero or 1 and
q is one in the case of ρ = zero and one in the case of ρ = 1, zero or 1, or copolymers of a) at least one maleimide of the formula Ia Λ " ij Vr ¹⁵ da) wherein R is a group of the formula III or IX, and b) at least one comonomer of the formula Ha, CH ₂ = CH-R ¹⁶ (Ha) 16
where R is hydrogen or C -C -alkyl, wherein the number average molecular weight of the copolymer is 1,000 to 50,000, in particular 1,000 to 10,000. 2. Copolymer according to claim 1, characterized in that R in the formulas III, IV, V, VI, VII, VIII and IX is hydrogen. 3, copolymer according to claim 1, characterized in that 1 R is R or H or CC ₁₀ -AIkVl, ^{L 18} R is hydrogen, C -C -alkyl, phenyl, C -C -alkoxy, acetoxy or 11th
-COOR is R CC -alkenyl, C -C -alkanoyl, C -C -alkenoyl, benzyl, -CH ₀ CN 12 it - * ² or -CON (R) (R ¹ " ³ ) is, R is hydrogen, 8th
R hydrogen, C ^ -Cg-alkyl, C ₃ -C -alkenyl, C -C ^ alkanoyl, C ₃ -C- Is alkenoyl, benzyl or -CH ₂ CN, ' R is hydrogen, C -C -alkyl, allyl or benzyl, R is hydrogen or C -C alkyl, ^{l 8th} R C -C alkyl, C -C hydroxyalkyl or a group of the formula III, IV, V, VI or IX denotes, in which R ^{1 is} ^ H or C ₁ -C, -alkyl, 13 1 R and RC ₁ -C-AIlCyI, cyclohexyl or benzyl and R, X, Y, R, R, R and R have the meanings given in claim 1, where ■ the number average molecular weight of the copolymer 1000 to lO'OOO, in particular 1000 to 5000. 4. Copolymer according to claim 1 from a) a compound of the formula I in which R is a group of the formula III 2 1
is, R is R or is C -C -alkyl, X and Y is oxygen 5 6 and in formula III R is allyl, benzyl or acetyl and R is hydrogen is and b) a compound of the formula II ', in which R is H or CH "and R is H, 11 11 C -C -alkyl or -COOR and R is C -C -alkyl or a group 5 6 of the formula III denotes in which R is acetyl or benzyl and R is hydrogen or R is a group of the formula IX in which R is H 14th
and RH ader CH-, or off 15th a) a compound of the formula Ia in which R is a group of the formula IX is where R is H and R is H or CH ", and b) a compound of the formula Ha, in which R has the meaning given in claim, where the number average molecular weight of the copolymer 1000 to 10000, in particular 1000 to 5000 amounts to. 5. A copolymer according to claim 1 from a) a compound of the formula I or Ia according to claim 1 and b) ethylene in an approximate molar ratio of 1: 1. 6. Containing polymer stabilized against damage by exposure to light as a light stabilizer 0.01 to 5% by weight, preferably 0.1 to 2% by weight, of at least one copolymer according to claim 1. 7. Stabilized polymer according to claim 6, characterized in that that it is a polyolefin, a styrofoam polymer, a polyamide, a polyurethane or a varnish resin. 8. Stabilized polymer according to claim, characterized in that that it contains other additives in addition to the copolymeric light stabilizer.