FR2511380A1 - STABILIZING COPOLYMERS, BASED ON UNSATURATED POLYALKYLPIPERIDINE DERIVATIVE, AND POLYMERS CONTAINING SUCH A STABILIZING AGENT FOR THE EFFECTS OF LIGHT - Google Patents

Abstract

THE INVENTION CONCERNS COPOLYMERS WHICH ARE POLYMER STABILIZERS WITH REGARD TO THE EFFECTS OF LIGHT. THE COPOLYMERS COME FROM AN UNSATURATED POLYALKYLPIPERIDINE DERIVATIVE: (CF DRAWING IN BOPI) AND FROM A COMONOMER: (CF DRAWING IN BOPI) (R: POLYALKYLPIPERIDINE; R: R OR H, ALKYL, ALCENYL OR H, ALKYL, ALCENYL OR ARCALKYL, XCALKYL OR ARALKYL, Y: O OR NR; R: H, CH; R: H, ALKYL, PHENYL, CL, CN, ALCOXY, ALCANOYLOXY, CONH). APPLICATION: PROTECTION OF VARIOUS POLYMERS AGAINST LIGHT AND ULTRAVIOLET EFFECTS.

Description

The invention relates to novel copolymers of unsaturated

  polyalkylpiperidines and one or more

  unsaturated comonomers, their production as well as their

  It is known that polyalkylpiperidine derivatives are known to protect organic polymers against light.

  are outstanding agents of protection against the

  primarily used to stabilize polymers

  The problem of volatility

  In addition, it is known that this stabilization can be avoided to a large extent when a stabilizer is used as a stabilizer for a polyalkylpiperidine derivative. polymer stabilization

  unsaturated polymers with polymeric stabilizers

  However, the problem of mutual compatibility

  The compatibility is mainly influenced by the chemical structure as well as by the molecular weight of the stabilizer. As is known from various publications, therefore, limited molecular weight polyalkylpiperidine derivatives are preferred. According to the chemical constitution, it is therefore has molecular weights of about 1,000 to 20,000, which in each case is well below the

  molecular weight of the polymers to be stabilized.

  Such a limitation of the molecular weight is

  latively simple in case of polycondensation and can be obtained

  by the use of an excess of a constituent or by

  However, it is more difficult to reproducibly limit the molecular weight in the case of the polymers. In EP-A 496, it is recommended, in order to limit the molecular weight, to add regulators, for example mercaptans. or aldehydes

  Another solution is to use monomers that

  slowly merge and lead only to polymers with a limited molecular weight A known method for this purpose is

  copolymerization of maleic acid derivatives or

  with other unsaturated compounds, which takes place in

  most cases alternately and leads to copo-

  Limited Molecular Weight Molecules This principle has already been used for the production of Piperidine-based Polymer Protection Agents as described

  in DE-OS 2 920 918 The copolymers thus obtained do not

  however, do not lay down all the requirements of the practice.

  They are not very compatible with certain substrates or are not very soluble there, as for example in varnishes; in other substrates, they show a relatively weak effect of

  protection against light.

  It has been surprisingly found that one can

  significantly improve the effect and compatibility of such

  polymers of maleic acid or fumaric acid of polyalkylpiperidines when the nitrogen

  piperidine with certain substituents.

  The subject of the invention consists of copolymers of: a) at least one unsaturated polyalkylpiperidine derivative of formula I

0 O

He there 2 ()

R 1 -X-C-CH = CH-C-Y-R (I)

  and b) at least one comonomer of formula II R

CH 2 = -R (II)

  Formulas wherein R 1 is a group corresponding to one of formulas III, IV, V, VI, VII or VIII:

R CH 2 / CHR 3 / R 6 R

/ 3 C H 3 / CH 2 R 7

R 3 R 5 -N (III) N / -CH 2 -H (Iv)

R 6 C 82 CH 3 C 3 CH 2 R 6

6 6 6 6

RCH CHR O CH 3 2H R

\ 12- / / H HJN_ \ 2

R 8 -New> CRH \ * -d R 6 2 2 a R 6

RC 2 C 3 3 2

  (VI) (V) R 6, CH 3, R 6, 17, x / c 2 R (VII)

O \ q CI) (CH) -

2 p 2 q RC 2 CH 3 p 2

2

  7 R 6 C o 2 / CH 3 17 R 3 17 H 2 R 1 -CH-CH 2-N (/ d HC / 7 (VIII)

/ / 17

AT O H)

R 6 CH 2 CH 3

  R 2 is one of groups III, IV, V, VI, VII or VIII where it represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an alkyl group interrupted by -O-, a group alkynyl having 3 to 5 carbon atoms, aralkyl having 7 to 11 carbon atoms, or cycloalkyl having 5 to 12 carbon atoms, X and Y are, independently of one another, O or

NR 12,

  R 3 is a hydrogen atom or a methyl group, R 4 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, phenyl, Cl, CN, alkoxy having 1 to

  18 carbon atoms, alkanoyloxy having 2 to 5 carbon atoms

  bone, -COOR 11, -CONH 2 or CON (R 12) (R 13), R 5 represents an alkenyl group having 3 to 5 carbon atoms, alkynyl having 3 to 5 carbon atoms, -CH 2 -CH (OH ) -R 7,

  -CH 2 CN, aralkyl (having 7 to 11 carbon atoms, non-substituted

  killed or substituted nrtn alkyl group having 1 to 4 carbon atoms

  B), alkanoyl having 2 to 18 carbon atoms, alkenyl having 3 to 5 carbon atoms, -OH, -O (Oxygen of oxo or hydroxyl group), -COO alkyl (having 1 to 4 carbon atoms) or -CON (R 12) (R 13), R 6 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, phenyl, alkoxy-methyl, having 1 to 4 carbon atoms, phenoxy-methyl or alkyl-phenoxymethyl (in the alkyl group with 1 to 4 carbon atoms), R 8 represents a hydrogen atom, an alkyl group (1 to 18 atoms of carbon), alkenyl (3 to 5 carbon atoms), alkynyl (3 to 5 carbon atoms), alkanoyl (2 to 18 carbon atoms), alkenoyl (3 to 5 carbon atoms), aralkyl with 7 to 11 atoms of carbon, unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms, -CH 2 CN, CH 2 -CH (OH) -R 7 or -CON (R 12) (R 13) R represents an atom of hydrogen, an alkyl group having 1 to 18 carbon atoms, alkenyl having 3 to 5 carbon atoms or aralkyl having 7 to 11 carbon atoms, R 10 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, cyclohexyl, aralkyl having 7 to 11 atoms of carbon, phenyl or a group of formula III, R 11 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, hydroxyalkyl having 2 to 4 carbon atoms, glycidyl or a group of formula III, IV , V, VI, VII, or VIII, or a group of formula IX: R 6 cCH 3 6

R 14 (IX),

  R d 2 \ CH 3 (wherein R 14 is a hydrogen atom of the alkyl group having 1 to 18 carbon atoms),

  R 12 represents an alkyl group having 1 to 12 carbon atoms;

  carbon, cycloalkyl having 5 to 8 carbon atoms, phenyl, benzyl or a group of formula III or IX and, R 13 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, cycloalkyl having 5 to 8 atoms carbon or benzyl, or

12 13

  R and R, taken together with the nitrogen atom to which they are attached, form a 5- to 7-membered heterocyclic ring, R 1 is a hydrogen atom or a methyl or ethyl group, p is zero or is 1, q is 1 if p is zero and, if p is 1, q is 0 or 13, or copolymers of (a) at least 1 maleinimide of formula Ia, Ia, (Ia) (wherein R 15 is a group of formula III or IX) and (b) at least one comonomer of formula I Ia, CH 2 CH-R 16 (Ia)

16 2

  (wherein R 6 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms),

  the number average molecular weight of the copoly-

  mother between 1,000 and 50,000 and in particular between

1000 and 10,000.

2 4 6 7 8 9 10

  When the symbols R 2 R 4 R 6 R 7, R 8 R R O

R 11 12 13 14 16

  R 11, R 2, R 3, R 4 or R 1 substituents represent an alkyl group, this may be a branched or unbranched alkyl group Examples are, within the indicated number of carbon atoms, a methyl, ethyl, iso-propyl, butyl, sec-butyl, tert-butyl, isoamyl, n-hexyl, 2-ethylbutyl, n-octyl, 2-ethylhexyl, n-decyl, isodecyl, n-dodecyl, n -tétradécyle,

n-pentadecyl or n-octadecyl.

2 5 8 9

  When the symbols R, R 5 R or R 9 substituents represent an alkenyl group, this group may

  for example an allyl, methallyl or dimethyl-

  allyl R and R may, as the alkynyl group, be

  a propargyl, butyne-2-yl or pentyne-2-yl group.

2 5 9

  R, R, or R as aralkyl may, for example, be benzyl, phenylethyl, phenyl, R, or naphthylmethyl.

R 2 12 13

  R, R and R as an alkyl group may be

  for example a cyclopentyl, cyclohexyl or cyclooctyl group.

8

  R and R, as an alkenoyl or alkenoyl group may be, for example, an acetyl, propionyl, butyryl group,

  hexanoyl, lauroyl, acryloyl, methacryloyl or crotonoyl.

12 13

  When R and R form, with the nitrogen atom to which they are attached, a heterocyclic ring having 5 to 7

  This may be, for example, a pyrotechnic nucleus

  lidine, piperidine, morpholine or 4-alkylpiperazine.

  Copolymers in which the polyalkylpiperidine groups are 2,2,6,6-tetramethylpiperidine groups are preferred are copolymers in which, in the groups of the formula III, IV, V, VI, VII, VIII and IX, the

  symbol R 6 represents a hydrogen atom.

  Also preferred are copolymers of a compound of formula I and at least one comonomer of formula II, wherein: R 2 represents R or H, or an alkyl group having 1 to 18 carbon atoms, R 4 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, phenyl, alkoxy having 2 to 6 carbon atoms, acetoxy or -COOR 11,

  R 5 represents an alkenyl group having 3 to 5 carbon atoms;

  B, alkanoyl having 2 to 6 carbon atoms, alkenoyl having 3 to 5 carbon atoms, benzyl, -CH 2 CN or

-CON (R 12) (R 13),

  R 6 is a hydrogen atom, R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, alkenyl having 3 to 5 carbon atoms, alkanoyl having 2 to 6 carbon atoms, alkenoyl having 3 to 5 carbon atoms, benzyl or -CH 2 CN, R 9 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, allyl or benzyl, R 10 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 11 represents an alkyl group (1 to 8 carbon atoms), hydroxyalkyl (2 to 4 carbon atoms) or a group of formula III, IV, V, VI or IX (where R 14 is H or an alkyl group having 1 to 4 carbon atoms), R 12 and R 13 each represent an alkyl group having 1 to 8

1 3

  carbon atoms, cyclohexyl or benzyl, and R, X, Y, R 3

7 15 16

  R, R and R 6 have the meanings indicated above, the number average molecular weight of the copolymer being between

  1,000 and 10,000 and in particular between 1,000 and 5,000

  Particularly preferred are copolymers of a) a compound of formula I, wherein R is a group of formula III, R is R 1 or an alkyl group 3 (1 to 8 carbon atoms), X and Y are each a hydrogen atom. oxygen and, in formula III, R represents an allyl, benzyl or acetyl group and R 6 a hydrogen atom, and b) a compound of formula II, in which R 3 is a hydrogen atom or a methyl group and R 4 is a hydrogen atom, an alkyl group (1 to 6 carbon atoms) or COOR 11 and R 1 is an alkyl group (1 to 4 carbon atoms), or a group of formula III in which R 5 is an acetyl or benzyl group and R 6 is a hydrogen atom, or R 11 is a group of formula IX in which R 6 represents H and R 14 H or CH 33, or copolymers of

33 15

  a) a compound of formula Ia, wherein R 5 is a group of formula IX, wherein R 6 is a hydrogen atom and R 14 is H or CH 3, and

3 16

  b) a compound of formula I Ia, wherein R 16 has the meaning

indicated above.

  The compounds of formula I are maleic or fumaric acid derivatives of polyalkylpiperidine-alcohols or amines. In this case, it is in part a matter of known compounds which have been described, for example, in German Offenlegungsschrift 2,258,752, DE-OS 2. 623,422, DE-OS 2,349,962 and DE-OS 2,627,688. The compounds of formula Ia are described in EP-A 496. In the present invention, novel compounds of formula I or Ia are used. , these can be produced from

  analogously to obtaining the known compounds.

  Examples of monomers of formula I are:

  Bis (1-acetyl-2,2,6,6-tetramethylpiperamine maleate

  dyl-4), fumarate dt ,, S (benzyl-1-tetramethyl-2,2,6,6-piperidyl-4),

  Bis (allyl-1-tetramethyl-2,2,6,6-piperan fumarate

Dyle-4),

  Bis (1-acryloyl-2,2,6,6-tetramethylpiperamine) fumarate

  dyl-4) bis (propargyl-1-tetramethyl-2,2,6,6-piperidyl-4) maleate

  Bis (oxy-1-tetramethyl-2,2,6,6-piperyl) maleate

  dyl 4) Bis (1-hydroxyethyl-2,2,6-tetramethylpiperidyl4 fumarate)

  Bis-E fumarate (2'-phenoxy-2 'hydroxy) ethyl-1 tetra-

  2,6-methyl-2,6-piperidyl-40> Bis-cyanomethyl-1-trimethyl-2,3,6-diethyl-2,6-piperyl fumarate 4)

  Mono-benzyl-1-tetramethyl-2,2,6,6-piperinate maleate

  dyl-4) Last butyl fumarate and mono (1-acetyl-2,2,6-tetramethyl, 6,6-piperidyl)

  N, N'-bis (1-benzyl-2,6,6-tetramethyl-4-piperidyl) fumarate

rodiamide

  N, N'-bis (1-benzyl-2,6,6-tetramethyl-4-piperidyl) -N, N-

  dibutyl-fumarodiamide A 'Bisl fumarate (2,2,6,6-tetramethylpiperidino) -2 ethylel. Bis l fumarate (2,2,6,6-tetramethylpiperidino) -propyl (e) Bis C fumarate (1,3,3-triazo-2,4-dioxo-7,8,8-pentamethyl) -spiro 4,5-decyl-3) -ethyl ZO Bis C fumarate (triaza-1,3,8-dioxo-2,4-tetramethyl-7,7,

  9.9 dodecyl-3-spiro-4,5-dodecyl-8) propyl).

  N (1-Butyroyl-2,6-tetramethyl-4-piperidyl) -monoamide

monoethyl fumarate -

  Examples of the monomers of formula Ia: 1 are N- (1,2-pentamethyl-2,6,6-piperidyl) -maleinimide N (2,2,6,6-tetramethyl-4-piperidyl) maleimide

  N (1-Benzyl-2,6,6-tetramethyl-4-piperidyl) -maleide

nimide.

  N (acetyl-1-tetramethyl-2,6,6-piperidyl-4) -maleic

nimide.

  Since the comonomers of formula II and IIa do not contain any piperidine residues, this is

  commercial monomers, such as ethylene,

  pylene, butene-1, isobutylene, hexene-1, octene-1,

  3 octadecene-1, styrene, alpha-methylstyrene, chlo-

  vinyl acetate, vinyl acetate, vinyl alkyl ether, alkyl (meth) acrylates, hydroxyalkyl (m 4th) acrylates, alkyl crotonates, acrylamide,

  N-alkylacrylamide S, N-hydroxyalkylacrylamides, methacrylamide,

  crylamide or acrylonitrile.

  copolymers comprising ethylene as a comonomer

  are in a molar ratio of 1: 1. Inasmuch as the comonomers of formula II are polyalkylpiperidine derivatives (when R is a -COO R11 group and Ri 1 is a group of formula III, IV, V, VI or IX), such compounds are known from DE-OS 2 040 983, DE-OS 2 258 752 and DE-OS 2 623 422, for example, or they can be produced according to the indications given in the documents cited. Examples of such compounds of formula II are tetramethyl. -2,2,6,6-acryloxy-4-piperidine, allyl-1-tetramethyl-2,2,6,6-acryloxy-4-piperidine, acetyl-1-tetramethyl-2,2,6,6-acryloxy-4-piperidine 1-Cyanomethyl-2,6,6-tetramethyl-4-acryloxy-piperidine, 1-benzyl-2,2,6,6-tetramethyl-methacryloxy-4-piperidine, 1,2-pentamethyl-2,2,6,6-methacryloxy-4-piperidine piperidine, 2,2,6,6-tetramethyl-4-acrylamido piperidine, 1,2-pentamethyl-2,2,6,6-acrylamido-4-piperidine, 1,2-pentamethyl-2,2,6,6-n-butyl 4-acrylamide-4-piperidine, 1-benzyl-2,2,6,6-tetramethyl-4-methacrylamido piperidine born,

  2,2,6,6-tetramethyl (N-dodecyl) -methacrylamido-4-piperidine.

  The copolymers of the invention can be produced by direct copolymerization of compounds of formula I o Ia

  with compounds of formula II or I Ia or with a reaction

  polymerization of precopolymers with (polyalkyl) -piperidine S derivatives. Direct copolymerization can be carried out with

  or without solvents; we work preferably in soil

  The polymerizations can be initiated by ionic catalysts, and the reaction is carried out at room temperature or at a temperature which is only slightly high.

  however, the polymerization using radical catalysts

  such as, for example, peroxide compounds or azoles. In this case, the process is carried out at elevated temperature,

11380

  advantageously at 400 up to 1500 C Si, at a temperature of

  polymerization, the comonomer is gaseous, the co-product is

  polymerization under high pressure, advantageously in an autoclave. Comonomer II or I Ia is used in a quantitative

  at least equimolar, and preferably an excess is used.

  Even when an excess of II or Ia is used, we obtain over-

  all of the alternating copolymers that contain the two con-

  approximately in the molar ratio of 1: 1.

  When II is a derivative of acrylic acid or methacrylate

  In this way, copolymers having a ratio corresponding to the existing ratio are obtained between the two constituents.

  between the monomers that are used.

  It may be advantageous in special cases to copolymerize more than one compound of formula I or Ia, or

  more than one compound of formula II or Ia In these cases also

  In this way, predominantly alternate copolymers are obtained.

  The polymerization is generally carried out in

  in an organic solvent or by dispersing in water

  the total amount of the monomeric constituents with the amorphous

  and starting the polymerisation with a slow heating

  However, it is also possible to start the polymerization with only a part of the two constituents and to add

  then constantly, drop by drop, the mixture of mono-

  In general, the copolymerizations of I with II and

  Ia with I Ia are relatively slow and

  require a polymerization time of several hours at elevated temperature, until the monomers of formula I

  or Ia are incorporated by polymerization

  the copolymers thus obtained have a weight

  relatively low molecular weight, which lies in the

  In general, copolymers are obtained

  having a number average molecular weight between

  between 1 000 and 20 000, and in some cases the

  However, copolymers having a number-average molecular weight of between 1,000 and 10,000, and especially of 1,000, are preferred.

and 5,000.

  Examples of organic solvents in which the copolymerization can be carried out are hydrocarbons such as toluene or xylene, esters such as ethyl acetate or butyl acetate, or oxides such as dibutyl or dioxane When working in aqueous dispersion, an emulsifier is advantageously added, for example sodium lauryl sulphate or sodium dodecylbenzene sulphonate. The isolation of the copolymer from the solution may be carried out for example by precipitation at room temperature. Using a non-solvent or by evaporative concentration If the copolymer is not soluble in the solvent that is used, it separates as a dispersion and can be isolated by simple filtration, as it can The copolymers according to the invention are for the most part solid and they soften on top of

   , which is desired for their use as sta-

bilisants.

  As already indicated, however, it can also be

  Indirectly, copolymers of the invention

  producing first of all a precopolymer, which is

  then forms, by a reaction analogous to polymeric

  In the copolymer according to the invention, for example, it is possible to produce, by copolymerization, a monomer.

  with the comonomer II, a precopolymer I '/ II which is transferred

  then forms, by a chemical reaction analogous to

  polymerization, to a copolymer I / II or Ia / II.

  Suitable monomers I 'are, for example, maleic anhydride, a dialkyl maleate or a dialkyl fumarate. Precopolymers comprising maleic anhydride have the structure X R 3 I

-CH CH-CH -C-

g1 2 U_ (X) / \ / W

O O O

  and they can be transformed, by reaction with a derivative

  piperidine of the formula R 1 -XH in the half-esters or hemi-esters

  amides analogous to polymers and of structure XI or X Ia

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

1 O 1 OOH

R -X-CO COOH

(XI)

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

/ OOH 2 O-X-R 1

  In a second reaction stage, it is possible to obtain, using an excess of R 1 -XH, a product of structure XII: embedded image

-CI H CH 2 C (R 3) (R) -

R1-x-CO O-X-R1 (XII)

  or in the second stage a R 2 -YH body is used.

  before reacting and which is different from R 1 -XH and one then obtains the polymers of structure XIII or XII Ia:

-CH-H CH 2 -C (R) (R) -

iii 2 R -X-c O O-Y-R

(XIII)

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

R 2 -Y O O -X-RI

  (XII Ia) From a copolymer of olefin and maleic anhydride of structure XIV, is obtained by reaction with a 1

  primary amine of the formula R 15 -NH 2, passing through the

  intermediate feeds XI Va, a copolymer Ia / I Ia of structure XV: (XIV) o o_ o -CH 2 H o 1 /

+ R 16-NH

-uH- H-CH -H

  O OH CONHR 15 (XI Va) -H 20 (xv) o / '/ 2' 16

0 H / 0

  Copolymers can be obtained commercially.

  maleic anhydride, of structure X or XIV, having a molecular weight of

  The reaction of such precopolymers with R 1 -XH, R 2 -YH or R 15 -NH 2 is preferably carried out in a solvent. The opening of the precopolymer ring using a molar equivalent of R 1 -XH-with formation of hemi-esters or hemi-amides XI structure is then obtained quantitatively, already at relatively low temperatures, for example between 50 and 100, in a short

time space.

  For the second reaction stage giving XII or XIII or for the formation of imides giving XV, higher temperatures, between about 80 and

    The second stage can also be carried out under conditions

  tions, when reacting

  intermediaries of structure XI first with an equiva-

  molar thionyl chloride and then add the

  molar equivalent of R 1 -XH or R 2 -YH.

  In addition to the precopolymers of maleic anhydride

  with comonomers of formula II or I Ia, it is also possible to use

  precopolymers of dialkyl or furan maleates

  These copolymers have the structure XVI 0 oo Alkylk 5

* 2-H-CH-C (R 3) (R) ((XVI)

00 A kylce

  and they are also known compounds, which can be obtained

part of the trade.

  We can transform them by reaction with a

  molar value of R 1-XH in mixed diesters or esteramides

  By reaction with two molecular equivalents

  R 1 -XH, we obtain the copolymers of structure XII.

  If the precopolymers of structure XVI are reacted

  first with a molar equivalent of R 1 -XH and then with a

  If R 2 -YH is different from the first one, products of structure XIII are obtained. If in the second stage of the reaction, less than one molar equivalent of R 2 -YH is used or if the precopolymer is reacted with more of one, but less than two, molar equivalents of R 1 -XH, partially reacted copolymers, which also constitute an object

  of the invention and can be used as pro-

protection against light.

  The reactions can be carried out without solvent or in organic solvents. If R 1 -XH or R 2 -YH is an alcohol, the reaction is carried out according to the procedures

  for transesterifications

  in the presence of transesterification catalysts and at temperatures of 110 to 180 Si R -XH or R 2 -YH is an amine, the reaction is carried out according to the procedure

  Ester amidation is then advantageous.

  with basic catalysts such as, for example,

  alkali alkoxides and at temperatures of 120 to 170.

  When reacting a precopolymer of structure (XVII)

0 OO Alkyl-

-H H CH 2 -CH (R 16) (XVII)

  COO Alkylt 2 with a molar equivalent of a primary amine R 15 -NH 2, firstly an ester-amide is obtained which can be converted by heating at temperatures of 130-180, for example

  in dimethylformamide, to a copolymer of imide of

XV.

  Finally, one can also introduce on the atom

8 14

  piperidine nitrogen substituents R 5, R and R 14 by reacting with

  with a precopolymer can be used for this purpose.

R 5 8 14

  precopolymer in which R 5, R 8 or R 14 is a hydrogen atom.

  and can be reacted with, for example, an alkyl, alkenyl, alkynyl, aralkyl, alkanoyl, or alkenoyl halide.

  acetyl with acetic anhydride, a cyano-

  methyl by reaction with CH 2 O / HCN, a methyl group using CH 2 O / HCOOH In the examples, a few of these precopolymer transformations are described in more detail.

  copolymers according to the invention.

  The copolymers according to the invention are

  protection agents, with regard to light, poly-

  which are sensitive to light, in particular

  bind to ultraviolet light Examples of such poly-

  light-sensitive mothers are: 1) Polymers of mono and diolefins, e.g.

  polyethylene (which may be cross-linked), poly-

  propylene, polyisobutylene, polybutene-1, polymethyl-

  pentene-1, polyisoprene or polybutadiene, as well as

  polymers of cycloolefins such as, for example,

pentene or norbornene.

  2) Blends of the polymers mentioned in (1), for example mixtures of polypropylene with polyethylene or with polyisobutylene. 3) Descopolymers of mono and di-olefins with each other or with other vinyl monomers, for example butylene and propylene copolymers, copolymers of propylene and butene-1, copolymers, propylene and isobutylene, copolymers of ethylene and butylene-1, copolymers of propylene and butadiene, copolymers of isobutylene and isoprene, copolymers of ethylene and an alkyl acrylate, copolymers of ethylene and an alkyl methacrylate, copolymers of ethylene and vinyl acetate or copolymers of ethylene and acrylic acid and its salts (ionomers), and that-ter terpolymers of ethylene with propylene and

  a diene, such as hexadiene, dicyclopentadiene or ethyl-

ylidene-norbornene.

4) Polystyrene.

  ) Copolymers of styrene or alpha-methylstyrene with dienes or acrylic derivatives, for example

  styrene-butadiene, styrene-acrylonitrile, styrene

  ethyl methacrylate, styrene-butadiene-ethyl acrylate, styrene acrylonitrile methyl acrylate; mixtures,

  having a high impact resistance, the copolymers of the styrene

  and another polymer such as a polyacrylate,

  a diene polymer or a terpolymer of ethylene, propylene

  lene and diene; as well as block copolymers or

  long sequences 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, for example, styrene on polybutadiene, styrene and acrylonitrile on polybutadiene, styrene and maleic anhydride on polybutadiene, styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and acrylonitrile on terpolymers of ethylene, propylene and diene, styrene and acrylonitrile on poly (alkyl acrylates) or poly ( methacrylates

  alkyls), styrene and acrylonitrile on copoly-

  acrylate and butadiene, and their mixtures with copolymers mentioned in (5), such as those

  are known as ABS, MBS, ASA or AES polymers.

  7) Polymers containing halogen, such as polychloroprene, chlorinated rubber, polyethylene

  chlorinated or chlorosulphonated, des-homo- and copolymers of the epi-

  chlorohydrin, especially polymers of halogenated vinyl compounds such as, for example, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride,

  poly (vinylidene fluoride); as well as their copoly-

  such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or

vinylidene / vinyl acetate.

  8) Polymers which derive from unsaturated acids in alpha-

  beta and their derivatives, such as polyacrylates and poly-

  methacrylates, polyacrylamides and polyacrylonitriles.

  9) Copolymers of the monomers mentioned in (8), with each other or with other unsaturated monomers, such as, for example, copolymers of acrylonitrile and butadiene, copolymers of acrylonitrile and an acrylate, alkyl,

  copolymers of acrylonitrile and an alkoxyacrylate

  alkyl, copolymers of acrylonitrile and a vinyl halide, terpolymers of acrylonitrile, an acrylate

alkyl and butadiene.

  Polymers derived from alcohols and unsaturated amines

  or their acylated derivatives or their acetals, as

  cool polyvinyl, poly (acetate, stearate, benzoate, vinyl maleate), polyvinyl butyral, poly (phthalate

  allyl), polyallylmelamine.

  11) homo and co polymers of cyclic ethers, such as polyalkylene glycols, poly (ethylene oxide), poly (propylene oxide) or copolymers thereof with

glycidyl bis-ethers.

  12) Polyacetals, such as polyoxymethylene, as well as polyoxymethylenes which contain comonomers such as

for example, ethylene oxide.

  13) poly (oxides and sulfides of phenylenes).

  14. Polyurethanes derived from polyethers, poly-

  esters and polybutadienes having hydro-

  terminal xyls on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as their precursors

  (polyisocyanates, polyols, prepolymers).

  polyamides and copolyamides, which are derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or corresponding lactams, such as polyamide 4,

  polyamide 6, polyamide 6/6, polyamide 6/10, poly-

  amide 11, polyamide 12, poly (2,4,4-trimethyl hexamethyl)

  ethylene terephthalamide), poly (m-phenylene isophthalamide), as well as their copolymers with polyethers such as polyethylene glycol, polypropylene glycol, for example

or polytetramethylene glycol.

  16) Polyureas, polyimides and polyamide-imides.

  17) Polyesters, which are derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids or corresponding lactones, such as poly (terephthalate)

  ethylene), poly (butylene terephthalate), poly-

  (1,4-dimethylol cyclohexane terephthalate),

  (2- (4-hydroxyphenyl) propane terephthalate, polyhydroxybenzoates, as well as block polyether-esters, which are derived from polyethers having hydroxyl groups 5,

  dialkoolset of dicarboxylic acids.

18) Polycarbonates.

  19) Polysulfones and polyethersulfones.

  ) Crosslinked polymers, which are derived from aldehydes on the one hand and phenols from urea or melamine on the other hand, such as phenol-formaldehyde resins, urea-formaldehyde,

and melamine-formaldehyde.

  21) Drying and drying non-drying alkyd resins. 22) Unsaturated polyester resins derived from copolyesters of dicarboxylic-saturated and unsaturated acids with polyalcohols, as well as vinyl compounds as crosslinking agents, and also their modification products which are difficult to combust and which contain

halogen.

  23) crosslinkable acrylic resins, which are derived from substituted acrylic salt esters, for example

  epoxyacrylates, urethanes-acrylates or polyesters

acrylate esters.

  24) Alkyd resins, polyester resins and acrylic resins which are crosslinked with melamine resins, urea resins, polyisocyanates or polyesters.

epoxy resins.

  25) Crosslinked epoxy resins, which derive from poly-

  epoxides, for example bi-glycidyl ethers or di-

cycloaliphatic epoxides.

  26) Natural polymers, such as cellulose, rubber

  natural rubber, gelatins and their chemical derivatives

  modified and which are analogous polymers, such as acetates, propionates and butyrates of cellulose, or

  cellulose ethers such as methylcellulose.

  The stabilization of polyolefins, polymers of styrene, polyamides, polyurethanes and resins for lacquers and varnishes such as alkyd resins, acrylics

  and polyesters is particularly important.

  Stabilizers are added to plastics

  copolymers in a concentration of 0.01 to 5% by weight,

  on the material to be stabilized.

  pore 0.1 to 2% by weight of the compounds, the proportions being calculated on the basis of the material to be stabilized, in this material. The incorporation can take place during or after the polymerization, for example by mixing the compounds and possibly other additives in the melt, according to methods customary in the art, before or during the forming, or also by application of the compounds dissolved or dispersed on the polymer, optionally with evaporation

subsequent solvent.

  The new compounds can also be added in the form of a "masterbatcher", which contains these compounds for example in a concentration of 2.5 to 25% by weight,

polymers to stabilize.

  The invention therefore also relates to stable polymers

  bilized by the addition of 0.01 to 5% by weight of a compound of formula I and may optionally also contain other known and customary additives. The plastics thus stabilized may be used in various forms, for example example in the form of sheets, fibers, small strips, profiles or as binders for

  lacquers and varnishes, adhesives or sealants.

  As other additives, with which one can use

  stabilizers which can be used according to the invention include, for example: anti-oxygen compounds, such as 2,6-dialkyl phenols, alkylated hydroquinone derivatives, thiodiphenyl oxides,

  hydroxyls, alkylidene bisphenols, O-, N-

  and S-benzyls, hydroxybenzyl malonic esters, aromatic hydroxybenzyls, S-triazine compounds, beta- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid amides, esters of beta- (3,5-di-tert-butyl-4-hydroxy-3-methyl-3-phenyl) -propionic acid, esters of 3,5-di-tert-butyl-4-hydroxy-4-phenylacetic acid, acylaminophenols, benzylphosphonates, derivatives amino-aryls, ultraviolet absorbers, and agents for the protection against the effects of light,

  2- (2-hydroxyphenyl) benzotriazoles,

  (2-hydroxy-phenyl) -2,4-alkyl-6-triazinkymetric

  2-hydroxybenzophenones, bis (2-hydroxybenzoyl) -1,3-

  benzenes, esters of benzoic acids which may be

  acrylates, as well as nickel compounds, hindered amines, oxalic acid diamides, metal deactivating agents, phosphites, compounds which break down peroxides,

  stabilizing polyamides, basic stabilizers such as

  Co-stabilizers of PVC (polyvinyl chloride), nucleating agents having particular additives such as, for example, plasticizers, lubricants or release agents, emulsifiers, fillers, soot or carbon black, asbestos, kaolin, talc, glass fibers, pigments, optical brighteners,

  flame retardants, anti-inflammatory agents,

static electricity.

  Examples of other additives that can be used

  with stabilizers usable according to the invention

  can be found on pages 18 to 24 of DE-OS 2 427 853.

  When known stabilizers are used, synergistic effects can occur, which is often the case, especially when agents are also used.

absorption of ultraviolet.

  The copolymers according to the invention can also be used in the form of their salts.

  R do not represent acyl groups,

  The copolymers of the invention are capable of

  salts with acids, for example acid-chlorine

  water, phosphoric acid or sulfonic acids.

  Such copolymers, which contain free carboxyl groups, for example those in which component I of the group -YR represents -OH or those in which, in component II, group R 4 represents COOH, may also form salts, particular alkali metal salts,

with strong bases.

  The copolymers can also be used according to the invention.

  These are complex complexes with nickel acetate, nickel stearate or nickel acetylacetonate, as are their complexes with heavy metal compounds, particularly nickel or cobalt compounds. The following examples illustrate the production of the copolymers according to the invention and their use as agents for protecting against the effects of light.

  temperatures are given in C.

Example 1

  In a 1-liter autoclave (in "Hastelloy B"), comprising a magnetic stirrer stirrer or pallet, 34.5 grams (0.06 mol) of bis (1-benzyl-2-tetramethyl) fumarate are placed. , 2,6,6-piperidyl-4) (melting point: 177-178), dissolved in 250 ml of butyl acetate and 1.0 gram of azoisobutyronitrile (AIBN) is added. ethylene up to a pressure of 50 bar and the reaction mixture is heated for 8 hours with stirring at 88-90, obtaining a final pressure of 75 bar at 90. The reaction mixture is then concentrated, dissolved in chloroform and filtered through a layer of kieselgu ("hyflo"). The filtrate is concentrated to about 100 ml and stirred at room temperature under strong turbination in about 1 liter of methanol; the colorless fine powder which has thus been separated is filtered off and dried under high vacuum at 50 ° C. The copolymer of ethylene and bis (benzyl-1-tetramethyl-2,2) fumarate,

  6.6 piperidyl-4) thus obtained has a softening point

  approximately 100 and has an average molecular weight

  (Mn) of 7,300 (copolymer number 1).

  (C 38 H 54 N 204) calculated: N 4.65% (602.8) found: N 4.4%

Example 2

  In a similar manner to Example 1, 33.3 grams (0.07 mole) of bis (allyl-1-tetramethyl-2,2,6,6-piperidyl-4) fumarate are placed in a 1-liter autoclave ( melting point 121-122), 250 ml of butyl acetate and 0.8 gram of AIBN ethylene is extruded to 50 bar and copolymerized with vigorous stirring for 7 hours at

  88-90 The final pressure is 84 bar (at 90) Isolation

  The copolymer of ethylene and bis (allyl-1-tetramethyl-2,2,6,6-piperidyl-4) fumarate is

  in a manner similar to Example 1, the copolymer is obtained

  mother (number 2) in the form of a colorless powder whose softening point is approximately 65 and which has Mn of

3,900.

Example 3

  In a similar manner to Example 1, 31.1

  grams (0.065-mole) of bis- (acetyl-1 tetra-

  2,2,6,6-methyl-4-piperidyl) (mp 151-152), produced by transesterification of diethyl fumarate

  with 2 molar equivalents of acetyl-1-hydroxy-4-tetramethyl

  2,2,6,6-piperidine, (mp 129-130 ° and 1.0 gram of AIBN in 250 ml of butyl acetate, ethylene is blown to 50 bar and is heated for 6 hours with stirring at 88-90, obtaining a final pressure.

  (at 90) of 77 bar. The solvent of the copolymer is then removed.

  raw polymer under the depression of a water tube,

  The residue is dissolved in dichloromethane and filtered for

  clarify through a layer of "hyflo" After concentrating

  The filtrate is precipitated under strong turbination in 500 ml of hexane at room temperature, the precipitate is dissolved in a little dichloromethane and the solvent is completely removed in vacuo to obtain the ethylene copolymer. and bis (1-acetyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate in the form of a white sprayable mass having a softening point of

    and which has an Mn of 5,300 (copolymer number 3).

Example 4

  In a similar manner to Example 1, 10

  grams (0.04 moles) of N- (1,2,2,6,6-pentamethyl-4-piperidyl)

  Maleinimide (m.p .: 118-119;

  extraction of maleic anhydride and 4-amino-pentamethyl-1,2,6,6-piperidine) and 0.2 gram of AIBN in 80 ml of debutyl acetate in a 3-liter autoclave; we compress

  ethylene up to 50 bar and then copolymerized

  5 hours at 88-90 with powerful stirring.

Final at 88 is 70 bars.

  To isolate the copolymer from ethylene and N- (pentamethyl-1, 2,2,6,6-piperidyl-4) -maleinimide, the reaction mixture is filtered through "hyflo", then washed with

  dichloromethane, the filtrate is evaporated, the filtrate is dissolved again

  in a little dichloromethane and poured under

  powerful solution of the copolymer in 400 ml of acetonitrile.

  The precipitated copolymer (nu-

  mero 4): it softens to about 190 and has a weight

Mn average molecular weight of 7,300.

  Similarly, 10 grams (0.04 moles) of N-pentamethyl-1,2,6,6,6-piperidyl-4-malinimide and 0.5

  gram of AIBN in 80 ml of butyl acetate to a copolymer of

  The copolymer obtained has a softening point of 150 and a molecular weight, and is isolated in the same manner as in Example 4.

  average of 1900 (copolymer number 4a).

Example 5

  Z A) Copolymer of ethylene and bis (tetrachloride) fumarate

  2,2,6,6-methyl-4-piperidyl): In a similar manner to Example 1, 31.6 grams (0.08 mol) of bis (2,2,6,6-tetramethyl) fumarate were subjected to piperidyl-4) (melting point: 157-158) and 0.35 gram of AIBN in 250 ml of butyl acetate to copolymerization in a one-liter autoclave under a pressure of 40 bar

  of ethylene at 75 and the copolymer

lissement: about 800-820.

  B) Copolymer of ethylene and bis (allyl-1-tetramethyl-2, 2,6,6-piperidyl) fumarate by allylation of (A):

  To a solution of 9.3 grams (0.022 mol) of

  polymer produced according to (A) in 50 ml of methyl ethyl ketone,

  6 grams of allyl bromide and 7 grams of

  anhydrous potassium bonate (finely pulverized) and

  3 heated under nitrogen for 28 hours at 78-80.

  The reaction mixture is then filtered while hot and the solvent is removed in vacuo.

  little dichloromethane and slowly poured under

  powerful stroke in 300 ml of methanol The precipitate is separated

  and dried under high vacuum at room temperature The copolymer (number 5) allylated by reaction

  polymerization-like has a softening point

  approximately 90% and 1% of 11,800.

  (C 30 H 50 N 204) n calculated N 5.57% d O (502.7) n found N 5.3

Example 6

  A solution of 17.3 grams (0.03 mole) of fumarate (benzyl-1-tetramethyl-2,2,6,6-piperidyl-4) was subjected to

  12 grams (0.12 moles) of ethyl acrylate and 0.6 grams.

  5% of tert-butyl perbenzoate in 50 ml of butyl acetate to a copolymerization with stirring in a nitrogen atmosphere 115-116 for 26 hours At the end of this time,

  can no longer detect any monomeric constituents in the

  Polymerization mixture The reaction mixture is then concentrated, and it is stirred under powerful turbulence at room temperature in 400 ml of ethanol. The entrained methanol is separated from the copolymer (number 6) of ethyl acrylate and bisphenol fumarate. (2,2,6,6-benzyl-2,2,6,6-tetramethylpiperidyl) precipitated and dried under high vacuum at

    Softening point: 88-90; Mn: 3,700.

not

Example 7

  In a similar manner to Example 6, one submits a

  24 grams (0.05 mole) of bis- (1-acetyl-2,2,6,6-tetramethylpiperidyl-4) fumarate, 22.5 grams (0.1 mole)

  of pentamethyl-1,2,6,6-piperidyl-4 and 0.6 gram-

  me of tertiobutyl perbenzoate as an initiator in

  ml of anhydrous toluene to a copolymerization in atmospheric

  The toluene is then distilled off in a rotary evaporator, the residue is dissolved in a little methylene chloride, poured under vigorous stirring into 800 ml of acetonitrile,

  the precipitated copolymer is separated from fumarate

  1-tetramethyl-2,2,6,6-piperidyl-4) and pentamethyl-1,2,2,6,6-piperidyl-4 acrylate and is dried under high vacuum at 50 It has a softening point of

  108-110 and an Mn of 2900 (copolymer number 7).

Example 8

  In a similar manner to Example 6, a solution of 14.24 grams (0.03 mole) of bis (allyl-1-tetramethyl-2,2,6,6-piperidyl) fumarate 4, 6 grams 0.6 mol) of ethyl acrylate and 0.3 gram of tert-butyl perbenzoate as initiator in 130 ml of butyl acetate copolymerized under nitrogen for 20 hours at 1100. Then the solution of the copolymer under After emptying, the residue is dissolved in methylene chloride, filtered for clarification and the concentrated filtrate is poured into 1 liter of methanol to precipitate under strong turbination at -10. The precipitate is filtered off and dried under vacuum. The copolymer thus obtained of ethyl acrylate

  Zo and bis- (allyl-1 2,2,6,6-tetramethylpiperamine fumarate)

  ridyl-4) has a softening point of about 135 and an average molecular weight (Mn) of 8000 (copolymer

number 8).

Example 9

In a similar manner to Example 6, a solution of 20:11 was refluxed for 28 hours under nitrogen.

  grams (0.035 moles) of bis- (benzyl-1 tetramethyl) fumarate

  2,2,6,6-thyl-4-piperidyl), 3.93 grams (0.035 mole) of octene-1 and 0.2 gram of tert-butyl benzoate in ml of toluene. The copolymer is precipitated by pouring the solution into toluene. of the cold acetonitrile and purified by further dissolution in methylene chloride and precipitation with acetonitrile After drying under vacuum, the copolymer of octene and fumarated bis- (benzyl-l)

  % $ 2,2,6,6-tetramethyl-4-piperidyl) softens to 125 and pre-

  has an Mn of 2,600 (copolymer number 9).

Example 10

  A) Copolymer of ethylene and diethyl maleate:

  The mixture is refluxed for 12 hours at 126.2 grams.

  mols (1 mole) of a copolymer of ethylene and maleic anhydride ("EMA-1103" resin from Monsanto) in 600 ml of absolute ethanol with addition of 0.4 gram of p-acid. toluenesulphonic The homogeneous solution is then cooled to a completely clear solution and 131 grams (1.1 mol) of thionyl chloride are added dropwise under strong stirring for 4 hours. The reaction mixture, cooled to 0, separates at rest after a short time in two phases. The lower phase is separated and washed.

  three times at 0 with 100 ml of ethanol, and eliminates

  The copolymer of ethylene and diethyl maleate thus obtained still has 8 x 10-5 equivalents of free carboxyl group per gram, i.e. about 99 2% of all carboxyl groups are present in ester form

ethyl.

  B) Copolymer of ethylene and bis (benzyl-1-tetramethyl-2, 2,6,6-piperidyl) maleate: 20 grams (0.1 mole) of the copolymer obtained according to (A) were subjected to 24 hours at about 130-135 to transesterification with 50 grams of 1-benzyl-4-hydroxy-2,2,6,6-tetramethyl piperidine and 0.4 ml of tetrabutyl ortho-titanate in 400 ml of anhydrous xylene under a low The stream of nitrogen is continuously distilled off from the reaction mixture. The xylene is then completely distilled off and the residue is heated to a pressure of about mbar for a further 8 hours at 165.degree. The copolymer is then redissolved in 150 ml of hot xylene and this solution is poured under powerful turbination into a liter of a 1: 1 mixture of methanol and ethanol,

  causes the precipitation, in the form of a powder, of the copo-

  ethylene amine and bis (1-benzyl) tetramethyl maleate

  2,2,6,6-piperidyl-4) The precipitate is filtered off, washed with a 1: 1 mixture of methanol and ethanol and

  it is dried under high vacuum at 60-70 o softening point

  approximately 120; Mn 300 (copolymer number 10).

  (C 38 H 54 N 204) n calculated: N 4.65% (602.8) found: N 4.35%

Example 11

  A) Copolymer of ethylene and of dibutyl maleate: In a similar manner to Example 10 A, 63.1 grams (0.5 mole) of a copolymer of ethylene-Ao and of commercial maleic anhydride (Monsanto "EMA-1103" resin) with 300 ml of n-butanol followed by 77.4 grams of thionyl chloride (freshly distilled) to obtain a copolymer of ethylene and dibutyl maleate. After distilling off the excess of n-butanol, the crude copolymer is washed again with cold methanol and then completely removed.

  the volatile constituents under high vacuum at 130 / 0.01 bar.

  The resinous copolymer of ethylene and butyl maleate has a residual free acid content of 7 x 105

Zo equivalents / grams.

  B) Copolymer of ethylene and bis (allyl-1-tetramethyl-2,2,6,6-piperidyl) maleate: The preparation is carried out analogously to Example 10B by reaction of the copolymer, product according

  11.A, with allyl-1-hydroxy-4-tetramethyl-2,2,6,6-piperine

  Z 6 dine and constant distillation of butanol The copolymer thus obtained of ethylene and of bis- (allyl-1) maleate

  tetramethyl-2,2,6,6-piperidyl-4) has a softening point

  about 100 and a molecular weight M of about

not

  11,500 (copolymer number 11).

  (C 30 H 50 N 204) n calculated: N 5.57% (502.7) found: N 5.1% n

Example 12

  39 grams of a commercial maleic anhydride / methyl oxide / vinyl copolymer having a weight Mn of 16,000 ("Gantrez AN119" resin from GAF Corp.) are dissolved in 350 ml of methyl ethyl ketone and a solution of 72 grams of butylamino-4-benzyl-1-tetramethyl-2,6,6,6-piperidine is added dropwise thereto under stirring at 70 (under N 2) over a period of 4 hours, followed by stirring for 8 hours. 70-75 The fine granular precipitate which precipitated during the reaction was filtered off, washed with methyl ethyl ketone and dried at 60 ° C. under high vacuum. methyl and

  vinyl and 1-benzyl-2,2,6,6-tetramethylpiperidyl-4-mono-

  amide of maleic acid softens to 200 (copolymer

number 12).

  (C 27 H 42 N 204) n -calculated: N 6.11% (458.6) found: N 5.75%

Example 13:

  A solution of 36.3 grams (0.08 mole) of bis (1-acetyl-2,2,6,6-tetramethyl) fumarate is copolymerized.

  piperidyl-4) (melting point: 151-152) and 16.8 grams

  Zo mes (0.12 mol) of decene-1 in 200 ml of pure toluene in the presence of 0.4 gram of tert-butyl perbenzoate under nitrogen for 24 hours at 106-108. Then about half of the toluene is distilled off. under vacuum and poured slowly, under powerful turbines at room temperature,

  the solution thus concentrated in 500 ml of hexane

  The precipitated copolymer is washed with hexane and

  it is completely dried at 60 under high vacuum.

  mother of decene-1 and bis- (acetyl-1-tetramethyl-2,2,6,6-piperidyl-4) fumarate thus obtained has a softening point

  about 90 and an average molecular weight

  (Mn) of 3300 (copolymer number 13).

  (C 36 H 62 N 20) n calculated: N 4.53% (618.6) found: N 4.8%

Example 14

  Analogously to Example 13, 10 grams (0.04 moles) of N- (pentamethyl-1,2,6,6,6-piperidyl-4) -melineimide were copolymerized under argon at 106 ° -107 for 24 hours. 8.75 grams (0.052 mole) of dodecene-1 in 70 ml of pure toluene

  by addition of 0.2 gram of tert-butyl perbenzoate.

  The toluene is then distilled off in vacuo, the residue is dissolved in a little dichloromethane and the mixture is poured slowly with vigorous stirring by stirring at 0-5 into 500 ml of acetonitrile. first soft, washed with acetonitrile

  and completely dried under high vacuum at about 70.

  The copolymer of dodenene-1 and N- (pentamethyl-1,2,6,6,6-piperidyl-4) maleinimide thus isolated has a point of

  softening of about 140 and a weight Mn of 1850 (copro-

not

lymere number 14).

Example 15

  The mixture is heated in an N 2 atmosphere with stirring of

  17 hours at about 35.1 grams (0.1 mole) of a 1: 1 copolymer of octadecene-1 and commercial maleic anhydride ("Gulf PA-18") and 17, 1 gram (0.1 mole) of 4-amino pentainethyl-1,2,2,6,6-piperidine dissolved in 250 ml of dimethylformamide, and the water formed is slowly distilled off and the dimethylformamide

  have distilled off the greater amount of

  thylformamide, the temperature at 175-180 was

  The bath temperature is then maintained for another hour at 180 under a vacuum corresponding to 30 mm of mercury (about 40 mbar). The product is then cooled to about 800, dissolved in 1,2-dichloroethane. This methane solution is slowly poured under vigorous stirring by tumbling into a liter of methanol so that the imide copolymer precipitates out. It is separated from the methanol which covers it and dried under high vacuum at 80.degree. , 02 mm of mercury (2.66 x 10-2 mbar) The imide copolymer thus obtained, of structure:

CH-CH-CH-CH -

16 33 O /, YO

I.

CH "CH

3 \ j 1/3

CH \ N \ C

31 3

  CH 3 n has a softening point of about 130 and a weight Mn of 10,500 (copolymer number 15). It dissolves easily in hexane to give a clear solution. The 13 C nuclear magnetic resonance spectrum corresponds to the structure indicated

Example 16

  In a manner analogous to Example 14,

  from 42.1 grams (0.12 mole) of the octadecane copolymer

  and maleic anhydride (Gulf "PA-18") and 18.8 grams (0.12 mole) of 4-amino-2,2,6,6-tetramethylpiperidine in dimethylformamide imide copolymer having the repeated structural pattern:

-CH CH -CH-CH

{I I

C 16 H 33%

3

CH \ CH

3 \ j il / 3

CH 3 / V CH 3

  c 3 x T'Xc 3 H n Precipitation in 1.2 liters of methanol gives a powder

  virtually colorless that is dried under high vacuum at 80.

  This product has a softening point between 120 and 130 and an Mn of 11 000. It can dissolve in hexane to give a clear solution (copolymer

number 16).

  Examples 17 to 28: In analogy to Example 13, 1: 1 copolymers are produced from the following pairs of monomers: Copolymer No. 17: Debis-benzyl-1-tetramethyl-2,2,6,6-piperidyl fumarate 4) and octadecene-1; softening temperature: about 64;

M 2 600.

n copolymer n 18:

  N, N'-bis- (benzyl-1-tetramethyl-2,2,6,6-piperidyl-4) -fumarone

  diamide and octene-1; softening temperature: about

140; M 2 260.

  Copolymer No. 19: Bis (2,2,6,6-tetramethylpiperidino) ethyl fumarate and

  octene-1; softening temperature: 57.65; Mn 1,930.

  Copolymer No. 20: Bis (allyl-1-tetramethyl-2,2,6,6-piperidyl) fumarate and

  butyl oxide and vinyl; softening temperature

approximately 90; N 3,000.

  n-21 Copolymer: Bis (1-benzyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate

  and vinyl acetate; softening temperature: approx.

142; Mn 3 100.

Copolymer n 22:

C 3,, CH 3 CLQ 3 / CH 3

CH-N "/ 3 NH- = O N / 3

  -CH 2 -OOC-CH =CH-COO-CH 2 CH 3 3 G 3 c H 3 6 222 C 2 c H 3

  and decene-1; softening temperature: 110; Mn 3 030.

  Copolymer No. 23: Bis (1-acetyl-2,2,6,6-tetramethyl-4-piperidyl) fumarate

  and N-vinylpyrrolidone; softening temperature: approx.

170; M 4,600.

  Copolymer No. 24: Ce 3 / CH 3 Ct 3, CH 3

  0 = NH-CH CH OOC-CH = CH-COOCCH -N / O

  ## STR1 ## wherein: ## STR1 ## and octene-1; softening temperature (Tr) about 98;

M 4,300.

  Copolymer No. 25: Bis (benzyl-1-tetramethyl-2,2,6,6-piperidyl) fumarate and styrene; softening temperature (Tr) 140;

M 2 250.

  Copolymer No. 26: Bis (benzyl-1-tetramethyl-2,2,6,6-piperidyl) fumarate and octene-1; softening temperature (Tr) about; Copolymer No. 27: Bis (benzyl-1-tetramethyl-2,2,6,6-piperidyl) fumarate and dodecene-1; softening temperature (Tr) about

 ; M 2 100.

  Copolymer No. 28: Bis (acetyl-1-tetramethyl-2,2,6,6-piperidyl) fumarate and 1-acetyl-2,2,6,6-tetramethyl-4-piperidyl acrylate;

  softening point (Tr) about 86; Mn 1 960.

  Examples 29 and 30: In a similar manner to Example 4, 1: 1 copolymers of the following structure are produced: Copolymer n 29: Tr about 230 M about 16,000 n Copolymer n 30 n T about 210 r C 1 -i "CH 3 CH 2 H 3 3 HM about 2,200 n

Example 31:

  In a similar manner to Example 12, from 1: 1 copolymer of maleic anhydride and commercial octadiene ("Gulf P-18") and 1-acetyl-2,2-tetramethyl are produced, 6.6 piperidinol-4 a copolymer (n 31) which is a half-ester of structure -r 1 H CH 1 n

16 33 OOH

CH./ * CH 3

H 3

C $ OCH 3

  C 3 which softens to 190 and is poorly soluble in most

solvents.

Example 32

  Protection effects with regard to light, in polypropylene sheets 10 minutes at 2000 ° C. in a Brabender plastograph 100 parts of polypropylene powder ("Moplen", quality for fibers, from the Montedison Company) were homogenised with 0.2 part

  beta-bis (3,5-ditertiobutyl-4-hydroxyphenyl) propionate

  tadecyl, 0.1 part calcium stearate and 0.25 part

  of a stabilizer from Table 1 below.

  As quickly as possible, the composition thus obtained is compressed in a knee press to obtain a plate 2 to 3 mm thick. A part of the raw molded part thus obtained is cut out and compressed between two sheets of hard aluminum with high gloss using a laboratory hand-held hydraulic press, for 6 minutes at 2600, to obtain a sheet of 0.1 mm thickness that

  it is cooled immediately in cold water.

  die-cut on this sheet of pieces that

  "Xenotest 1200" is illuminated in

  vales of time, these specimens are removed from the

  light exposure and the carbonyl content is checked in an infrared spectrometer The increase in carbonyl extinction, at 5.85 microns

  exposure to light is a measure of decomposition

  position, by photooxidation, of the polymer (see L Balaban et al., Polymer Sci, part C; 22, 1059-1071 (1969)) and it is found experimentally that this is related to a

  decrease in the mechanical properties of the polymer.

  As a measure of the protective effect, time is used

  that to obtain a carbonyl extinction of about 0.3 for which the comparison sheet is brittle For an unstabilized test specimen, this time amounts to about

900 hours.

  Stabilizing Copolymer Effect of exposure to light number (in hours)

1 3 220

2 4 900

3 3,600

  Stabilizing copolymer number Effect on light exposure (in hours) 4,200 3,730 3,720,000 3,000 4,800

> 5,500

> 4,300

> 5,000

4,500 3,870

2 3,000

> 2,900

74 400 -

4,360

> 5,500

770

> 2,350

2 511380

Claims (5)

claims   1. Copolymers of a polyalkylpiperine derivative   unsaturated ridine, characterized in that they derive from a) at least one unsaturated polyalkylpiperidine derivative of formula I o o 1 il II 2 R -XC-CH = CH-C-Y-R   and b) at least one comonomer of formula II R 3 I_ 4 CH 2 = C-R   In which R 1 represents one of the groups of formula III, IV, VI, VII or VIII (1) R -CH, CH R 6 \ 7- / 3 / 6 6 R C 2 / CH 3, R 8 _N / \ / IN-1 R 6 / N-H -It RCI CH 2H- R H 2 C 3 6 CH 6 C \ 3, CH 2 R R 7 \ N__II '2 C \ 3 C 2 R (IV) 6 C 113 CH R 6 R 7 9 <> CH 2 H- R 3 (y) (VI) (V) R 6 C 2 / CH 3 / R 6 17 R 5 _ / R / 0 - O \ CH 2) (VII) 6 R Ci 12 CH Ct 2 3 R R 2/3 17 1 / O \ / - C 12 / R -CII-CH -N * C (VIII) 6 2 \   Is one of groups III, IV, V, VI, VII or VIII or a hydrogen atom, an alkyl group (1 to 18 carbon atoms) or an alkyl group interrupted by -O-, alkenyl (3 to 5 carbon atoms), aralkyl (7 to 11 carbon atoms) or cycloalkyl (5 to 12 carbon atoms), 2 OX and Y are each, independently, O or NR 10 R is an atom of hydrogen or a methyl group, R 4 represents a hydrogen atom, an alkyl group (1 to 18 carbon atoms), phenyl, C 1, CN, alkoxy (1 to 18 carbon atoms), alkanoyloxy (2 to 5 carbon atoms), -COOR 1, -CONH 2 or -CON (R 12) (R 13), 2 R is alkenyl (3 to 5 carbon atoms), alkynyl (3 to 5 carbon atoms) , -CH 2 -CH (OH) -R, -CH 2 CN, unsubstituted or substituted aralkyl for example alkyl (1 to 4 carbon atoms), alkanoyl (2 to 18 carbon atoms), alkenoyl (3 to 5 carbon atoms) of carbon), -OH, -O (Oxygen of the oxy group), COO-alkyl (1 to 4 carbon atoms) or -CON (R 12) (R 13),   R 6 is a hydrogen atom or an alkyl group (1 to 5 carbon atoms),   R 7 is a hydrogen atom or an alkyl group (1 to 3 atoms)   carbon monoxide), phenyl, alkoxymethyl (1 to 4 carbon atoms   carbon in the alkoxy group), phenoxymethyl or alkylphenyl   Noxymethyl (1 to 4 carbon atoms in the alkyl group), R 8 is a hydrogen atom, an alkyl group (1 to 18 carbon atoms), alkenyl (3 to 5 carbon atoms), alkynyl   (3 to 5 carbon atoms), alkanoyl (2 to 18 carbon atoms),   bone), alkenoyl (3 to 5 carbon atoms), aralkyl (7 to 11 carbon atoms), unsubstituted or substituted with an alkyl group (1 to 4 carbon atoms), -CH 2 CN, -CH 2 CH (OH) -R or -CON (R 12) (R 13), R represents a hydrogen atom, an alkyl group (1 to 18 carbon atoms), alkenyl (3 to 5 carbon atoms) or aralkyl (7 to 11 carbon atoms), R 10 is a hydrogen atom or an alkyl group (1 to 18 carbon atoms), cyclohexyl, aralkyl (7 to 11 carbon atoms), phenyl or a group of the formula III, R 1 l represents a hydrogen atom, an alkyl group (1 to   18 carbon atoms), hydroxyalkyl (2 to 4 carbon atoms)   bone), glycidyl or a group of formula III, IV, V, VI, VII or VIII or a group of formula IX, R 6 XR 6 R Ct ,, CH 3 / R R 14 _-N (IX), R 6 Cf 12 \ CH 3 - RC 2 C 3   (wherein R 1 is a hydrogen atom or an alkyl group (1 to 18 carbon atoms)), R 1 represents an alkyl group (1 to 12 carbon atoms), cycloalkyl (5 to 8 carbon atoms), phenyl, benzyl or a group of formula III or IX and R 13 represents a hydrogen atom, an alkyl group (1 to 12 carbon atoms), cycloalkyl (5 to 8 carbon atoms) or benzyl, or: 12 13   R and R, taken together with the nitrogen atom to which they are attached, form a heterocyclic ring having 5 to 7 carbon atoms, R 17 represents a hydrogen atom or a methyl or ethyl group, p is zero or is 1, and q is 1 if p is zero and is zero or is 1 if p is 1 i, or copolymers characterized in that they are derived from: a) at least one maleinimide of formula Ia o il (Ia) (in which R 15 is a group of formula III or IX) and b) at least one comonomer of formula I Ia CH 2 = CH-R 16 (I Ia)   (wherein R 16 is a hydrogen atom or a group   alkyl having 1 to 18 carbon atoms), the number average molecular weight of the copolymer being   between 1,000 and 50,000 and in particular between 1,000 and 10,000.   2 Copolymers according to claim 1, characterized   in that R represents a hydrogen atom in the   formulas III, IV, V, VI, VII, VIII and IX.   3. Copolymers according to claim 1, in that 2 1   R represents R, or a hydrogen atom or an alkyl group (1 to 18 carbon atoms), R 4 represents a hydrogen atom, an alkyl group (1 to 6 carbon atoms), phenyl, alkoxy (2 to 6 carbon atoms), acetoxy or -COOR, R is alkenyl (3 to 5 carbon atoms), alkanoyl (2 to 6 carbon atoms), alkenoyl (3 to 5 carbon atoms), benzyl, -CH 2 CN or CON (R 12) (R 13), R 6 is a hydrogen atom, R 8 represents a hydrogen atom, an alkyl group (1 to 6 carbon atoms), alkenyl (3 to 5 carbon atoms ), alkanoyl (2 to 6 carbon atoms), alkenoyl (3 to 5 carbon atoms), benzyl or CH 2 CN, R 9 represents a hydrogen atom, an alkyl group (1 to 12 carbon atoms), allyl or benzyl,   R 10 is a hydrogen atom or an alkyl group (1-8 atomic);   carbon number), Ril represents an alkyl group (1 to 8 carbon atoms),   hydroxyalkyl (2-4 carbon atoms) -, or a group of   mule III, IV, V, VI or IX or R 14 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 12 and R 13 represent an alkyl group (1 to 8 carbon atoms), cyclohexyl or benzyl, and R 1, X and Y, R 3, R 7, R 15 and R are as defined in claim 1, the number average molecular weight of the copolymer being between   1,000 and 10,000 and in particular between 1,000 and 5,000.   4. Copolymers according to claim 1, characterized   derived from: a) a compound of formula I (in which R is a group of formula III; R is R or an alkyl group (1 to   8 carbon atoms); X and Y are each an oxy-   gene; and in formula III, R 5 is an allyl, benzyl or acetyl group and R 6 is a hydrogen atom), and, b) a compound of formula II (wherein R 3 is H or CH 3; R represents H, an alkyl group (1 to 6 carbon atoms) or -COOR 1; R 1 is an alkyl group (1 to 4 carbon atoms or a group of formula III, in which   R 5 is acetyl or benzyl and R 6 is a hydrogen atom   or R 1 is a group of formula IX, in the   wherein R is H and R 14 is H or CH 3), or in that they are derived from: a) a compound of formula Ia (wherein R 15 is a group V of formula IX in which R 6 is H and R 14 is H or CH 3), and   b) a compound of formula I Ia (in which R 5 has the indi-   as claimed in claim 1), the number average molecular weight of the copolymer being   3 between 1,000 and 10,000 and in particular between 1,000 and 5,000.   5. Copolymers according to claim 1,   as derived from (a) a compound meeting the requirements of   formulas I or Ia according to claim 1, and (b) ethyl   in a molar ratio of approximately 1: 1.   A copolymer stabilized against the deleterious effects of light as it contains, as a light-protective agent, 0.01% by weight, preferably 0.1-2% by weight. , at least   a copolymer according to claim 1.   A stabilized polymer according to claim 6, characterized in that it is a polyolefin, a styrene polymer, a polyamide, a polyurethane, or a resin for lacquers or varnishes.   Stabilized polymer according to Claim 6, characterized in that it contains still other additives, in addition to the protective copolymer agent with respect to effects of light.   Forty-one pages Company known as: CIBAGEIGY AG Representative: CABINET ARMENGAUD NE 23, Bouleva e Strasbourg, PARIS (1 (