EP0000769A2

EP0000769A2 - Polymers containing polyalkylpiperidines and use thereof as stabilizers

Info

Publication number: EP0000769A2
Application number: EP7878100573A
Authority: EP
Inventors: Nobuo Soma; Syoji Morimura; Takao Yoshioka; Tomoyuki Kurumada
Original assignee: Sankyo Co Ltd
Current assignee: Sankyo Co Ltd
Priority date: 1977-08-08
Filing date: 1978-08-02
Publication date: 1979-02-21
Also published as: US4265803A; IT1097576B; EP0000769B1; IT7826310A0; EP0000769A3; JPS6332782B2; JPS5429400A; DE2860899D1

Abstract

Polymers containing polyalkylpiperidines and use thereof as stabilizers for synthetic polymer compositions are described. In said polymers, sterically hindered polyalkylpiperidines are linked in the main chain via bridging members containing 2-hydroxy-1,3-trimethylene groups, or derivatives thereof. The polymers are distinguished by an improved stabilizing effect in various synthetic polymer compositions, such as polyolefins, against light- and/or heat-induced deterioration thereof. The polyaikylpiperidine-containing polymers of the invention are hardly volatile upon heat- processing or during storage of shaped articles containing said polymers, and are resistant to extraction with solvents.

Description

The present invention relates to novel polymers containing sterically hindered polyalkylpiperidines and which are useful as stabilizers for synthetic polymers, and synthetic polymer compositions stabilized against light- and heat-deterioration containing said novel polymers.
It is known that polyalkylpiperidine derivatives in which the 1- and/or 4-positions are substituted are effective polymer stabilizers against light- or heat-induced degradation thereof. For example, 4-spirohydantoins of 2,2,6,6-tetramethylpiperidine or 2,6-diethyl-2,3,6-trime- thylpiperidine are disclosed in U.S. Patents nos. 3,542,729, 3,705,126, 3,941,744, 4,005,094 and 3,898,303 and German Offenlegungsschrift no. 2,623,464; amino derivatives are disclosed in U.S. Patents nos. 3,684,765 and 3,904,581 and German Offenlegungsschrift no. 2,621,870; esters, ethers and carbamates of 4-piperi- dinols are disclosed in U.S. Patents nos. 3,640,928, ₃,₈4₀,4₉4, 4,₀21,4₃₂, ₃,94₀,363, ₃,₉₉₃,6₅₅ and 4,075,165 and German Offenlegungsschrift 2,647,452; ketals of 4-oxo compounds are disclosed in U.S. Patents nos. 3,899,464 and 3,940,363 and German Offenlegungsschrift no. 2,621,855; and pinacol type derivatives are disclosed in U.S. Patents nos. 4,061,616 and 4,055,536 as well as Japanese'Provisional Patent Publication no. 51-145548, respectively. Furthermore, polymers containing 4-amino- polyalkylpiperidines as the side chain are proposed in German Offenlegungsschriften nos. 2,611,208, 2,636,144 and 2,636,130.
The invention provides polymers in which groups containing polyalkylpiperidines represented by the general Formulae:
wherein R1 represents a hydrogen atom or a methyl group, are linked in the main chain via bridging members containing groups having the formula
, or derivatives thereof.
The new polymers show improved stabilizing effect in various polymeric materials against light- and heat-degradation thereof, with less sublimation and exudation therefrom.
The polymers of the present invention containing polyalkylpiperidines are represented by the following formula (I) :
In the above formula, 1 represents an integer of from 2 to 50, preferably 2-10, and most preferably 2-6.
Both m₁ and m₂ represent 0, or one of them represents 1 and the other represents 0.
X represents a group of formula
R' represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
n₁ represents an integer of from 1 to 10, preferably 1.
n₂ represents 0 or an integer of from 1 to 10, preferably 0.
W represents a group of formula
n₃ represents an integer of from 1 to 10, preferably 4 to 10, most preferably 4. As such groups may be mentioned, for example, the malonyl, succinyl, adipoyl, suberoyl, sebacoyl or decane-1,10-dicarbonyl group.
W further represents a group of formula
e.g. isophthaloyl or terephthaloyl, preferably phthaloyl, ) or a group of formula
e.g. cyclohexane-1,2-dicarbonyl.
Y represents, when both m_l and m₂ are 0, one of the following formulae (II) to (IV):
in which R₁ represents a hydrogen atom or a methyl group, preferably a hydrogen atom, and R₂ represents a hydrogen atom or an alkyl group having from 1 Lo 18 carbon atoms, e.g. methyl, ethyl, n-propyl, n-butyl, octyl, dodecyl or octadecyl, particularly methyl. Preferably, R₂ is a hydrogen atom.
in which R₁ has the meaning given above.
in which R₁ has the meaning defined above, R₃ represents a group of formula -CH₂ or
-CH₂ C R₄, and R₄ represents the methyl or ethyl group.
Y represents, when one of m_l and m₂ is 1 and the other is 0, a group of the following formulae (V) to (XI):
in which: R₁ and R₂ have the meanings defined above.
A represents an alkylene group having from 2 to 12, preferably 2 to 6, and most preferably 6 carbon atoms, e.g. ethylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene; a xylylene group, e.g. o-, m- or p-xylylene, preferably p-xylylene; a group of formula
a group of formula -CH₂COO-R₅-OCOCH₂- in which R₅ is an alkylene group having from 2 to 8 carbon atoms, e.g. ethylene, tetramethylene, hexamethylene or 2-ethyl-1,6-hexylene, preferably ethylene; a group of formula
in which R₆ represents a hydrogen atom, a methyl group or a phenyl group, preferably a hydrogen atom, and R₇ represents an aliphatic, aromatic or alicyclic diacyl group havhg up to 12 carbon atoms, for example, an alkanedicarbonyl group having from 4 to 12 carbon atoms and which is optionally interrupted by sulfur, such as malonyl, succinyl, adipoyl, sebacoyl, decane-1,10-dicarbonyl or 3.3'-thiodipropionyl, phthaloyl, isophthaloyl, terephthaloyl or cyclohexane-1,4-dicarbonyl; or a group of formula
in which p is 0 or 1, preferably 1, R₈ has the same meaning as the above-defined X, and Z has the meaning defined below.
in which:

R₁ has the meaning defined above. R₉ represents an alkyl group having from 1 to 18, preferably 1 to 8 carbon atoms, e.g. methyl, ethyl, n-propyl, n-butyl, n-octyl, 2-ethylhexyl, undecyl or octadecyl; a phenyl group; a benzyl group; a cyclohexyl group; or an aliphatic, aromatic, araliphatic or alicyclic acyl group having up to 18 carbon atoms, for example, an alkanoyl group having from 2 to 18 carbon atoms such as acetyl, propionyl, hexanoyl, octanoyl, 2-ethyl- hexanoyl, lauroyl or stearoyl, benzoyl, toluoyl or 3-(2,4-di-tert-butyl-4-hydroxyphenyl)propionyl.R₉ most preferably is an alkyl group having from 1 to 4 carbon atoms or the acetyl group.

B represents an alkylene group having from 2 to 10, preferably 2 to 6 carbon atoms, e.g. ethylene, tetramethylene, hexamethylene, octamethylene or decamethylene; a xylylene group, e.g. o-, m- or p-xylylene, preferably p-xylylene; a group of formula
a group of formula -CH₂COO-R₅-OCOCH₂- in which R₅has the meaning defined above; a group of formula
in which R₆ arid R₇ have the meanings defined above; or a group of formula
in which R₈ and p have the meanings given above and Z has the meaning defined below.
in which:

R₁ has the meaning defined above.

D represents an aliphatic, aromatic, araliphatic or alicyclic diacyl group having up to 36 carbon atoms, for example diacyl groups as described under R_7' an alkanedicarbonyl group having from 4 to 12 carbon atoms and which is optionally interrupted by sulfur, phthaloyl, isophthaloyl, terephthaloyl or cyclohexane-l,4-dicarbonyl, or a diacyl group derived from a dimeric acid, or a group of formula
in which R₁₃ represents an alkyl group having from 1 to 4 carbon atoms, a benzyl group or a 3,5-di- tert-butyl-4-hydroxybenzyl group and R₁₄ has the same meaning as R₁₃ or represents a hydrogen atom; or a group of formula -CONH-R₁₀-NHCO- in which R₁₀ represents an alkylene group having from 2 to 10, preferably 6 carbon atoms, e.g. ethylene, tetramethylene, hexamethylene, octamethylene or decamethylene, a phenylene group optionally substituted with methyl, e.g. o-, m- or p-phenylene, particularly 2,4-tolylene, a naphthylene group, e.g. 1,5-naphthylene, a xylylene group, e.g. p-xylylene, a cyclohexylene group optionally substituted with methyl, e.g. 1,4-cyclohexylene or methyl-2,4-cyclohexylene, a group of formula
in which R₁₁ represents an oxygen atom or a methylene group, a group of formula
a group of formula
or a group of formula

in which:

R₁ and R₃ have the meanings given above.
G has the same meaning as the above-defined D, or it represents an alkylene group having from 3 to 10, preferably 4 to 6 carbon atoms, e.g. trimethylene, tetramethylene, hexamethylene, octamethylene or decamethylene; a xylylene group, e.g. o-, m- or p-xylylene, preferably p-xylylene; a group of formula
or a group of formula
in which R₈ has the meaning defined above and Z has the meaning defined below.
in which R₁ has the meaning defined above.
in which R₁ has the meaning defined above.
in which R₁ has the meaning defined above.

All of Z in the molecule represent a hydrogen atom; an alkyl group having from 1 to 18 carbon atoms, e.g. methyl, ethyl, n-propyl, n-butyl, octyl, dodecyl or octadecyl, particularly methyl; an aliphatic, aromatic, araliphatic or alicyclic acyl group having up to 18 carbon atoms, for example as described under R₉, an alkanoyl group having from 2 to 18, preferably 2 to 4 carbon atoms, benzoyl, toluoyl or 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl; a group of formula -CONHR₁₂ in which R₁₂ is an alkyl group having from 1 to 18, preferably 1 to 4 carbon atoms, a phenyl group or a cyclohexyl group.
Alternatively, a part of Z in the molecule may represent hydrogen atoms while the remaining Z represent above-defined groups other than hydrogen.
Preferably, all of Z in the molecule represent hydrogen atoms, acetyl or benzoyl groups, or a part of Z in the molecule are hydrogen atoms and the remaining Z are acetyl or benzoyl groups.
In formula (I), the terminal groups -CH₂-CH-CH₂- may be present as groups of formula
OH which impart a similar stabilizing effect and are included within the scope of the polymers of the invention.
Among the polymers of formula (I), preferred groups are as follows:

1) in formula (I), when both m₁ and m₂ represent 0;
1-a) polymers in which Y is a group of formula (II) and R₁ and R₂ are hydrogen atoms,
1-b) polymers in which Y is a group of formula (III) or (IV) and R₁ is a hydrogen atom;
2) in formula (I), when one of m₁ and m₂represents 1 and the other represents 0, X represents a group of formula -OCH2CH20- or -OWO- in which W represents a group of formula

(n₃ represents an integer of from 4 to 10, preferably 4), or a group of formula
most preferably X is a group of formula
2-a) polymers in which Y is a group of formula (V), R₁ and R₂ are hydrogen atoms and A is an alkylene group having from 2 to 6, particularly 6 carbon atoms, or a group of formula
wherein R₈ has the same meaning as the above-defined X,
2-b) polymers in which Y is a group of formula (VI), R₁ is a hydrogen atom, and R₉ is an alkanoyl group having from 2 to 4 carbon atoms or an alkyl group having from 1 to 8 carbon atoms and B is an alkylene group having from 2 to 6 carbon atoms, or R₉ is an alkyl group having from 1 to 8 carbon atoms and B is a group of formula
wherein R₈ has the same meaning as X;
2-c) polymers in which Y is a group of formula (VII), R₁ is a hydrogen atom and D is an alkanedicarbonyl group having from 4 to 12 carbon atoms,particularly 10 carbon atoms, or a benzene dicarbonyl group;
2-d) polymers in which Y is a group of formula (VIII), R₁ is a hydrogen atom and G is an alkanedicarbonyl group having from 4 to 12 carbon atoms or a group of formula
wherein R₈ has the same meaning as the above-defined X,
2-e) polymers in which Y is a group of formula (IX), (X) or (XI) and R₁ is a hydrogen atom.

The following is a non-limiting list of recurring units of the polymers of the invention:
The polymers of the invention having formula (I) may be either homopolymers or copolymers. In other words,each of W, X and Y may be all the same, partly different, or all different in their structures. In some instances, copolymers give better physical and/or stabilizing properties than homopolymers.
Polymers having the above-mentioned recurring units wherein a part or all of the hydroxy groups of the polymer are etherified, esterified or converted into carbamate groups are also representative polymers of the invention. Preferred such polymers with Z # hydrogen are, e.g. methyl ethers, ethyl ethers, acetates, propionates, benzoates, N-methyl carbamates, N-ethyl carbamates, N-phenyl carbamates and N-cyclohexyl carbamates.
The polymers of formula (I) according to the invention may be prepared by any one of the following methods which are performed under conditions known per se.

1) Polymers in which Z is a hydrogen atom and both m₁ and m₂ are 0 may be prepared by polymerizing an epoxy compound having the formula
in which Y₁ is a group of formulae (II) to (IV), with the proviso that the 2,3-epoxypropyl group is linked to the nitrogen atom at 3-position, the oxygen atom at 4-position or the oxygen atom of -CH₂0- in formulae (II), (III) and (IV), respectively.

The reaction is performed preferably by heating the starting compound (XII) at 60 to 230°C in the presence or absence of an inert solvent. Suitable solvents are, e.g., ethers such as dioxane or diethyleneglycol dimethyl ether; dialkylamides such as dimethylformamide or dimethylacetamide; chlorinated or non-chlorinated aromatic hydrocarbons such as benzene, toluene,xylene,chlorobenzene or p-dichlorobenzene; and alcohols or mixtures thereof with water such as methanol, ethanol, n- or tert-butanol, n-octanol, aqueous methanol or aqueous ethanol.
In performing the reaction, there may be employed a catalyst, if necessary. Suitable catalysts are for instance those used for curing epoxy resins, e.g. tertiary amines such as triethylamine, triethanolamine or 1,5-diazabicyclo-[5.4.0]undecene-5 (DBU) or Lewis acids such as boron trifluoride or zinc borofluoride.
The starting compounds (XII) may be prepared by reacting a compound of formula H-Y₁ -H with one mole equivalent of an epihalohydrin.
2) Polymers of formula (I) in which Z is a hydrogen atom and one of m₁ and m₂ is 1 and the other is 0 may be prepared by polymerizing an epoxy compound of formula
with a piperidine compound of formula H-Y₂-H, or by polymerizing an epoxy compound containing a piperidine of formula
with a compound H-X-H in which Y₂ is an above-defined group of formula (V) to (XI) and X has the meaning defined above.
The reaction is performed under similar conditions as in the aforementioned process variant 1).
The starting compounds (XIV) may be prepared by reacting a compound of formula H-Y₂-H with two mole equivalents of an epihalohydrin.
3) Compounds of formula (I) in which a part or all of Z are other than hydrogen may be prepared by introducing a substituent into a compound in which Z is a hydrogen atom and obtained in accordance with the above-mentioned process variants 1) or 2), by the methods described below:

3-a) Compounds in which Z is an alkyl group may be prepared by reacting the corresponding compound in which Z is a hydrogen atom with a strong basic alkali metal compound such as sodium hydride or potassium tert-butyrate and then with the desired alkyl halide.
3-b) Compounds in which Z is an acyl group maybe prepared by reacting the corresponding compound in which Z is a hydrogen atom with a reactive derivative of the corresponding carboxylic acid. As reactive derivatives acid halides, acid lower alkyl esters or acid anhydrides, preferably acid anhydrides, may be employed.
3-c) Compounds in which Z is an N-substituted carbamoyl group may be prepared by reacting the corresponding compound in which Z is a hydrogen atom with the corresponding isocyanate.

The polymers of formula (I) according to the invention can effectively stabilize a wide variety of synthetic polymers, such as:

olefin and diene polymers, including homopolymers of olefins and dienes (e.g. low-density, high-density and crosslinked polyethylenes, polypropylene, polyisobutylene,poly- methylbutene-1, polymethylpentene-1, polyisoprene and polybutadiene), mixtures of such homopolymers (e.g. mixtures of polypropylene and polyethylene, polypropylene and polybutene-1, or polypropylene and polyisobutylene), and copolymers of olefins and dienes (e.g. ethylene/propylene copolymers, propylene/butene-1 copolymers, propylene/iso- butylene copolymers, ethylene/butene-1 copolymers, and terpolymers of ethylene and propylene with dienes such as hexadiene, dicyclopentadiene or ethylidene norbornene);
styrene polymers, including polystyrene, copolymers of styrene and of a-methylstyrene (e.g. styrene/butadiene copolymers, styrene/acrylonitrile copolymers, styrene/acrylo- nitrile/methylmethacrylate.copolymers, styrene/acrylonit- rile/acrylic ester copolymers, styrene/acrylonitrile copolymers modified with acrylic ester polymers to provide impact strength, and styrene polymers modified with ethy- lene/propylene/diene elastomers to provide impact strength), and graft copolymers of styrene (e.g. polymers in which styrene is grafted onto polybutadiene, and polymers in which styrene and acrylonitrile are grafted onto polybutadiene as well as mixtures thereof with the aforementioned styrene copolymers, commonly known as acrylonitrile/buta- diene/styrene or ABS plastics);
halogenated vinyl and vinylidene polymers, including polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, chlorinated rubbers, vinyl chloride/viny- lidene chloride copolymers, vinyl chloride/vinyl acetate copolymers, and vinylidene chloride/vinyl acetate copolymers;
polymers derived from a,R-unsaturated acids, and derivatives thereof, including polyacrylates and polymethacrylates, polyacrylic amides and polyacrylonitrile;
polymers derived from unsaturated alcohols and amines,and from the acyl derivatives thereof or acetals, including polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, and polyallyl melamine, and copolymers thereof with other ethylenically unsaturated monomers (e.g. ethylene/vinyl acetate copolymers);
epoxy polymers, including homopolymers and copolymers derived from epoxides (e.g. polyethylene oxide), and polymers derived from bis-glycidyl ethers;
.polyacetals, polyalkylene oxides and polyphenylene oxides, including polyoxymethylene, oxymethylene/ethylene oxide copolymers, polyoxyethylene, polypropylene oxide, polyisobutylene oxide and polyphenylene oxides;
polyurethanes and polyureas;
polycarbonates;
polysulphones;
polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from amino-carboxylic acids or the corresponding lactams, including nylon-6, nylon-6,6, nylon-6,10, nylon-11 and nylon-12;
polyesters derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids and the corresponding lactones, e.g. polyethylene glycol terephthalate and poly-1,4-dimethylol-cyclohexane terephthalate;
crosslinked polymers derived from aldehydes together with phenols, ureas or melamines, e.g. phenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde resins;
alkyd resins, e.g. glycerol/phthalic acid resins and mixtures thereof with melamine/formaldehyde resins;
unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols as well as from vinyl compounds as crosslinking agents, and also halogenated flame-resistant modifications thereof.

The amount of stabilizers of the invention needed for effective stabilization of organic polymers will depend on a variety of factors, such as the type and properties of the polymer concerned, its intended use, and the presence of other stabilizers. It is generally satisfactory to use from 0.01 to 5.0% by weight of the stabilizers of the invention, based on the weight of the polymer, but the most effective range will vary with the type of the polymer; viz. 0.01% to 2.0%, preferably 0.02% to 1.0%, by weight for olefin,diene and styrene polymers; 0.01% to 1.0%, preferably 0.02% to 0.5%,by weight for vinyl and vinylidene polymers; and 0.01% to 5.0%, preferably 0.02% to 2.0%, by weight for polyurethanes and polyamides. If desired, two or more of the polymeric stabilizers of the invention may be used together.
The polymeric stabilizers of the invention may readily be incorporated into synthetic polymers to be stabilized by conventional techniques at any convenient stage prior to the manufacture of shaped articles therefrom.For example, the polymeric stabilizer may be mixed with the polymer to be stabilized in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension or emulsion of the polymer to be stabilized.
The stabilized polymeric composition of the invention may optionally also contain one or more of various additives conventionally used in polymer technology, such as the additives listed in British Patent Specification no. 1,401,924, at pages 11-13.In the following Examples the mean molecular weight was measured by the vapour pressure depression method.
1.4 g of 3-(2,3-epoxypropyl)-7,7,9,9-tetramethyl-1,3,8-triazaspirot4.5]decane-2,4-dione were heated at 180-190°C for 20 minutes in the absence of a solvent. Ethyl acetate was added to the reaction mixture, and insoluble residues were filtered off. A precipitate formed by adding n-hexane to the ethyl acetate solution, and said precipitate was collected by filtration and dried under reduced pressure, giving a white powder (Compound no. 1) softening at 205-208°C and having a mean molecular weight of 1,350.
3.0 g of 4-(2,3-epoxypropoxy)-2,2,6,6-tetramethylpiperidine were heated at 210-220°C for 5 hours under an argon stream. Upon cooling, the reaction product solidified, yielding a vitreous solid which was triturated giving a pale yellow powder (Componnd no. 2) softening at 140-145°C and having a mean molecular weight of 3,800.

Example 3

Acetate of compound no. 2. A mixture of 1.0 g of the pale yellow powder obtained according to Example 2 and 10 g of acetic anhydride was heated at 100-110°C for 5 hours under a nitrogen stream. The reacti.on mixture was poured into ice-water, neutralized with aqueous ammonia and extracted with ethyl acetate. The organic phase was washed with water and dried over anhydrous magnesium sulfate. The ethyl acetate was removed by evaporation under reduced pressure, yielding the desired compound (Compound no. 3) softening at 103-106°C. Examination of the compound by infrared and NMR spectrometry revealed that all of the hydroxy groups of the compound were acetylated.
3.0 g of 2-(2,3-epoxypropoxymethyl)-7,7,9,9-tetramethyl- l,4-dioxa-8-azaspiro[4.5]decane were heated in a similar manner as in Example 2. Further treatment of the reaction product as described in said Example 2 yielded the desired compound (Compound no. 4) as a pale yellow powder softening at 128-135°C and having a mean molecular weight of 14,000. By heating the starting material to 210-220°C for 2 hours under an argon stream and treating the reaction product as described in Example 2, a pale yellow powder (Compound no. 5) was obtained, softening at 80-85°C and having a mean molecular weight of 2,200.
To 6.0 g of 2-hydroxymethyl-8-(2,3-epoxypropyl)-7,7,9,9-tetramethyl-1,4-dioxa-8-azaspiro[4.5]decane were added 20 ml of 10% aqueous potassium hydroxide solution and the mixture was refluxed for 5 hours while stirring. The reaction mixture was then extracted with benzene and the benzene solution was washed with water and dried over potassium carbonate. The residue obtained by removing the solvent was purified by column chromatography (silica gel; ethyl acetate:triethylamine = 19:1), giving the desired compound (Compound no. 6) as a pale yellow viscous oily product having a mean molecular weight of 600.
5.0 g of 3-ethyl-3-(2,3-epoxypropoxymethyl)-8,8,10,10-tetramethyl-1,5-dioxa-9-azaspiro[5.5]undecane were heated to 220-230°C for 10 hours under an argon stream. The reaction mixture was then treated in a manner similar to that described in Example 2, yielding the desired compound (Compound no. 7) as a pale yellow powder softening at 130-140°C and having a mean molecular weight of 14,000.
By heating the above-mentioned starting material to 210-220°C for 2 hours under an argon stream and treating the reaction product as described in Example 2, the desired compound (Compound no. 8) was obtained in the form of a white powder softening at 55-60°C and having a mean molecular weight of 1,200.
7.9 g of 2,2-bis(p-[2-hydroxy-3-(7,7,9,9-tetramethyl-2,4-dioxo-1,3,8-triazaspiro[4.5]dec-3-yl)propoxy]phenyl)propane and 3.4 g of 2,2-bis[p-(2,3-epoxypropoxy)phenyl]propane were heated to 180-190°C for 20 minutes in the absence of a solvent. The reaction mixture was washed with ethyl acetate and dried under reduced pressure, giving the desired compound (Compound no. 9) as a white powder softening at 175-180°C and having a mean molecular weight of 3,200.
5.0 g of 3,3'-hexamethylene-bis-(7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione) and 3.3 g of 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane were heated at 230°C for 3 hours under an argon stream. The reaction mixture was dissolved in chloroform and the solution was poured into n-hexane, whereby a precipitate was formed. The precipitate was collected by filtration and dried under reduced pressure, giving the desired compound (Compound no. 10) in the form of a white powder softening at 139-141°C and having a mean molecular weight of 1,900.

Example 9

Benzoate of Compound no. 10. 2.0 g of the white powder obtained according Example 8 and 8.0 g of benzoic anhydride were heated to 150°C for 15 hours under argon. The reaction mixture was dissolved in ethyl acetate, washed with 5% aqueous potassium carbonate solution and water, and dried over sodium sulfate. The residue obtained by removing the solvent was purified by column chromatography. At first,elution with ethyl, acetate gave a white powder (Compound no. 11) softening at 115-120°C. The NMR spectrum of the compound showed that the benzoylation rate was 95%. A second elution with ethyl acetate:ethanol:triethylamine = 20:1:1, gave a greyish white powder (Compound no. 12) softening at 115-118°C. The NMR spectrum of the compound showed that the benzoylation rate was 45%.
4.8 g of N,N'-hexamethylenebis[N-(2,2,6,6-tetramethyl-4-piperidyl)acetamide and 3.4 g of 2,2-bis[p_-(2,3-epoxypro- poxy)phenyl]propane in 25 ml of n-octanol were refluxed at 180-200°C for 8 hours. n-Octanol was removed under reduced pressure and the residue was purified by column chromatography (silica gel; ethyl acetate:triethylamine: methanol = 8:1:1) giving a white powder (Compound no. 13) softening at 108-115°C and having a mean molecular weight of 2,600 from the first eluate, and a white powder (Compound no. 14) softening at 90-110°C and having a mean molecular weight of 1,650 from the second eluate.
The above-mentioned starting material was heated to 200-220°C for 3 hours in the absence of a solvent and then treated and purified in a similar manner as described above, giving a white powder (Compound no. 15) softening at 150-160°C and having a mean molecular weight of 6,000 from the first eluate, and a white powder (Compound no. 16) softening at 120-130°C and having a mean molecular weight of 2,650 from the second eluate.
4.8 g of N,N'-hexamethylenebis[N-(2,2,6,6-tetramethyl-4-piperidyl)acetamide] and 2.8 g of bis(2,3-epoxypropyl)-1,2-cyclohexanedicarboxylate were heated to 200°C for 5 hours under a nitrogen stream. The reaction mixture was purified by column chromatography (silica gel; ethyl acetate:triethylamine:methanol = 8:1:1) and the crude product thus obtained was dissolved. in benzene. The benzene solution was poured into n-hexane and the precipitate formed was collected by filtration, giving a white powder (Compound no. 17) softening at 115-125°C and having a mean molecular weight of 2,700.
3.0 g of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate and 2.1 g of 2,2-bis[p-(2,3-epoxypropoxy)phenyl]propane were heated to 190-200°C for 4 hours under argon. The reaction mixture was purified by column chromatography (silica gel; ethyl acetate:triethylamine= 20:1), giving a pale yellow solid product (Compound no. 18) softening at 85-90°C and having a mean molecular weight of 2,500 from the first eluate, and a pale yellow solid procuct (Compound no. 19) softening at 74-77°C and having a mean molecular weight of 1,900 from the second eluate.
2.2 g of bis[1-(2,3-epoxypropyl)-2,2,6,6-tetramethyl-4-piperidyl] sebacate and 0.55 g of adipic acid were refluxed in 5 mol of n-butanol for 24 hours. The n-butanol was removed from the reaction mixture and the residue was washed with n-hexane and then treated with ethyl acetate. The ethyl acetate soluble fraction was purified by column chromatography (silica gel; ethyl acetate:ethanol = 4:1). giving the desired compound (Compound no. 20) as a pale yellow oil having a mean molecular weight of 1,600.
2.7 g of bis[1-(2,3-epoxypropyl)-2,2,6,6-tetramethyl-4-piperidyl] sebacate and 0.95 g of 1,10-decanedicarboxylic acid were refluxed in 6 ml of n-amyl alcohol for 17 hours. The reaction mixture was then treated in a similar menner as described in Example 12, yielding the desired compound (Compound no. 21) as a pale yellow oil having a mean molecular weight of 1,820.
₃.0 g of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate and 1.1 g of ethyleneglycol diglycidyl ether were. heated at 200-200°C for 8 hours under an argon stream. The reaction mixture was purified by column chromatography (silica gel; . ethyl acetate:ethanol:triethylamine = 20:1:1), giving a pale yellow viscous oil (Compound no. 22) having a mean molecular weight of 3,000 from the first eluate, and a pale yellow viscous oil (Compound no. 23) having a mean molecular weight of 2,300 from the second eluate.
4.4 g of 2,2,4,4,14,14,16,16-octamethyl-7,11,18,21-tetra- oxa-3,15-diazatrispiro[5.2.2.5.2.2]heneicosane and 3.4 g of 2,2-bis[p-(2,3-epoxypropoxy)phenyl]propane were heated to 180°C for 8 hours under a nitrogen stream. The reaction mixture was purified by column chromatography (silica gel; ethyl acetate: triethylamine = 9:1), and the product was dissolved in benzene and precipitated with n-hexane, yielding the desired compound (Compound no. 24) as a white powder softening at 180-200°C and having a mean molecular weight of 3,450.

Example 17

Acetate of Compound no. 24. 2 g of the white powder obtained according toExample 16.and 10 g of acetic anhydride were refluxed in 20 ml of benzene for 5 hours. The reaction mixture was washed with 10% aqueous potassium carbonate solution, and the benzene layer was dried over potassium carbonate. The residue obtained.by removing the solvent was purified by column chromatography (silica gel; ethyl acetate) and the obtained crude product was dissolved in in benzene. By pouring the benzene solution into n-hexane, a precipitate was formed which precipitate was collected by filtration yielding a white powder (Compound no. 25) softening at 155-175°C. The IR and NMR spectra showed that the hydroxy groups of the polymer had been completely acetylated
2.1 g of 3.15-bis(2,3-epoxypropyl)-2,2,4,4,14,14,16,16-octamethyl-7,11,18,21-tetraoxa-3,15-diaza-trispirol[5.2,2. 5.2.2]heneicosare and 0,8 g of sebacic acid were refluxed in a mixture of 10 ml of tert-butanol and 10 ml of tolaene for 14 hours. After removal of the solvent under reduced pressure the residue was purified by column chromatography (silica gel; ethyl acetate: methanol = 1:1), giving the desired compound (Compound no. 26) as a white powder softening at 149-158°C and having a mean molecular weight of 5,100.
4.1 g of 2,2,4,4,14,14,16,16-octamethyl-7,11,18,21-tetra- oxa-3,15-diazatrispiro[5.2.2.5.2.2]heneicosane and 1.74 g of ethyleneglycol diglycidyl ether were heated to 200°C in 4 ml of octanol for 20 hours while stirring. After removal of the octanol under reduced pressure, the residue was purified by column chromatography (silica gel; ethyl acetate: methanol: triethylamine = 2:2:1), giving the desired compound (Compound no. 27) as a pale yellow powder softening at 140-154°C and having a mean molecular weight of 2,770.
6.4 g of 4,4'-bis(2,2,6,6-tetramethyl-4-piperidinol) and 6.8 g of 2,2-bis[p-(2,3-epoxypropoxy)phenyl]propane were heated in 80 ml of octanol to 150-160°C for 8 hours while stirring. After removal of the octanol under reduced pressure, the remaining vitreous mass was triturated, giving the desired compound (Compound no. 28) as a white powder softening at 106-109°C and having a mean molecular weight of 1,850.
1.5 g of 2,2,2',2',6,6,6',6'-octamethyl-4.4'-bipiperidyl- ydene and 1.8 g of 2,2-bis[p-(2,3-epoxypropoxy)phenylJpro- pane were heated to 180-220°C for 2 hours under an argon stream. The reaction mixture was dissolved in chloroform, methanol was added thereto whereupon a precipitate formed. The precipitate was collected by filtration, washed with methanol and dried under reduced pressure, giving the desired compound (Compound no. 29) as a white solid softening at 170-180°C and having a mean molecular weight of 5,300.
A mixture of 5.24 g of bis(2,2,6,6-tetramethyl-4-piperidyl) adipate and 4.2 g of 2,2-bis[p-(2,3-epoxypropoxy)phenyl] propane was heated to 160-170°C for 6 hours under a nitrogen stream. The reaction mixture was purified by column chromatography through silica gel eluted with ethyl
ate, giving the desired compound (Compound no. 30) in the form of a white powder softening at 95-115°C and having a mean molecular weight of 3,700.
A mixture of 8.5 g of
adipate and 5.2 g of bis(2,3-epoxypropyl) 1,4-butanedicarboxylate was heated to 160-170°C for 4 hours under a nitrogen stream. The reaction mixture was dissolved in ethyl acetate and the solution was poured into n-hexane yielding an oily substance which was insoluble in n-hexane. The oily substance was dried under reduced pressure, giving the desired compound (Compound no. 31) in the fcrm of a colourless solid softening at 97-115°C and having a mean molecular weight of 3,700.
A mixture of 4.8 g of N,N'-hexamethylenebis[N-(2,2,6,6-tetramethyl-4-piperidyl)acetamide] and 2.6 g of bis(2,3-epoxypropyl) 1,4-butanedicarboxylate was heated to 200°C for 3 hours under a nitrogen stream. The reaction mixture was washed with hot n-hexane and dried under reduced pressure, yielding the desired compound (Compound no. 32) in the form of a pale yellow powder softening at 50-60°C and having a mean molecular weight of 2,020.
A mixture of 4.8 g of N,N'-hexamethylenebis[N-(2,2,6,6-tetramethyl-4-piperidyl)acetamide] and 1.74 g of ethylene glycol diglycidyl ether was heated to 250°C for 1 hour under a nitrogen stream. The reaction mixture was dissolved in benzene and the solution was poured into n-hexane to give a precipitate. The precipitate was collected by filtration and dried under reduced pressure, affording the desired compound (Compound no. 33) in the form of a pale yellow powder softening at 85-95°C and having a mean molecular weight of 2,360.
A mixture of 4.25 g of bis(2,2,6,6-tetramethyl-4-piperidyl) adipate and 2.84 g of bis(2,3-epoxypropyl) 1,2-cyclohexanedicarboxylate was heated to 170-180°C for 16 hours under an argon stream. The reaction mixture was dissolved in benzene and the solution was poured into n-hexane to give a
A mixture of 3.5 g of bis(2,2,6,6-tetramethyl-4-piperidyl) isophthalate and 2.0 g of bis(2,3-epoxypropoxy)adipate was heated to 180°C for 7 hours under a nitrogen stream. The reaction mixture was dissolved in benzene and the solution was filtered and poured into n-hexane to give a precipitate. The precipitate was collected by filtration and dried under reduced pressure to give the desired compound (Compound no. 37) in the form of a pale yellow powder softening at 90-100°C and having a mean molecular weight of 3,000.
A mixture of 3.5 g of bis (2,2,6,6-tetramethyl-4-piperidyl) isophthalate and 1.4 g of ethylene glycol diglycidyl ether was heated to 180°C for 7 hours under a nitrogen s;tream. The reaction mixture was dissolved in benzene and the sol- ution was poured into n-hexane to give a precipitate.The precipitate was collected by filtration and dried under reduced pressure, yielding the desired compound (Compound no. 38) in the form of a pale yellow powder softening at 98-105°C and having a mean molecular weight of 3,200.

Example 31

Stabilization of polypropylene. Mixtures were prepared from 100 parts of unstabilized polypropylene powder (melt flow index = 18), 0.2 parts of stearyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (a conventional antioxidant) and 0.25 parts of each of the stabilizers listed in the following Table 1. [All parts are parts by weight]. The mixtures were blended and homogenized with a Brabender Plastograph at 200°C for 10 minutes and the obtained mass was pressed into a sheet of 2-3 mm thickness with a laboratory press. The sheet was then pressed in a hydraulic press at 260°C for 6 minutes (12 tons) and put immediately into cold water to form a film of 0.5 mm thickness, from which a film of 0.1 mm thickness was obtained by the same procedure.
The film was cut into test specimens of 50 x 120 mm. The test specimens were exposed to light in a Sunshine Weather Meter at a black panel temperature of 63+3°C and examined periodically to determine the percentage of elongation at break. From the test results the ratio of the time required for the test specimens containing stabilizer to reach 50% elongation at break was determined, to the .time required for an unstabilized test specimen to reach 50% elongation at break. The results are summarized in Table 1.

Example 32

Stabilization of polystyrene . Mixtures were prepared from 100 parts of polystyrene ("Styron 666", trade name, manufactured and sold by Asahi Dow Co. Ltd.) and 0.25 parts of each of the stabilizers listed in the following Table 2. The resultant mixtures were blended and homogenized by means of a Brabender Plastograph at 200°C for 5 minutes, then compression-molded at 180°C for 2 minutes, forming sheets of 1.5 mm thickness. Each test sheet was exposed to light in a Xenon Weather-O-Meter (6.5 kw; ASTM G 26-77) for 1500 hours, and the yellowness index of the sheet before and after irradiation was determined in accordance with ASTM D 1925. The results are shown in Table 2.

Example 33

Stabilization of polyurethane. Mixtures were prepared from 10 g of polyurethane ("Paraprene 22S", trade name, manufactured and sold by Nippon Polyurethane Kogyo KK),and 0.05 g of each of the stabilizers given in the following Table 3. Each mixture was dissolved in 30 ml of dimethylformamide and the resulting solution was drawn on a glass plate to form a sheet of 0.4 mm thickness. The sheets were maintained at 60°C for 20 minutes and dried at 120°C for 15 minutes to cast films of 0.1 mm thickness. The films thus obtained were exposed to ultraviolet radiation in a Sunshine Carbon Arc Lamp Weather Meter (type "WEL-SUN-HC", trade name of Suga Test Instruments Co. Ltd.) for 300 hours and the yellowness index before and after irradiation was determined in accordance with ASTM D1925.The results are shown in Table 3.

Claims

1. A polymer represented by the formula (I):

wherein

1 is an integer of from 2 to 50,

m₁ and m₂ are 0, or one of them is 1 and the other is 0,

X represents a group of formula

in which

R' is a hydrogen atom or a methyl group,

n₁ is an integer of from 1 to 10,

n₂ is 0 or an integer of from 1 to 10, CH3

W represents a group of formula

in which

n₃ is an integer of from 1 to 10, and

Z has the meaning defined below,

Y represents, when m₁ and m₂ are 0, a group of the following formulae II to IV:

in which:

R₁ represents a hydrogen atom or a methyl group,

R₂ represents a hydrogen atom or an alkyl group having from 1 to 18 carbon atoms,

in which R₁ has the meaning defined above,

in which R₁ has the meaning defined above,

R₃ represents a group of formula

and

R₄ represents the methyl or ethyl group,

Y represents, when one of m₁ and m₂ is 1 and the other

is 0, a group of the following formulae V to XI:

in which:

R₁ and R₂ have the meanings defined above,

A represents an alkylene group having from 2 to 12 carbon atoms, a xylylene group, a group of formula

in which

R₅ represents an alkylene group having from 2 to 8 carbon atoms,

R₆ represents a hydrogen atom, the methyl or phenyl group,

R₇ represents an aliphatic, aromatic or alicyclic diacyl group having up to 12 carbon atoms,

R₈ has the same meaning as the abcve-defined X,

p is 0 or 1, and

Z has the meaning defined below,

in which:

R₁ has the meaning defined above,

R₉ represents an alkyl group having from 1 to 18 carbon atoms, a phenyl group, a benzyl group, a cyclohexyl group, or an aliphatic, aromatic, araliphatic or alicyclic acyl group having up to 18 carbon atoms,

B represents an alkylene group having from 2 to 10 carbon atoms, a xylylene group, a group of formula

-CH₂COO-R₅-OCOCH₂- _'

in which

R₅, R₆, R₇, R₈ and p have the meanings defined above, and Z has the meaning defined below,

in which:

R₁ has the meaning defined above,

D represents an aliphatic, aromatic, araliphatic or alicyclic diacyl group having up to 36 carbon atoms or a group of formula -CONH-R₁₀-NHCO- in which

R₁₀ represents an alkylene group having from 2 to 10 carbon atoms, a phenylene group optionally substituted with methyl, a naphthylene group, a xylylene group, a cyclohexylene group optionally substituted with methyl, a group of formula

in which

R₁₁ represents an oxygen atom or the methylene group,

in which:

R₁ and R₃ have the meanings defined above,

G has the same meaning as the above-defined D, or represents an alkylene group having from 3 to 10 carbon atoms,

a xylylene group, a group of formula

or a group of formula

in which

R₈ has the meaning defined above, and

Z has the meaning defined below,

in which R₁ has the meaning defined above,

in which R₁ has the meaning defined above,

in which R₁ has the meaning defined above, and

all cf Z in the molecule represent a hydrogen atom, an alkyl group having from 1 to 18 carbon atoms, an aliphatic, aromatic, araliphatic or alicyclic acyl group having up to 18 carbon atoms or a group of formula -CONHR₁₂ in which

_R12 represents an alkyl group having from 1 to 18 carbon atoms, a phenyl or cyclohexyl group,

or a part of Z represents a hydrogen atom and the remaining Z represent above-defined groups other than hydrogen.

2. A polymer as claimed in claim 1, wherein Y is a group of formula (II) to (XI) and R₁ is a hydrogen atom.

3. A polymer as claimed in claim 2, wherein both m₁ and m₂ are 0, Y is a group of formula (II) in which R₁ and R₂ are hydrogen atoms.

4. A polymer as claimed in claim 2, wherein both m_l and m₂ are 0, Y is a group of formula (III) in which R₁ is a hydrogen atom.

5. A polymer as claimed in claim 2, wherein both m₁ and m₂ are 0, Y is a group of formula (IV) in which R₁ is a hydrogen atom.

6. A polymer as claimed in claim 2, wherein one of m₁ and m₂ is 1 and the other is 0, X is a group of formula -OCH₂CH₂0- or -OWO- in which

W is a group of formula

-CO-(CH₂)-CO-, n₃being an integer of from 4 to 10, or

7. A polymer as claimed in claim 6, wherein Y is a group of formula (V) in which R₁ and R₂ are hydrogen atoms and A is an alkylene group having from 2 to 6 carbon atoms or a group of formula

wherein R₈ has the same meaning as X.

8. A polymer as claimed in claim 6, wherein Y is a group of formula (VI) in which R₁ is a hydrogen atom, and R₉ is an alkanoyl group having from 2 to 4 carbon atoms or an alkyl group having from 1 to 8 carbon atoms, and B is an alkylene group having from 2 to 6 carbon atoms, or R₉ is an alkyl group having from 1 to 8 carbon atoms, and B is a group of formula

wherein R₈ has the same meaning as X.

9. A polymer as claimed in claim 6, wherein Y is a group of formula (VII) in which R₁ is a hydrogen atom and D is i an alkanedicarbonyl group having from 4 to 12 carbon atoms or a benzene dicarbonyl group.

10. A polymer as claimed in claim 6, wherein Y is a group of formula (VIII) in which R₁is a hydrogen atom and G is an alkanedicarbonyl group having from 4 to 12 carbon atoms or a group of formula

wherein R₈ has the same meaning as X.

11. A polymer as claimed in claim 6, wherein Y is a group of formula (IX), (X) or (XI) in which R₁ is a hydrogen atom.

12. A polymer as claimed in any one of claims 7 to 11, wherein X is a group of formula

13. A polymer as claimed in claim 1 wherein all of Z in the molecule are hydrogen atoms.

14. A polymer as claimed in claim 1, wherein all of Z in the molecule are acetyl or benzoyl groups, or a part of Z are hydrogen atoms and the remaining Z are acetyl or benzoyl groups.

15. A polymer as claimed in claim 1, wherein 1 is an integer of from 2 to 10.

16. A synthetic polymer composition stabilized against light- and heat-degradation thereof, which is characterized in that there is incorporated into a synthetic polymer to be stabilized from 0.01 to 5.0% by weight, based on the weight of said synthetic polymer, of at least one polymer represented by the formula (I):

wherein

1 is an integer of from 2 to 50,

m₁ and m₂ are 0, or one of them is 1 and the other is 0,

X represents a group of formula

in which

R' is a hydrogen atom or a methyl group,

n₁ is an integer of from 1 to 10,

n₂is 0 or an integer of from 1 to 10,

W represents a group of formula

in which

n₃ is an integer of from 1 to 10, and

Z has the meaning defined below,

in which:

R₁ represents a hydrogen atom or a methyl group,

in which-R₁ has the meaning defined above,

in which R₁ has the meaning defined above,

R₃ represents a group of formula

and

R₄ represents the methyl or ethyl group,

Y represents, when one of m₁ and m₂ is 1 and the other is 0, a group of the following formulae V to XI:

in which:

R_I and R₂ have the meanings defined above,

in which

R₅ represents an alkylene group having from 2 to 8 carbor atoms,

R₆ represents a hydrogen atom, the methyl or phenyl grou_f

R₈ has the same meaning as the above-defined X,

p is 0 or 1, and

Z has the meaning defined below,

in which:

R₁ has the meaning defined above,

-CH₂COO-R₅-OCOCH₂- ,

in which

in which:

R₁ has the meaning defined above,

in which

R₁₁ represents an oxygen atom or the methylene group,

in which:

R₁ and R₃ have the meanings defined above,

G has the same meaning as the above-defined D, or represents an alkylene group having from 3 to 10 carbon atoms, a xylylene group, a group of formula

or a group of formula -CH_2,CHCH₂-R₈-CH_2,CHCH₂- in which OZ OZ

R₈ has the meaning defined above, and

Z has the meaning defined below,

in which R₁ has the meaning defined above,

in which R₁ has the meaning defined above,

in which R₁ has the meaning defined above, and all of Z in the molecule represent a hydrogen atom, an alkyl group having from 1 to 18 carbon atoms, an aliphatic, aromatic, araliphatic or alicyclic acyl group having up to 18 carbon atoms or a group of formula -CONHR₁₂ in which R₁₂ represents an alkyl group having from 1 to 18 carbon atoms, a phenyl or cyclohexyl group.

17. A synthetic polymer as composition as claimed in claim 16, wherein the synthetic polymer is an olefin or diene polymer, a styrene polymer or a polyurethane.