DE2326010C3 - Polymer masses stabilized against photo- and thermal degradation - Google Patents

Description

(1)

contains, where R is an alkyl group, an alkenyl group, an alkenoyl group optionally substituted by an aryl group, a hydroxyalkyl group, Alkoxyalkyl group, alkoxycarbonylalkyl group, acyloxyalkyl group, cyanoalkyl group or denotes a nitroso group and X and Y are, depending on one another, an oxygen or egg Represent sulfur atom.

2. Synthetic polymer composition according to claim 1, characterized in that it is the piperidine! spirohydantoin derivative in an amount of 0.01 to 5 percent by weight, based on the amount of de | synthetic polymers.

3. Synthetic polymer composition according to claim 1, characterized in that it contains at least eii Piperidine-spirohydantoin derivative of the formula I contains, in which R is an alkyl group with 1 to 8 carbons material atoms, an alkenyl group with 3 or 4 carbon atoms, an alkenoyl group with or 4 carbon atoms, an alkoxyalkyl group with 1 to 8 carbon atoms in the alkoxy group Alkyl part, an alkoxycarbonylalkyl group having 1 to 4 carbon atoms in the alkyl part and 1 bi 18 carbon atoms in the alkoxy part, an acyl oxyalkyl group with 1 to 4 carbon atoms in the Alkyl part and an unsaturated or saturated aliphatic or aromatic acyl part, or a Cyanoalkyl group with 1 to 4 carbon atoms in the alkyl part and X and Y are each an oxygen represent atom.

The invention relates to photo- and thermal degradation stabilized polymer compositions which in an amount sufficient to avoid degradation, at least one piperidine spirohydantoin derivative of formula I.

(D

H ₁ C

contain, wherein R is an alkyl group, an alkenyl group, one optionally by an aryl group substituted alkenoyl group, a hydroxyalkyl group, alkoxyalkyl group, alkoxycarbonylalkyl group, Acyloxyalkyl group, cyanoalkyl group or nitroso group and X and Y independently of one another mean an oxygen or a sulfur atom.

In the above formula I, alkyl groups R preferably have 1 to 8 carbon atoms. When Examples are: the methyl, ethyl, n-propyl, η-butyl, isobutyl, pentyl, hexyl, heptyl or Octyl group. Alkenyl groups preferably have 3 or 4 carbon atoms, such as the allyl or trans-2-butenyl group. As alkenoyl groups, which optionally are substituted by an aryl group, especially those with 3 or 4 carbon atoms in the alkenoyl part and 6 to 10 carbon atoms in the aryl part, z. B. the acryloyl, Crotonoyl or cinnamoyl group. Hydroxyalkyl groups R preferably have 1 to 4 carbon atoms. Examples of such groups are Hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl and the 4-hydroxybutyl group. Alkoxyalkyl groups preferably each have 1 to 8 carbon atoms in both the alkoxy and the alkyl part and are ζ. Β the 2-methoxyethyl, ethoxymethyl, 2-ethoxyethyl, 4-propoxybutyl or 2-octoxyethyl group. Acyloxy alkyl groups preferably have 1 bi in the alkyl part:

4 carbon atoms and can be a saturated or unsaturated aliphatic or aromatic Have acyl part. Examples are the 2-acetoxy ethyl, 2-prot) ionyloxyethyl, 3-butyryloxypropyl-benzoyloxymethyl, 2-Benzoyloxyethyl, 2-AcryloyI oxyäthyl or the 2-methacryloyloxyäthylgruppe As alkoxycarbonylalkyl groups R are in particular especially those with 1 to 4 carbon atoms in the alkyl part and 1 to 18 carbon atoms in the alkoxy part into consideration, such as the MethoxycarbonylmethyK

Ethoxycarbonylmethyl, 2-butoxycarbonylethyl, octoxycarbonylmethyl or stearyloxy carbonylmethyl group. Cyanoalkyl groups preferably have in the alkyl part 1 to 4 carbon atoms. Examples are: the cyanomethyl, 2-cyanoethyl, 3-cyanopropyl or the 4-cyanobutyl group.

Piperidine-spirohydantoin derivatives of the formula I are preferred, in which R is an alkyl group having 1 to 8 carbon atoms, an alkenyl group with 3 or 4 carbon atoms, an alkenoxyl group with 3 or 4 carbon atoms, an alkoxyalkyl group each having 1 to 8 carbon atoms in the alkoxy and alkyl part, one Alkoxycarbonylalkyl group having 1 to 4 carbon atoms in the alkyl part and 1 to 18 carbon atoms in the alkoxy part, an acyloxyalkyl group having 1 to 4 carbon atoms in the alkyl part and an unsaturated one or saturated aliphatic or aromatic acyl moiety or a cyanoalkyl group with 1 bi 4 carbon atoms in the alkyl part and X and Y each represent an oxygen atom.

Representative examples of piperidine-spirohydantoin derivatives of the formula I, which are advantageous for stabilizing of polymer masses are listed below:

Compound Chemical name Light and heat stability. So z. B. Poly-

N * · olefins and polyurethane elastomers, if they are the

~~. "Exposed to light, for example the sun

1 1,3,8-rnaza-VJ.K ^ -pentamethyl- light or ultraviolet radiation, strongly degraded. spiro [4.5] decane-2,4-dione 5 are polyvinyl chloride and polyvinylidene chloride

2 l.S.S-Triaza-TJ.S. ^ - pentamethyl- by the joint action of light and spiro [4.5] decane-2,4-dithione heat is removed with elimination of hydrogen chloride.

3 l ^ .S-Triaza ^ J. ^ - tetramethyl-S-octyl- ^b . ^{aut and} discolored. The polyamides are also frequently subject to photodegradation of spiro [4.5] decane-2,4-dione. For stabilization

4 l, 3,8-Triaza-8- (2-ethoxyethyl) -7,7,9 9-tetra- " ? *? ^S y. ^Synthetic polymers against the degradation is methyl-spiro [4.5] decane-2 4- ^{A number of} stabilizers have already been proposed

, _OA 11100 · -i '·, _nn , e.g. B. Benzotriazole compound and benzo-

™ ί £ 2 η ri '^ ^naZa - ⁷ Sj ⁹ : *****' phenone compounds for polyolefins, phenolic compounds

methyl-spiro [4.5] decane-2,4KÜon _{solutions and} ßenzophenonverbindungen for polyurethane

6 lAS-Tnaza-cinnamoyl - ^^^ - tetra- 15thene and lead salts for polyvinyl chloride and polymethyl-spiro [4.5] decane-2,4-dione vinylidene chloride, e.g. B. basic lead silicate and three-

7 l ^ .S-Triaza ^ J ^^ - teiramethyl-e-nitroso-basic lead maleate, as well as organotin compounds, spiro [4.5] decane-2,4-dione such as dibutyltin laurate and dibutyltin maleate.

8 8-AJJyl-l, 3,8-triaza-7,7 ₎ 9,9-tetramethyl- ^{From the} German Offenlegungsschriften 20 30 908, spiro [4.5] decane-2,4-dione ^{20 18 13} " ^{4 and} 17 ⁶⁹ 646 are in the 8 position on the embroidery

'Q, substance atom unsubstituted piperidine-spirohydantoine

· ⁹ · ¹ " ^U " ^{d salts} f of. 7,7-dimethyl-9,9-disubstituted pipe

ο / - ■ »- ι, Λ ridin-spirohydantoin-8-oxyls or substituted in 3-position

10 8- (2-acetoxyethyl) -1,3,8-triaza-7,7 _> 9,9-te-tuiene piperidine-spirohydantoins as stabilizers

tramethyl-spiro [4.5] decane-2,4-dione _a5 known. Compared to these known stabilizers

H l, 3,8-Tnaza-8- (2-benzoyloxyethyl) - those which can be used according to the invention are distinguished

7,7,9,9-tetramethyl-spiro [4.5] decane compounds due to an increased light protection effect,

2,4-dione better compatibility with the substrates and /

12 l, 3,8-triaza-8- (2-cyanoethyl) -7,7,9,9-tetra- ^or better color fastness, alone or in methyl-spiro [4.5] decane-2,4-dione ³ ° Combination with common antioxidants.

13 l, 3,8-Triaza-8- (2-cvanoäthyl) -7,7,9,9-tetra- ^{The Men} S ^{e of the} compounds of the formula I, which for methyl-spiro [4.5] decane-2,4 -dithione effective stabilization of synthetic polymers

.. ι α ο τ, ·., ο-λ u ι ι. ι is required depends on a variety of factors

¹ "ί ^XyCar S ^methyl " ^{as the} type and properties of the

2'idfo'n ^{y PirOt] Can} " ^{35 kom} n ™ ^d « i polymers, the intended application

purpose and the presence of other stabilization

Compounds No. 3, 5, 10 and 12, are preferred. It is preferable to use the Verganz but especially the compounds No. 1, 4, 8 bonds of the formula I in an amount of 0.01 to and 14. 5.0 weight percent based on the weight of the

As used herein, "synthetic 4 ° synthetic polymer." The most effective area

Polymer "should include the following substances: but varies depending on the type of polymer. So amounts

Olefin, diene and styrene polymers, such as homopoly- these 0.01 to 2.0 percent by weight, preferably mers of olefins, dienes and styrene, e.g. B. poly 0.02 to 1.0 weight percent, for olefin, diene and low and high density ethylene, polypropylene, "styrene polymers, 0.01 to 1.0 percent by weight, preferred polystyrene, Polybutadiene and polyisoprene, as well as 0.02 to 0.5 percent by weight for vinyl chloride copolymers of olefins, dienes and styrene with mono- and vinylidene chloride polymers and 0.01 to 5.0 geanders or with other ethylenically unsaturated weight percent, preferably 0.02 to 2.0 weight monomers, z. B. ethylene-propylene copolymers, percent for polyurethanes and polyamides. Desired ethylene-butene copolymers, Ethylene-vinyl acetate-Co- tenfalls can two or more of the compounds of polymers, styrene-butadiene copolymers and acrylic 5 ° Formula I can be used.

nitrile-butadiene-styrene copolymers; The stabilizers to be used according to the invention

Vinyl chloride and vinylidene chloride polymers, such as horors, can be used at any stage prior to manufacture

mopolymers of vinyl chloride and vinylidene chloride, position of the moldings according to conventional working vinyl chloride-vinylidene chloride copolymers and co-wise incorporated into the synthetic polymers are polymers of vinyl chloride or vinylidene chloride with 55. So the stabilizers z. B. with the Vinyl acetate or other ethylenically unsaturated synthetic polymers in the form of a dry

Monomers; Powder can be mixed, or you can use one

Polyacetals, such as polyoxymethylene and polyoxy suspension or emulsion of the stabilizer with a

ethylene; Solution, suspension or emulsion of the synthetic

Polyesters such as polyethylene terephthalate; Mix 6 ° polymers.

Polyamides such as nylon-6, nylon-6.6 and nylon-6.10, the stabilized synthetic according to the invention

and finally polyurethanes. Polymer masses can also contain various conventional

Synthetic polymers are found on the basis of their borrowed additives, such as antioxidants, UV absorbers,

excellent properties in a wide variety of fillers and pigments. Examples are suitable

Forms application, for example as continuous threads, 65 antioxidants are: phenolic compounds, such as 2,6-di-

Fibers, yarns, films, plates, other moldings, t-butyl-p-cresol, 4,4'-thiobis (6-l.butyl-3-methylphe-

Latices and foams. These polymers have nol), 2,2'-thiobis (6-t.buty! -4-methylphenol), 4,4'-bis, however Disadvantages, for example a bad (2,6-di-t.butylphenol), 4,4'-BiS (^., 6-diisopropylphenol),

ι /

2,4,6-tri-isopropylphenol, 4,4'-butylidene-bis (6-t-butyl-3-methylphenol), l, l, 3-tris (5-t.butyl-4-hydroxy-2-methylphenyl) butane, Tetrakis - (/ 9-3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl) methane and 2,4,6-tris (3,5-di-t.buryl-4-hydroxybeaäyl) mesitylene, Thiodipropionates, such as dilauryltbiodipropionate, and alkyl, Aryl or aralkyl phosphites such as triphenyl phosphite, tris (p-nonyl) phenyl phosphite and diphenyl decyl phosphite.

The following substances are examples of suitable ultraviolet absorbers: Benzotriazoles, such as 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole and 2- (3 ', 5'-di-t.butyl-2'-hydroxyphenyl) - 5-chlorobenzotriazole, salicylates such as 4-t.butylpheiiylsalicylate, benzophenones such as 2-hydroxy-4-octoxybenzophenone, and 2 ', 4'-di-t.butylphenyl-SS-di-t.butyM-hydroxybenzoate, methyl- « -cyano /? - methyl - /? - (p-methoxyphenyl) acrylate and (2,2'-thiobis [4-t.octylphenolate]) - n.butylamine with Ni ⁿ . Such conventional stabilizers are preferably used in a weight ratio of 0.5 to 3: 1 in relation to the stabilizers according to the invention.

The piperidine-spirohydantoin derivatives of the formula I can be prepared by various methods will. Some of these methods are discussed below »5 explained:

ie by reacting a compound of the formula I with potassium cyanide and ammonium chloride to form the intermediate product of the formula III and reacting the latter with carbon disulfide and sulfur to give a compound of the formula 1-2, where R _{1 has} the meaning given below.

A.
H ₃ CI CH ₃ R ₂ -X ₁

H ₃ C

CH ₃

CH ₃ NaCN H ₃ C

(NH ₄ I ₂ CO ₃
CH ₃ H ₃ C

ie by reacting a compound of the formula IV with a halide in the presence of a base, where R _{2 is} an alkoxyalkyl group, an alkenoyl group optionally substituted by an aryl group or a nitroso group, X _{1 is} a halogen atom and X and Y have the meanings given.

30th

HN

35

ie by reacting a compound of the formula II with an alkali metal cyanide and with ammonium carbonate to give a compound of the formula 1-1, where R _{1 is} an alkyl group, a hydroxyalkyl group, an acyloxyalkyl group or an alkoxycarbonylalkyl group.

B. OH ₂ N CN

ν X

H, CII CH ₃ CH ₂ = CHCN H ₃ C

H ₃ C

CH,

H, C

H
(IV)

CH ₃

CH ₂ CH ₂ CN

(1-4)

d. H. by reacting compounds of the formula IV with acrylonitrile, where X and Y are the ones indicated Have meaning.

NH

55

HN-f
NH

/ X

HCHO Y

CH ₃ HCOOH H ₃ CI CH ₃

,, CH, H ₃ CI CH ₃

H 'CH,

(IV) (1-5) '

d. H. by reacting a compound of the formula IV with formaldehyde and formic acid, where X and Y have the meaning given.

Examples 1 to 9 below illustrate polymer compositions stabilized according to the invention.

example 1

From 100 parts of polypropylene (Noblen JHH-G from Mitsui Toatsu Chemicals, Inc., Japan, twice recrystallized from monochlorobenzene) and 0.25 parts of the stabilizers given in Table I were Mixtures made. The mixtures obtained were mixed and melted; the melt mixtures were formed into plates with a thickness of 0.5 mm under heating and pressure. there has been a Control plate made that did not contain any stabilizer.

The plates were ^{irradiated with ultraviolet light at 45 °} C. using a “standard fade meter type FA-I”. This instrument, manufactured by Toyo Rika Instruments Inc., Japan, is a modification of the Atlas Fade-O-meter type FDA-R and meets the requirements of the Japanese industrial standard L-1044, section 3.8. Table I shows the time in hours until the plates became brittle.

Example 2 Table II

Made of 100 parts of high-density polyethylene ("Hi-Zex" from Mitsui Toatsu Chemicals Inc., Japan, twice recrystallized from toluene) and 0.25 parts of the as Mixtures were prepared from the stabilizers given in Table I. The mixtures obtained were as in Example 1 described deformed into plates. A stabilizer-free control plate was made in the same manner manufactured.

The plates were irradiated with ultraviolet light as described in Example 1 and the time in hours until the plates became brittle was determined. The results are shown in Table I. Mixtures were prepared as shown in Table II stabilizers. The resulting mixtures were deformed mm at 18O ⁰ C under pressure to give plates with a thickness of Figure 1. A stabilizer-free control plate was also made.

The plates obtained in this way were exposed to UV light in the fade meter described in Example 1 at 45 ^° C. for 500 hours. A sample of the treated plate was examined for color difference by means of a color difference colorimeter according to Japanese Industrial Standard K-7103. The change in the yellow index of the plate was calculated using the following equation:

Δ YI = YI-YI ₀

Δ YI denotes the change in the yellow index, YI the yellow index after exposure and YI ₀ the yellow index of the unexposed plate.

The results are summarized in Table II.

Stabilizer connection Yh

Δ Yl

Table I.

Stabilizer time until it becomes brittle (in hours)

connection polypropylene polyethylene

No high density

560

2 260 3 580 4th 520 5 600 6th 540 7th 440 8th 520 9 530 10 500 11th 540 12th 540 13th 420 14th 580 control 60 Tinuvm 327 300

1040 640

1140 960

1180 980 720 880 740 760 800 860 720 940 400 300

1 4.3 + 4.6 2 5.0 + 5.4 3 4.4 + 3.9 4th 4.3 + 4.5 5 4.4 + 4.8 6th 4.2 + 4.3 7th 4.7 + 5.2 8th 4.5 + 3.8 9 4.3 + 4.2 10 4.4 + 4.3 control 4.8 + 16.8 Example 4

Example 3

From 100 parts of polystyrene (Styron * from Asahi-Dow Limited, Japan, from a mixture of benzene ucaA methanol crystallized) and 0.25 parts each of the

35

40 from 100 parts of an ABS resin ( "Kane Ace B-12" from the company. Kanegafuchi Spinning Co. Ltd., Japan) and 0.5 parts of the stated in Table III stabilizers were prepared mixtures. The resulting mixtures were kneaded at a kneading for 6 minutes at 160 ⁰ C and then added to plates having a thickness of 0.5 mm deformed. A stabilizer-free control plate was also made.
The panels thus obtained were aged as described below. The elongation at break of the panels was then measured as a percentage of the initial elongation and the tear strength as a percentage of the initial strength.

Aging test:

1. Weathering for 50 hours using a sunshine weathering device according to the Japanese industry nonn J [S Z-0230 entitled "Accelerated Weathering Test of Rust Proofing

Oils «, paragraph 2.

2. 30minutige aging at 180 ⁰ C in an aging device according to EER G, described in Japanese Industrienonn JIS K-6301 under the

609653/276

Title "Physical Testing Methods for Vulcanized Rubber", Paragraph 6.5.

The results are summarized in Table III.

Table HI

Stabilizer- Ventilation device Tear Aging device after connection Tear strength Geer / No. strain in the Discoloration in the Starting Starting strength strain

66
71
69
73

Control 53

75
79
77
80
69

Example 5

dirty yellow

light yellow

light yellow

light yellow

Brown

From 100 parts of nylon-6 ("CM 1011" from Toray Industries Inc., Japan) and 0.25 parts each of the in Mixtures were prepared as stabilizers indicated in Table IV. The mixtures obtained were melted and under pressure into films using a conventional compression molding machine deformed to a thickness of 0.1 mm. A stabilizer-free control film was also made.

The films thus obtained were aged as shown below. Then the Elongation at break of the films as a percentage of the initial elongation and the tear strength as a percentage of the initial strength measured.

Aging conditions:

1. Irradiation with UV light for 200 hours in the described fade meter at 45 ° C;

2. 2-hour aging at 160 ⁰ C in an aging device according to Geer.

The results are summarized in Table IV.

Table TV

Stabilizer connection
No.

Fade meter
Elongation at break
in the
Initial elongation

Tear resistance
in the
Output strength

Aging device according to Geer

Elongation at break in% of the initial elongation

Tear strength in% of the initial strength

68
72
66
63

Control 16

81
77
71
73
49

75 72 67 74 23

72 69 68 73 51

Example 6

Made from 100 parts of polyurethane, made from polycaprolactone ("E-5080" from The Nippon Elastollan Industries Ltd., Japan), and 0.5 parts each of the in table y! specified stabilizers mixtures were made: The resulting mixtures were melted

and formed into plates with a thickness of 0.5 mm. A stabilizer-free control plate was also used manufactured.

The plates obtained in this way were for 15 hours at 45 ° C in the example 1 described fade meter irradiated with UV light. The elongation at break of the panels was then determined in Percentage of the initial elongation and the tensile strength wedge measured as a percentage of the initial strength.

The results are summarized in Table V.

Table V

Stabilizer elongation at break tear strength

connection in% of in% of

No. Initial elongation Initial strength

1
3
5
control

86
91
82
72

77 73 84 54

Example 7

Mixtures were prepared from 100 parts of polyvinyl chloride ("Geon 103 EP" from The Japanese Geon Co., Ltd., Japan), 40 parts of dioctyl phthalate and 0.2 parts each of the stabilizers given in Table VI. The resulting mixtures were be for 5 ^minutes: 140 ⁰ C kneaded at a kneading roll and then deformed mm plates having a thickness of about. 1 A control plate was also made that did not contain any stabilizer.

The panels thus obtained were aged as shown below. Then their Discoloration determined.

Aging conditions:

1. Weathering for 200 hours in the sunshine weathering device described above;

2. Aging for 30 minutes at 160 ° C in a Geer aging device.

The results are summarized in Table VI.

Table VI

Stabilizer connection

Weathering device

Aging device
according to Geer

1 yellowish brown light brown 3 light brown light brown 55 5 light brown light brown control dark brown red-brown

Example 8

Mixtures were prepared from 100 parts of a polyester resin ("Ester-G 13" from Mitsui Toatsu Chemicals, Inc., Japan), 1 part of benzoyl peroxide and 0.2 parts each of the stabilizers given in Table VII. The mixtures obtained were preheated for 30 minutes to 60 ° C and then a lstündiges heating to 100 ⁰ C and cured. formed into plates with a thickness of 3 mm. A stabilizer-free control plate was also produced.

ΔΌ U 1 U

The panels thus obtained were subjected to the sunshine weathering device described in Example 4 weathered for 60 hours. The change in the yellowness index was then carried out according to that described in Example 3 Method determined. The results are shown in Table VII.

Table VII 2.4 Δ Yi stabilizer
connection
No. 2.2 + 7.3 1 2.3 + 8.9 3 1.8 + 9.0 5 Example 9 + 13.9 control

IR spectrum (in Nujol):

yNH3340; 3150 cm- ¹ .
yc-ol770, 1703 cm- ¹ .

Example 11

l ^. S-Triaza-S-ethoxycarbonylmethyl-7,7,9,9-tetramethyl-spiro [4.5] decane-2,4-dione

Mixtures were prepared from 100 parts of a polyacetal resin (“Delrin 500” from Showa Neoprene KK, Japan) and 0.5 parts each of the stabilizers given in Table VIII. The resulting mixtures were heated and melted at 200 ⁰ C. The mixtures were then aged in the atmosphere for 30 minutes at 222 ° C. Then, the percentage reduction in decomposition was measured. The results are shown in Table VIII.

Table VIII

5 g of 1-ethoxycarbonylmethyl-2,2,6,6-tetramethyl-4-oxopiperidine were added to a solution of 4 g of sodium cyanide and 22 g of ammonium carbonate in 50 ml of 50% strength aqueous ethanol. The mixture obtained was stirred at room temperature for 20 minutes and then at 45 to 50 ^° C. for 3 hours. The reaction mixture was then concentrated and the crystalline residue was washed with water and then dried. The recrystalline

Sation from 20% aqueous ethanol gave the above product in the form of white crystals a melting point of 193 to 194 ° C.

Analysis for C ₁₅ H ₂₅ N ₃ O ₄ :

Calculated .... C 57.86, H 8.09, N 13.50%;
found .... C57.90, H8.09, N 13.66%.

IR spectrum (in Nujol):

y _N H3350; 3180 cm " ¹ .
yc-o 1778; 1752; 1710 cm- ¹ .

The following compounds were produced according to the specified procedure:

Stabilizer connection No.

reduction of decomposition (i%)

1 0.53 3 0.58 5 0.47 control 0.80

The following is the manufacture of some according to the invention to be used piperidine spirohydantoine of the formula I described.

Example 10

1,3,8-triaza-7,7,9,9-tetramethyl-8-octylspiro [4.5] decane-2,4-dione

To a solution of 3 g of sodium cyanide and 16 g of ammonium carbonate in 40 ml of 50% aqueous Ethanol was 3.5 g of 2,2,6,6-tetramethyl-4-oxol-octylpiperidine given. The resulting mixture was stirred at room temperature for 30 minutes and then for an additional 3 hours at 45 to 55 ° C. Then the reaction mixture was concentrated. The crystalline residue was washed with water washed and dried. Recrystallization from a mixture of petroleum ether and benzene gave this above product in the form of white crystals with a melting point of 187-189 ° C.

spiro [4.5] decane-2,4-dione,
Melting point 241.5 to 243 ° C;
l, 3,8-Triaza-8- (2-hydroxyethyl) -7,7,9,9-tetramethyl-spiro [4.5] decane-2,4-dione,

Melting point 225 ° C (decomposition);

8- (2-acetoxyethyl) -1, 3,8-triaza-7,7,9,9-tetra-

methyl-spiro [4.5] decane-2,4-dione,

Melting point 212 to 213 ° C;

l, 3,8-Triaza-8- (2-benzoyloxyethyl) -7,7,9,9-tetra-

methyl-spiro [4.5] decane-2,4-dione,

Melting point 215 to 217 ° C.

Example 12

Analysis for

Calculated .... C 67.61, H 10.45, N 12.45%;
found .... C67.47, H 10.39, N 12.16%.

yA

spiro [4.5] decane-2,4-dione

7n a suspension of 3 g of sodium carbonate and 5 g of 3,8-triaza-7,7,9,9-tetramethyl-spiro [4.5] decane-2,4-dione in 40 ml of dimethylformamide was a solution of 3 g of acryloyl chloride in Given 10 ml of dimethylformamide at room temperature. After completion of the addition the resulting mixture at room temperature for 30 minutes and then a further 4 hours at 60 to 7O ⁰ C for Thereupon was concentrated the reaction mixture, and the crystalline residue was treated with a dilute aqueous solution of acetic acid The mixture was filtered, the insoluble crystalline substance to isolate. This was washed with water, dried and recrystallized from dioxane

the above product in the form of white crystals with a melting point of 346 to 347 ° C.

Analysis for C ₁₄ H ₂₁ N ₃ O ₃ :

Calculated .... C 60.19, H 7.58, N 15.04%; found .... C 60.35, H 7.60, N 15.20%.

IR spectrum (in Nujol):

? νη3320; 3170 cm- ¹ .
yc-ol770; 1735; 1630 cm " ^1. yc-c 1610 cm- ¹ .

The following compounds were produced according to the procedure given:

Analysis for C ₁₄ H ₂₂ N ₄ S ₂ :

Calculated ... C 54.18, H 7.15, N 18.05, S 20.62%:

found

% C 54.35, H 7.11, N 18.00, S 20.77%,

IR spectrum (in Nujol):
)>nh3310; 3110 cm- ¹ .

yc = N 2220 cm " ¹ .

B e i s ρ i e 1 15

methyl-spiro [4.5] decane-2,4-dione, melting point 138 to 139 ⁰ C;

spiro [4.5] decane-2,4-dione,
Melting point 331 to 332 ° C;

spiro [4.5] decane-2,4-dione,

Melting point 250 to 251 ° C (decomposition).

Example 13

Calculated
found

spiro [4.5] decane-2,4-dione

To a suspension of 2.3 g of 1,3,8-triaza-7,7,9,9-tetramethyl-spiro [4.5] decane-2,4-dione and 1 g of acrylonitrile in 20 ml of ethanol were added 0.5 ml a 40% Triton-B solution (benzyltrimethylammonium hydroxide) in methanol. The mixture obtained was ^{stirred at 40 to 50 °} C. for 90 minutes. The reaction mixture was then concentrated and the crystalline residue was recrystallized from benzene, the above product being obtained in the form of white crystals with a melting point of 190 to 191 ^° C.

Analysis for C ₁₄ K ₂₂ N ₁ O ₂ :

Calculated .... C 60.41, H 7.97, N 20.13%; found .... C 60.40, H 7.97, N 20.08%.

IR spectrum (in Nujol):

γ NH 3340; 3290 cm " ¹ .
γ c = N 2220 cm- ¹ ,
yc-o 1760; 1702 cm " ¹ .

Example 14

1,3,8-Triaza-8- (2-cyanoethyl) -7,7,9,9-tetramethylspiro [4.5] decane-2,4-dithione

The procedure of Example 13 was repeated with the exception that 2.6 g of 3,8-triaza-7,7,9,9-tetramethyl-spiro [4.5] decane-2,4-dithione and 1 g of acrylonitrile were used and that the crystalline residue was recrystallized from benzene. Found in this 6o manner there was obtained the above product in form of white crystals having a melting point 180-181 ⁰ C ^.

p
spiro [4.5] decane-2,4-dione

To 22.5 g of 1,3,8-triaza-7,7,9,9-tetramethyl-spiro [4.5] -

decane-2,4-dione were added to 256 g of 90% strength formic acid. Thereupon were in the course of 1 hour From 20 to 30 ° C. 162 g of 37% strength aqueous formaldehyde solution were added. After the completion of the dropwise The resulting mixture was added under

ao stirring about 7 hours slowly refluxed until the release of gaseous carbon dioxide stopped. After the completion of the reaction, the reaction mixture was cooled with 800 ml of water diluted and with 45% aqueous sodium hydroxide

solution neutralized to a pH of 9 to 9.5. The mass which separated out was separated off by filtration, washed with water, dried and recrystallized from isopropanol, whereby the above product was obtained in the form of white crystals with a melting point of 200 to 203 ^° C. Analysis for C ₁₂ H ₂₁ N ₃ O ₂ :

C 59.23, H 8.70, N 17.29%;
C 59.43, H 8.76, N 17.26%.

Example 16

1,3,8-triaza-7,7,8,9,9-pentamethylspiro [4.5] decane-2,4-dithione

4 ml of 30% strength aqueous formaldehyde solution were added to 2.6 g of 3,8-triaza-7,7,9,9-tetramethyl-spiro [4.5] -decane-2,4-dithione. Then 0.6 ml of 90% formic acid at 50 to 60 ^° C. and a further 0.5 ml of 90% formic acid at 70 to 80 ^° C. were added. The resulting mixture was stirred for 4 hours at the latter temperature. After cooling, a 30% strength aqueous solution of potassium hydroxide was added to the reaction mixture.

The crystalline mass which separated out was separated off by filtration, washed in water and dried and then recrystallized from benzene, giving the above product in the form of white crystals having a melting point of 135 to 136 ° C was obtained.

Analysis for C ₁₂ H ₂₁ N ₃ S ₂ :

Calculated ... C 53.12, H 7.80, N 15.49, S 23.59%; ... C 53.05, H 7.77, N 15.48, S 23.71%.

IR specirum (in Nujol):
33005 3100 cm- ¹ .

Claims (1)

Patent claims: 1, Polymeiüaasse stabilized with respect to photo- and thermal degradation, which in one to avoid of at least one sufficient amount of degradation. Piperidine spirohydantoin derivative of Formula I.