CS196295B2 - Stabilized materials based on polymers or copolymers vinylchloride - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to heat-stable polymeric materials on a polyvinyl chloride substrate. These materials can be subjected to. Elevated temperatures during their formation and use.

It is known that polymers and copolymers of vinyl chloride are used. to produce. articles by casting, extrusion, and the like, which require high temperatures to sufficiently soften the polymer. At these temperatures; which reaches 180 to 200 degrees Celsius are subject to polymers on the substrate. however, degradation, which results in a change in color and a change in mechanical properties! To avoid these changes. byto ^; It is proposed to incorporate stabilizers in the polymer, for example metal chelates with dicarbonyl-colored compounds, which may optionally contain metal salts of carboxylic acids as well as salts with southern elements, for example calcium, lead and cadmium salts. (U.S. Patent Nos. 2,669,548 and 2,230.75). Heavy metal salts with higher aliphatic acidic and organic phosphites as described in U.S. Patent No. 2,564,646) or polyols as described in U.S. Patent No. 2,711,401 may also be used. these compositions have not achieved sufficient effect when the polymer has been subjected to too high temperatures in the manufacture of clear or transparent articles because the high temperature induces less or more turbidity of the polymer, making it unusable in some fields. It is, for example, the production of transparent films or films, bottles and the like, where it is not possible to change the color of the polymer or change the transparency of the articles. .

It has now been found that this decomposition can be prevented by adding high temperatures to polymeric materials based on vinyl chloride. stabilizing agents which have hitherto not been used in the plastics field.

Accordingly, the present invention provides stabilized materials based on polymers or copolymers of vinyl chloride, characterized in that they contain from 0.1 to 5% by weight of one or more salts of aliphatic or aromatic acids with divalent metals such as calcium, barium or zinc; % To 5% by weight of an organic compound of formula (I)

R1-CO-CHR2-CO-R3 · (I) wherein

R 1 and R 3, identical or different, denote straight or branched chain alkyl or alkenyl of up to 30 carbon atoms, arylalkyl of 7 to 36 carbon atoms, aryl or

198295

198295 contain inter-carbon double bonds or R1 and R3 residues are altered by the presence of one or more --O-- groups.

—C — O—, ·· I - O!

—CO—, in the aliphatic chain, and may additionally form a bivalent alkylene residue of 2 to 5 carbon atoms, optionally containing oxygen or nitrogen, one of R 1 or R 3 may be hydrogen,

R @ 2 represents a hydrogen atom, an alkyl or alkenyl group of up to 30 carbon atoms, the latter optionally containing a group --O--,

-C —-O-10 or · -CO-, the remainder of the formula -CO-R 1, where R a is alkyl of 1 to 30 carbon atoms or aryl, and the remainder of the formula -R 5 -CH 3 -CO; —RÍ kde

R 5 represents an alkylene radical having 1 to carbon atoms;

R1 and R3 are as defined above.

The term "polyvinyl chloride backing materials" refers to materials containing a homopolymer or copolymer of vinyl chloride together with other additives which are commonly used to facilitate processing or processing. to achieve the desired properties of the resulting molded article any homopolymer type. The vinyl chloride can be used to produce the material of the invention without distinction in the process, production, type of polymerization, and the like. ,

Numerous copolymers of yinyl chloride can be stabilized against the effects of heat in the same manner as homopolymers, for example products resulting from the polymerization of vinyl chloride with other monomers. containing polyol-1-ol-1-ol. ethylene-type linkages such as ethylene, acrylic esters, styrene, vinyl esters, maleic acid or its anhydride and maleic acid esters. .

. These copolymers usually contain at least 50% by weight of vinyl chloride. However, the properties of the material according to the invention are particularly easily achieved when the copolymer contains at least 80% by weight of vinyl chloride, the other monomer being vinyl acetate or vinylidene chloride. These copolymers can be used as such or in admixture with other polymers, in particular polyvinyl chloride.

It is also possible to stabilize the materials to pQdkladu · polyvinylchlpridu perchloric ³ in the fourth

cycloallphatic • residue o; up to 14 carbon atoms in which the chlorine content can dock; wherein the cycloaliphatic residues may optionally reach up to 65 to 70% by weight, which are very sensitive to thermal decomposition at higher te. fences.

The divalent metal salts of carboxylic acids are preferably calcium, barium, zinc or lead salts or cadmium with aliphatic, saturated or unsaturated or saturated salts; with ar -aromatic acids. Among these salts, mention may be made in particular of acetates, diacetates, ethylhexanoates, actates, stearates, oleate, laurates, palminates, millingstates, orthicolates, benzoates and phthalates. These salts are generally used as a mixture of at least two of these salts, for example calcium and zinc salts. It's necessary; to mention that in the production of packaging for · food products or in the manufacture of bottles, salts of long-chain saturated aliphatic acids with alkaline earth metals are particularly suitable for their non-toxicity and sliding properties. Calcium and zinc stearates, laurates, 2-ethylhexanoates are very suitable compounds in this sense. These compounds are used in the range of 0.1 to 5% by weight, based on the weight of the polymer.

Dicarbonyl compounds used together with metal salts. The compounds may also be the aldehyde -? - ketones of formula I when the radicals R @ 1 or R @ 3 are hydrogen atoms.

Z-diketones are known products which can be produced by the method described in "Organic Reactions" by R. Adams, ed. 1954, VII, p. Various methods for producing the specified compounds are described in "Ed. Trav. Chem. Pays ^L Bas MJ Kramers 16 (1897) p. 116 or in J. Chem. Soc. ”GT Morgan and E. Holmes 127 (1925) p. 2891 · or · in“ J. Chem. · Soc, ”· R. Robinson and E. Seijo! (1941) p. 582 or in "Chemical Berichte" Clalsen 20 (1887) p. 2188. Aldehyde-β-ketones can be made by classical methods as described in "Organic" Reactions ”R., Adams, et al., 8, p. 59 et seq. (1954). '

These organic compounds are used in a ratio of 0.05. Up to 5%, preferably 0.1 to. . 1% by weight, based on the total weight of the polymer. ·;: .. '· - · .. ·; ...: / :::. .-. / - .:

Among these compounds are aliphatic diketones such as beptan-2,4-dione, decane-2,4-dione, nonane-2,4-dione, ethyl carboxylate, and the like. methyl-7-nonene-2,4-dione, acyloxyacetones, such as acetylacetone, 1'- (1'-tert-butyl) or triacetylmethane, (4'-stearoylacetone) and stearoylalkanone.

Aromatic β-diketones or aromatic-aliphatic compounds may also be mentioned; such as benzoyl acetone, tribenzoylmethane, diacetylacetobenzene, stearoylacetophenone. palmltoylacetofenon. Diketones in which a long aliphatic residue is found, such as stearoacetone, palmitoacetone, laurylacetone or steareylacetophenone, paimitoylacetophenone and laurylacetophenone, are particularly well suited for

190295 its extended-stabilization efficiency

Among the aldehyde / 3-ketohes, mention may be made in particular of 2-acyloxyacetyl aldehydes; Thus, for example, benzoylacetaldehyde as well as 2-acetyl-2-methyl (acetaldehyde) can be used.

Homopolymer and copolymers can be rigid or flexible. When solid polymers are used, agents that alter their impact resistance, such as butadiene-styrene or styrene terpolymers, styrene and acrylonitrile terpolymers, can be used as commonly used to improve the mechanical properties of the polymers. К materials according to the invention it is possible to add také'růz ^With adjuvants such as plasticizers, pigments, fillers, antioxidants, stabilizing the material against light and the like.

In addition to the stabilizers used in the material according to the invention, it is also possible to add other organic compounds whose stabilizing effect is known, for example pentaerythritol or trihydroxyethylisocyanurate. '

Stabilizers used in the material of the invention can be incorporated at the same time as the other auxiliary agents, or ^one may be admixed, optionally with other additives and then adding к resulting material so that the resulting stabilizing srfíěs which is incorporated into polyvinylchlorldp. The mixing can be carried out by any conventional method, a very suitable mixing method being homogenization.

The materials of the invention may be processed by any conventional method known for the processing of polyvinyl chloride and its copolymers, for example by injection molding, extrusion, calendering, casting and the like.

Concentration of the organic stabilizing agent and? -Contents metal allows delay yellowing and transparent získáhí resulting products, which are completely ^homogeneous. ·

The invention will be illustrated by the following examples. '2-' '·

Example 1 a d у i; аД 5

Material A is prepared which can be used for the production of dies by extrusion.

'In a cylindrical jeans, they prepare the following mixture: -i' - · ..... ''. '

1000 g of powdered polyvinyl chloride obtained by slurry polymerization, sold under the tradename Lučovyl RS 800, 100 g of a reinforcing agent, which is a copolymer of styrene butadiene and methyl methacrylate, which reduces the brittleness of the material, 10 g ... of a glidant which is a wax on a rosin ester substrate and is available under the trade mark Clear E, 10 g calcium stearate, 7 g zinc stearate, 30 g epoxidized soybean oil and 3 g trihonylphenyl phosphite.

The mixture is milled for 15 hours.

In 5 250 ml dusters containing several porcelain beads, 56 g of mixture A and some of the following mixtures are stored:

Substance В - 0.12 heptane-2,4-dione, boiling point 180 ° C at 0.1 MPa, substance C - 0.16 g decane-2,4-dione, substance D - 0.2 g nonane- 2,4-dionethylcarboxylate O-boiling point 130 ° C at 67 Pa, E - 0.21 g 1-benzoyl-2-hexanone and F - 0.15 g 2-methyl ^: 2-decanen-6, 8-dlon boiling point 234 ° C at 0.1 MPa,

The fabrics are mixed thoroughly for 15 hours to give a homogeneous mixture of В, C. D, E and F.

These materials are made by calendering at a temperature of 175 DEG C., a sheet having a thickness of 2.5 mm. ·,

10 x 20 mm samples are formed from these plates and stored in a ventilated chamber at 180 ° C for various periods.

After this time, the coloring of the sample on the Gartner scale is read using a Lovibund wheel.

The following results were obtained:

Minutes 0 7 14 21

Gařdner grades mixture A mixture V mixture C mixture D mixture E mixture F

8 9 10 11 2 3 3.5 '5 1 1 2 3 2 ' '4 5 '6 1 2 '. · 4 ... 5 1 1 1 2,

It can be shown that the samples containing the organic stabilizer are far less colored and are much more stable against the elevated temperature of the non-compound-containing sample A. ketone type. ir

Examples 6 a ^; Mixtures G < H, F, J, K, L, M were prepared according to Example *. 1 by using 56 g of mixture A, prepared in the same manner as in Example 1, with the addition of one of the following:

compound G - 0.17 g of dibenzoylmethane, m.p. 79 DEG C., compound H .0.18. g 2,2´-methylene-bis- (cyclohexane-1,3-dione), melting point 134 m Celsius,

compound I - 0.15 g of benzoylacetone, m.p. 56 ° C,

198295 substance J - 0.25 g tribenzoylmethane, melting point 248 ° C, substance K - 0.15 g triacetyl methane, boiling point 95 ° C at 13.3 Pa, substance L - 0.2 gl, 4-diacetylacetobeizene ··· . m.p. 184 DEG C. and M 0.2 g of 1-, 4-diphenylbutane-1,3-dione.

The mixture was stirred for 15 hours.

These materials are prepared by calendering at 180 ^Q C plate having a thickness of 2.5 mm.

These plates are divided into rectangular 10 x 10 mm samples which are stored in a ventilated chamber at 180 ° C for various times.

They then evaluate the coloring of the samples according to the Gardner scale using a Lovlbond disk. > ·: ·

The following results were obtained:

Duration in minutes 0 7 14. 21 smás AND 8 8 8 9 sm | s G 1 1 1.5 3.5 mixture H 1 2 2 3 mixture I ^! \ 1 1 1 1.5 mixture J 1 1.5 2 2 mixture К · 1.5 2.5 3 4 mixture L 3 3 4 4 mixture M - 1 1 1.5 3 - -

Example 13

The mixture Z is made by preparing a mixture in a ball mill:

1000 g of powdered polyvinyl chloride having a K value of 69, which material is obtained by suspension polymerization and is sold under the trade name Lucovyl GS. g of barium stearate and 9 g of barium stearate.

The resulting mixture is milled.

To a grinding machine with a capacity of 250 ml containing porcelain pellets. is given -56 g of the mixture. The mixture is milled 5. From mixtures P and P, it was prepared to prepare samples by the method of Example 1 by calibrating at 140 ° C.

These samples are stored in a ventilated chamber at 180 ° C for various periods of time, after which the color of the samples is read according to the Gardner scale using a Lovibond disk. ^J '

Duration in minutes 0 ‘7 14 21

It can be observed that the samples made of polyvinyl chloride are far less resistant to yellowing than the samples using the additional reagent. That is, organic; the stabilizing agent makes it possible to reduce the yellowing during production 1 during the heat treatment of the material produced on the substrate by vinyl poles.

Examples 14 and .15

A mixture of the same composition as Example A of Example 1 was prepared. A sample of this 56 grams was treated in the same manner, to which was added Q - 0.15 g benzoylacetone and a mixture of S - 0.15 g benzoylacetone and 0.15 g. g; pentaerythritu.

The control sample R contained only 0.60 g of pentaerythritol.

The results of the heat stability measurement on the Gardner scale led to the following values:

Duration in minutes 0 7 14 21. mixture A 6 7 8 8 mixture Q 1 1 2 3 mixture S 1 i 1.5 1.5 mixture R 3,5 4,5 6 6.5

From the results- it is obvious that pentaerythritium alone even in relatively high quantities is not sufficient to ensure.how good thermal stability as у if it is used in? mixtures with a diketone compound.

Examples 16 to 19

The procedure is analogous to Example 1, wherein the mixture is prepared from the following components:

800 g of polyvinylchloride, -200 g of vinyl chloride copolymer, wool acetic acid containing 15 percent vinyl acetate, 100 g of butadiene, styrene and methylriethethacrylate copolymer, 30 g of epoxidized soybean oil, .gig of Cire E, 5 g of calcium stearate and 2 g. .5 g stearate; evil. · Í ⁴

Into the mill, 57 g of this blend of bleaching agent was / charged and the plates were made in the same manner as in Example 1 _.; <

-Stálost heat at vzorků'měří so produced in a chamber at 170 ° ^C by the method of Gardner. In this way, the following results were obtained: (Gardner degrees):

mixture Ъ: 0 2 ¹ '2 i. ·· 2 mixture P 0 0 0 1

190295

10

Duration in minutes 0 ΐ = 7 ·· 14: 21 ^ onfroM: ·. '· <·. , - beige _; ^ acton and .4 ’ 5 6 benzylacetone 0.10 g 0 0 1 3 steajoylacetone 0.10 g stearoylacetophenone 0 O 1 3 Ф.15 g. · -: ... 8-Methyl-7-nonene- 0 0 5 3 rZ / α-dione. 0 0 1.5 3. Examples 20 and 21

In this example, the stabilization of the hot perchlorinated polymer with a total amount of 65% chlorine is illuminated. The procedure is to produce a mixture of the following components:

’1000 g of polymer, 10 g of Cire E, 15 g of calcium stearate and 1.5 g of zinc stearate.

TK 57 g of this mixture is added with a stabilizing agent to produce a plate thickness. 2 mm calendering at 190 ° C.

These samples were tested for thermal stability in a chamber at 180 ° C and the following results were obtained: (Gardner degrees):

minutes · 0 . .. 7 .. : 14. · .. control sample 11 13 18 stearoylacetone 0.50 g 6 10 111 benzoylacetone 0.30 g 5 9 11

Examples 2 2 to 2 6

The procedure is analogous to Example 1, using 56 g of component A, to which 0.2 g of stearoylacetophenone, 0 ', 2 g of palmitoylacetophenone, 0.3 g of 1-stearoyl-2-octanone or 0.3 g are added. of p-methoxystearoylacetophenone. By measuring the heat stability on these materials, the following results were obtained in Gardner stages:

Duration in minutes 1 7 14 21 control sample 8 9 10 11 stearoylacetophenone 1 1 1 1.5 palmitoyl- acetophenone 1 1 1 1.5 stearoyloctanone 1 1 1.5 2 p-methoxystearoyl- acetophenoin 1 1 1 1.5

Example 27

The procedure was as in Example 1 to produce a mixture consisting of the following components:

1000 g of polyvinyl chloride, 100 g of butadiene, styrene and methyl methacrylate polymer, 10 g of Cire E, 2.5 g of zinc stearate, 5 g of calcium stearate, 30 g of epoxidized soybean oil and 3 g of trinonylphenyl phosphite.

To the two batches, 56 g of this mixture, was added 10.08 in the experiment. g. stearoylacetone; in experiment 2 0.15 g of this substance and in experiment 3 0.25 g of this substance. At; Tests: the temperature stability of these materials were obtained, the following results in Gardner degrees: .......

Duration·.:

in minutes 0 ; .7; 14 21 . 28 35. control sample 7 9. · 9 9 10 10 - experiment 1 0 1 1.5 2 3 5 experiment 2 O. 0 0.5 • 2 2. = 4 pokus 3 0 0 .0 • 1 2 :. 4 ...

Example 28

Mixture (a) is produced which consists of the following components: ...

100 g of polyvinyl chloride, 10 g of ABS copolymer, 1 g of Cire E, 3 g of epoixidized soybean oil, 0.7 g of zinc stearate, 1.1 g of calcium stearate and 0.64, g of decane-2.4 -dionu. .

In addition, a mixture b) is prepared which differs from the first mixture in that the last two components of the first mixture, and the tp calcium salt and the dione, replace 0.71 g of the calcium chelate with decane-2,4-dione. Both mixtures are treated as described above. In the heat stability tests, the following results were obtained in the Gardner stages: ·

Duration in minutes ⁰ 7 14 21 control sample 8 8 8 8 mixture aj _; 0 0 0 2.5 mixture b) 5 2 8 brown-black coloration

Thus, it is clear that although the two mixtures are actually identical in terms of the molar amounts of β-diketone and calcium, they have very different thermal stability, which is much lower when used as a chelate.

Similar results were obtained when zinc stearate and decandione were replaced with the corresponding zinc chelate.

Examples 29 to 30

Using the mixture of Example 1 and the method of this example, two materials were prepared containing 56 g of the above mixture and 0.15 g of benzoylacetaldehyde or 0.15 g of 2-methyl-2-acetylacetaldehyde. Samples are made of materials whose thermal stability is tested in ventilated chambers. The following Gardner degrees were obtained:

Duration in minutes · '· O ·' '' 7 ‘г 14 21

Examples 5 9 to 6 8 control sample 6 '8 3' · 3 benzoylacetaldehyde 2 3 - 3,5 · 4

2-methyl-2-acetyl- '- ´ - acetaldehyde · - ^ /.

Obviously, the samples containing the organic stabilizer are 'far less' stained and have a higher heat stability. ...........

Examples · 31 to 4 4 · ''

14 samples are prepared from the following mixture with various additives. The method of sample processing, manufacturing and testing is the same as in the previous examples. The added zinc salts and .beta.-diketones are listed in the table as well as the results obtained. · '·

2.5 mm thick samples are prepared from the material on a calender, heated to 180 ° C. The coloring is determined using a Gardner scale. ;. ···. ' 1

PVC · 10 g, 'butadiene-styrene-methyl methecrelate copolymer 10 g, Cire E' 1 ·· 'g, calcium stearate 0.5 g and epoxidized soya. oil 3 grams. - ·. ·

Examples 45 to 58 of the samples are prepared as follows in the examples below as follows:

PVC 100 g, copolymer of butadiene, styrene and methyl methacrelate 10 g, Cire E 1 g, zinc stearate 2.5 g, and epoxidized soya oil 3 g.

To this mixture are added the other ingredients listed in the table, namely the calcium salts and optionally the [beta] -11] ketone.

The results are also shown in the following table.

The method according to. In the previous examples, 10 samples are prepared from the 'following' mixtures:

PVC resin (RS 8000) 100 g, copolymer of butadiene, styrene and methmethacrylate 10 g, Cire 1 g and epoxidized soybean oil 3 g. 'IN

To this 'mixture' are added the additives according to the following table, namely calcium salts and calcium salts. zinc and optionally 3-diketone. The results are also shown in the table.

Examples' 69 'to' 7 5.

When 0.5 g of acetylphenones are added to the mixtures of Examples 31, 33, 35, 37, 39, 41 and 43, see sample. · · '. ···, i

^J CH (CH _z) ^f CH «CH-

'' - · PATTERN · - '......? >. · <

the same 'as in' 'examples' 32,' 341 ', 36, 38, '40, 42' and 44 are obtained:

Examples 76 to 85 '

From the following 'blends', '10' samples are prepared as described in the previous examples:

PVC resin (RS 8000) 100 g, copolymer of butadiene, styrene and methyl methacrylate · 10 g, Cire · E 1 · g · and 'epoxidized soybean oil 3' g. T ^; The &quot; samples &quot; contain the other ingredients listed in the following table, namely barium and zinc salts and optionally. The results are shown in the following table.

19929 * 'Table

Examples . Ingredient Color according to Gar of the day of the scale in X minutes

0 '7 min. 14 less. 20 min. 28 iňin. 35 min.

0.25 g of zinc stearate 7 9 9 9 10 10

’О Q О ID About XF 0 ^ 0 ^ · ' About CM О H xjl 0 ^ 0 rH rH г — 1 rH rH rH rH rH - rH rH rH rH

N ON ON e й tH rH rH

1Л

0 rH 0 r1 rH rH

CM

CM 00 Mi ю CO O 00 OS Q rH CM

ОО CO со СО СО СО 00 Ф TJ1 Tfi CO m CO co 03 O rH CM

1ГЗ ID co ID in ID ID bcooo id id co m

1992115й «я — 4

and.· o · r4. r4 тЧ. O. гЧ O Ή ώ oo гЧ . 00 . гЧ. .. σ> í ^: см 1Л 00 - 1

О) тН гЧ

СО О cd. см

О оо О σ> о ·. tš о

Q% · Q. . . гЧ Ь * rH bs ·· гЧ ^; лСМ.

, ο

> 4 Ό ϋ>--t

r4 CM. 00 m what O. 00 , CD 00 O) O r4 WHAT what what what what what. ... CO > Cp - ··. b- bs bs bs 00 00

0.2 g of barium benzoate

0.5 g of barium stearate

0.2 g of benzoate benzoate + ‘0.6 g of DPM

0.5 g barium stearate + 0.6 g DPM

198286 ri ιη

CD

Q to bOQ CQ bo and o cq. + ° o + And Shield 44 o Stí gs gs > 6 sec CD P Os , S й N 43 .9 «J Я 43

1062Э5

Claims (10)

OBJECT OF THE INVENTION CLAIMS 1. Stabilized n-a materials based on polymers or copolymers of vinyl chloride, characterized in that they contain 0.1 to 5% by weight of one or more salts of aliphatic or aromatic acids with divalent metals, for example calcium, barium or zinc, and 0.05 to 5% by weight of an organic compound of formula (I) R 1 -CO-CHR 2 -CO-R 3 (I, where R 1 and R 3, the same or different, denote straight or branched chain alkyl or alkenyl of up to 30 carbon atoms, arylalkyl of 7 to 36 carbon atoms, aryl or cycloaliphatic of up to 14 carbon atoms, the cycloaliphatic optionally having inter-carbon double bonds optionally the radicals R 1 and R 3 are altered by the presence of one or more groups -O-, -C -O-, -CO-, II in the aliphatic chain and may additionally form a bivalent alkylene radical having 2 to 5 carbon atoms, optionally containing an oxygen or nitrogen atom and one of R 1 or R 3 may be a hydrogen atom, R2 represents a hydrogen atom, an alkyl or an alkenyl of up to 30 carbon atoms, which radical optionally contains a group ________, -Q, -C1-O-, -CO-, II o ......_____ the rest of the formula _- . _- —CO — R4 wherein R4 represents an alkyl group having from 1 to 30 carbon atoms or aryl, a radical of the formula wherein R5 represents an alkylene radical having from 1 to 6 carbon atoms, and R 1 and R 3 are as defined above. i. 2. Stabilized materials according to item; 1, characterized in that R2 to R5 are as defined above and R1 to R3 are as defined above except for hydrogen. 3. Stabilized materials according to point? 1, characterized in that R1 to R5 are as defined above, provided that one of the substituents R1. and R3 represents a hydrogen atom. ': I 4. The stabilized material of claim 1, wherein the polymer is a vinyl chloride homopolymer or copolymer obtained by copolymerizing vinyl chloride with one or more other monomers having an unsaturated ethylene bond, wherein the proportion of vinyl chloride in the copolymers is at least 50% w / w. : - 5. Stabilized materials according to boron. characterized in that the polymer is a copolymer in which the proportion by weight of the copolymerized vinyl chloride is greater than 80% by weight. ..; > 6. The stabilized material of claim 1, wherein the first component is a pair of salts of organic acids of calcium and zinc, or barium and cadmium. _ 7. The stabilized material of claim 1, wherein the compound of formula (I) is [beta] 3ketone. ’ 8. The stabilized material of claim 1, wherein the compound of formula (I) is (3-ketoaldehyde). 9. The stabilized material of claim 1, wherein the compound of formula I is a saturated or unsaturated aliphatic compound having from about 14 to about 30 carbon atoms. ··. 10. The stabilized materials according to claim 1, wherein the compound of formula I is stearcylacetone or stearoylbenzophenone. r. '·. —Rs — CH CO — Ri CO — R3