DE2354534A1 - Photodecomposable plastic compsns. - contg. thermoplastic and transition metal-polymer complex - Google Patents

Abstract

Plastic compsn. consisting of a conventional thermoplastic material (A) and a stransition metal contg. polymeric cpds. (B) which contain the transition metal complexed to 1,3-dicarbonyl gps. which are joined to the polymer. Pref. thermoplastics (A) are polyolefins and/or polystyrene. The compsns. can be obtd. by reacting components (A) and (B) or component (A), the 1,3-dicarbonyl gp.-contg. polymer and a transition metal cpd., at a temp. of 110-350 degrees C for 1-30 mins. The resulting compsn. pref. contains 0.1 to 250000 ppm of transition metal. The transition metals are the elements of the 4th Period, atomic nos. 21-30, 5th period atomic nos. 39-48 and 6th period, atomic nos. 57-79. Components (B) render the thermoplastics (A) decomposable under the influence of UV and/or sun light, so that objects, e.g. packing material, drinking beakers, etc. made from these plastics are made photo-decomposable. Pref. transition metals are Fe, Co, Ni, Mn, Cr, Cu and Zn. The 1,3-dicarbonyl gp.-contg. polymers are obtd. by reacting diketene with a polymer contg. -OH, -SH, amine, acid hydrazide, amide, or acetal gps. or aromatic ring systems, or by reacting diketene with corresp. monomers followed by polymerizn. The 1,3-dicarbonyl gp. contg. polymer is reacted with transition metal cpds. in suspension or soln. at a temp. between -50 degrees and +150 degrees C for a time of 5 min. to 6hrs. so that the transition metal is complexed to the polymer in amt. of 0.1 ppm-6 wt. % of light-decompsn.-producing cpds. e.g. benzophenones, and arylalkyl-ketones.

Description

Bayer Aktiengesellschaft 2354534

Central area of patents, trademarks and licenses

509 Leverkusen, Bayerwerk

E / Gi 30th OCT. 1973

Degradable plastic compositions

The invention relates to plastic compositions made of thermoplastic Plastics and transition metal-containing polymers, a process for their production and their Use as plastics that are degradable under the influence of ultraviolet radiation and / or sunlight.

Lately it has been getting stronger in the context of discussions raised the demand for degradable plastics about environmental problems. It seems extremely desirable for certain Areas of application to provide short-lived, rotable objects made of plastics; such as packaging materials, Drinking cups, etc. which are not always desirably disposed of in an orderly landfill or incineration will..

It is known to add polyolefins or other plastics to be set photodegradable by additives. Such additives are mentioned in DT-OS 2 I36 704, for example. Will Objects or foils made from these natural plastics When exposed to the elements, the sunlight causes it to break down more or less quickly into small particles one which then in turn causes biodegradation

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Microorganisms are accessible.

Low molecular weight components are added as additives, which are only dissolved in the polymers and therefore extractable are. As a result of the extraction of the additives, the photodegradability can occur partially or completely lost. Furthermore, unpredictable problems can arise when using additives Photo-degradable plastics are used for the packaging of food. Additives that The food that has migrated into can adversely affect its taste and smell. Toxicological problems require a particularly intensive examination and can approve such additives for plastics used in the food sector be used, make it difficult or impossible.

DT-OS 2 136 704 mentions that the complex-forming Groups can form part of a polymer chain, but there is no corresponding teaching on technical action, because the polymer not only has to have the ability to form complexes, but also its homogeneous compatibility must be given with the degradable plastic to be set.

Another way of producing photodegradable plastics is described in DT-OS 2 206 806, for example and leads to the incorporation of photosensitive groups into the corresponding polymer. The typical ' Disadvantages of low molecular weight additives, however, are said to be the light degradability due to the incorporation of reactive groups into the polymer must be achieved during the production of the plastic by polymerizing special, photosensitive Groups carrying comonomers a modification of the polymer can be made. This procedure leads

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therefore complicating the production of the degradable plastic to be set. Furthermore, a general one is missing Possible application, it must rather be checked on a case-by-case basis whether a copolymerization of the desired monomers seems possible at all,

The object of the present invention is now to provide plastic compositions to provide a process from thermoplastics and polymers containing transition metals to develop them for their production and to show their use as degradable plastics.

Such plastic compositions combine: the advantages of plastics made degradable with additives subsequent Incorporation of the additives - as well as the advantages of polymerized, light-sensitive groups - no migration problems -.

The invention thus plastic compositions consisting of a conventional thermoplastic resin (A) and a transition metal-containing polymeric compound (B) _s contain the transition metal via 1,3-dicarbonyl groups, which are bound to the polymer complexed.

Other objects include a method of making such Plastic compositions and their use as degradable plastics. . -.

The transition metal is in the transition metal-containing polymer Compound (component B) in an amount of 0.1 ppm to 6% by weight, preferably 10 ppm to 3% by weight, based on component B, included in complex bound.

The transition metal-containing polymers (B) become conventional ones thermoplastic plastics (A) are added in such amounts that transition metal-containing mixtures with a metal content

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of 0.1 Ms 25,000 ppm, preferably 1 to 1,000 ppm, arise.

The elements of the 4th period with ordinal numbers from 21 "up to and including 30, the elements of the 5th period with the ordinal numbers from 39 to 48 inclusive and the elements the 6th period with the ordinal numbers from 57 to 79 inclusive. Iron are preferred. cobalt Nickel, manganese, chromium, copper and zinc. Iron is considered to be particularly preferred.

The polymeric compounds (B) are macromolecular substances in the sense of H. Staudinger, "Organic Colloid Chemistry", F. Vieweg u. Sohn, Braunschweig, 1950, 3rd edition, i.e. compounds that contain 1000 or more atoms in the molecule.

The concept of the complex, especially that of the transition metal complex with organic ligands, has been introduced in general and requires no further explanation than that the transition metal is non-ionically bonded and is part of at least one four, but mostly six- or seven-membered ring is composed of one or more complex-forming groups as well as the transition metal is formed. See F. Hein, "Chemical coordination theory", S. Hirzel Verlag, Leipzig, 1950 and A.E. Mar tell, M. Calvin, "The Chemistry of Metal Chelate Compounds", Verlag Chemie, Weinheim / Bergstrasse, 1958.

Polymer systems in the sense of component (B) are all polymers who carry 1,3-dicarbonylgrappen.

These 1,3-dicarbonyl groups are obtained, for example by implementing diketen with. aliphatic and phenolic hydroxyl or mercapto groups, with aliphatic or aromatic bound primary or secondary amino groups, with acid hydrazide groups, with. Acid amide groups, with acetals and with aromatic ring systems.

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23545

The polymers bearing 1,3-dicarbonyl groups can have both by. Implementation of the functional groups mentioned above Polymers with diketene as well as by reacting corresponding ones functional group-bearing monomers can be obtained with diketene and subsequent polymerization. In the last In this case, monomers can of course be used in the polymerization without 1,3-dicarbonyl groups are used as comonomers.

According to the route listed first, the reaction of polystyrene with diketene, for example in a solution of trichlorethylene and in the presence of a Lewis acid, leads to an acetoacetylated polystyrene. The reaction of acetals of polyvinyl alcohols, such as polyvinyl butyral, with diketene also gives polymers with 1,3-dicarbonyl groups. Polymers containing acid hydrazide groups are formed, for example, in the reaction of styrene-maleic anhydride copolymers with hydrazine according to US Pat. No. 3,679,640. Further reaction with diketene then leads in turn to polymers with 1,3-dicarbonyl groups. Polymers containing acid amide groups are formed, for example, in the homopolymerization or copolymerization of (meth) acrylamide. Further reaction with diketene then gives polymers containing 1,3-dicarbonyl groups. Acetoacetylated polymers also result from diketene and polymers with primary and / or secondary amino groups, for example certain aminoplasts such as melamine-formaldehyde condensates. Polymers with mercapto groups, such as the reaction products of hydroxyl-containing polymers, such as polyvinyl alcohols and mercaptocarboxylic acids, such as mercaptoacetic acid, or the reaction products of carboxyl-containing polymers, such as polyacrylic or polymethacrylic acid and mercaptoalkanols, such as 2-mercaptoethanol, yield 1,3-dicarbonyl groups by reaction with diketene Polymers. Finally, polymers containing 1,3-dicarbonyl groups can be obtained from all polymers containing hydroxyl groups, such as polyvinyl alcohols or certain phenol-formaldehyde condensates, by reaction with diketene.

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The reaction of the above polymers with diketene takes place in a solvent that is inert to diketene. Such solvents are, for example, chlorinated hydrocarbons, such as methylene chloride and chloroform, aromatic hydrocarbons, such as toluene, also dioxane, dimethylformamide, methyl ethyl ketone. Generally a solvent is used which dissolves the polymer to be reacted with diketene, so that, after the reaction has taken place, the polymer bearing 1,3-dicarbonyl groups can be precipitated in, for example, methanol.

But it is also possible to use a solvent which does not dissolve the polymer to be reacted with diketene. Naturally, the reaction then takes place essentially only in a thin surface layer of the polymer particles. One Precipitation is not required here.

The reactions with diketene can be catalyzed acidic or basic, for example with tertiary amines. The reaction temperatures are approximately between 15 ° C. and 140 ° C., the reaction times varying between 30 minutes and 24 hours.

Polymers containing 1,3-dicarbonyl groups can also by homopolymerization of monomers containing 1,3-dicarbonyl groups or by their copolymerization with other suitable monomers. 1,3-dicarbonyl groups containing monomers are e.g. vinyl and allylacetoacetic esters as well as hydroxypropyl (meth) acetoacetylated with diketene acrylate, hydroxyethyl (meth) acrylate and N-methylol (meth) acrylamide. Suitable comonomers are, for example, alkyl and / or aryl olefins such as ethylene, propylene and / or styrene and d & -Methylstyrene, acrylic acid, methacrylic acid, acrylates, methacrylates, Acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl esters such as vinyl acetate, maleic anhydride, vinyl chloride.

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In the following, the above way is an example of the reaction of hydroxypropyl (meth) acrylate with diketene and subsequent copolymerization with styrene. Every professional It is possible to transfer this system described to the other listed monomers containing 1,3-dicarbonyl groups.

The acetoacetylation of hydroxypropyl (meth) acrylate is achieved by adding diketene with stirring. The reaction can under tert. Amine catalysis, and at 15 ° C to 80 ⁰ C carried out "will be. In a solvent can be dispensed with. The homo- or .Copolymerisation to 1,3-dicarbonyl-bearing polymers is carried out according to the general methods for Homobzw. Copolymerization of monomers. so can copolymerize with styrene is, for example, acetoacetylated hydroxypropyl (meth) acrylate, by initially introducing the first component in toluene and, at 11O ⁰ C, the styrene, in which a polymerization catalyst such as dibenzoyl peroxide is dissolved is added. After several hours, the 1,3 - Polymers bearing dicarbonyl groups precipitated in methanol.

Polymers carrying 1,3-dicarbonyl groups can also pass through Transesterification of polymers containing hydroxyl groups with ethyl acetate, such as ethyl acetoacetate can be obtained. This transesterification can also be carried out with monomers containing hydroxyl groups, such as hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylol (meth) acrylamide can be carried out. the subsequent homopolymerization or copolymerization with suitable listed above. Comonomers that do not contain 1,3-dicarbonyl groups must contain, then also leads to polymers bearing 1,3-dicarbonyl groups. The transesterification step can be accelerated by titanium tetrabutanolate or acidic catalysts. Other transesterification catalysts are known to the person skilled in the art.

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In terms of the component (B) used, all polymers are suitable which contain 1,3-dicarbonyl groups as discussed in the previous sections. The type of Residual molecule is not important. If, for example, one starts from a polymer containing hydroxyl groups, then by no means have to all hydroxyl groups are converted with diketene to 1,3-dicarbonyl groups. The distribution of the 1,3-dicarbonyl groups along the polymer chain is arbitrary. It can be statistical, such as possible in a copolymer, or not statistical, such as in a block polymer composed of a 1,3-dicarbonyl group bearing monomer and one of the above-mentioned suitable comonomers, but which do not contain 1,3-dicarbonyl groups contain. The remainder of the molecule, however, must be such that the 1,3-dicarbonyl group-bearing is compatible Polymer is given with the degradable thermoplastic to be set.

The above-described, 1,3-dicarbonyl group-containing polymers are reacted with transition metal compounds to transition metal-containing polymers, the transition metal in an amount of 0.1 ppm to 6 wt .-%, preferably 10 ppm to 3 wt .-%, based on contain the polymer bound in a complex. The reactions can be carried out in a wide temperature range, for example between -50 ° C. and + 150 ° C., in suspension or in solution, and are complete within five minutes to six hours. Any person skilled in the art can choose an appropriate suspension or solvent. The type of procedure has no influence on the properties of the product with regard to its degradability. The reaction conditions are, however, to be chosen very differently depending on the polymer used and carrying 1,3-dicarbonyl groups.

For example, a polyethylene bearing 1,3-dicarbonyl groups is used suspended in a non-solvent, the desired Transition metal compound added and the transition metal-containing polymer isolated after a few hours.

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In another case, solution polymerization of a monomer bearing 1,3-dicarbonyl groups with styrene results in a copolymer produced, which is reacted in dissolved form with the desired transition metal compound. The implementation is done by mixing the components. The transition metal-containing polymer is finally by precipitation, for example Methanol.

However, the complex formation can only occur in the process according to the invention Plastic composition can be carried out by in the thermoplastics contain 1,3-dicarbonyl groups carrying polymer and the transition metal compound simultaneously or successively, for example by extrusion, incorporated will.

A typical embodiment of the process in which the finished Transition metal-containing polymer (component B) is incorporated into the thermoplastic material, ie the complex formation has taken place before the incorporation, is as follows listed: ·

An acetoacetic ester group-containing obtained as described Polymer is in a solvent in which the polymer is not soluble, e.g. in an alcohol, such as Ethanol or in water or in a water-alcohol — Gtemisah slurried in the form of fine particles and emanated with the j ^ Amount of a transition metal compound, e.g. FeCl ^ TE replaced. The product obtained now turns red as a result of complex formation shows, is coextruded with e.g. polyethylene.

A typical embodiment of the process in which the formation of component B, i.e. the complex formation between 1,3-dicarbonyl groups carrying polymer and the transition metal compound, only during incorporation into the thermoplastic Plastic is going on, be noted as follows:

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A polymer containing acetoacetic ester groups obtained as described is extruded together with, for example, polyethylene

_3 dated so that a product is obtained that is about 10 to Contains 10 moles of acetoacetic ester groups per 100 g of product. Simultaneously or subsequently, the desired amount of a suitable transition metal compound is made by extrusion or compounding incorporated.

The following inorganic salts of the transition metals already defined may be mentioned, for example, as suitable transition metal compounds: chlorides, bromides, sulfates and / or nitrates. Suitable organic compounds of these transition metals are, for example, the salts of mono- and polyfunctional carboxylic acids such as ^A cetate, octoates, palmitates, stearates, oleates, naphthenates, oxalates, such as K ^ Fe (CPO, K, tartrates and citrates, further acetylacetonates, acetoacetates, such as ethyl or dodecyl acetoacetate, N, N-dialkyl dithiocarbamate and / or dialkyl dithiophosphate. The respective iron, cobalt, nickel, manganese, chromium, copper and / or zinc compounds are preferred. Iron chloride, iron stearate, iron ethyl acetoacetate are particularly preferred , Iron acetylacetonate and / or iron naphthenate.

Suitable thermoplastics (A) are all relevant customary thermoplastics, such as homo- and / or copolymers from ά-olefins and / or styrene. For example, are preferred Polyethylene, polypropylene and polystyrene.

The transition metal-containing, preferably iron-containing masses represent degradable plastics that are under the influence of natural weather, especially under the influence of ultraviolet radiation and / or sunlight depending on the metal content more or less rapidly degraded, while they are filtered through sunlight that has been filtered through approximately 3 mm thick window glass, not noticeably changed.

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The mixtures consisting of the transition metal-containing polymers (B) and the conventional thermoplastics (A) can be produced by the masterbatch method. First, a masterbatch with a transition metal content of 1 ppm to 6% by weight, preferably 100 ppm to 5% by weight , is produced. The masterbatch consists of a conventional thermoplastic material and the desired amount of the transition metal-containing, polymeric compound and is; obtained for example by joint extrusion of the conventional thermoplastic material and a transition metal-containing polymer or by joint extrusion of the conventional thermoplastic material, a polymer containing 1,3-diaconyl groups and a suitable transition metal compound. In order to obtain the end product, the masterbatch is coextruded or compounded with the amount of thermoplastic material required for the desired metal content, which has already been used to produce the masterbatch or which is homogeneously compatible with it. In general, it is also possible to make plastic alloys degradable. When producing the masterbatch or In the production of the degradable plastic compounds, one or more of the transition metal-containing polymers or transition metal compounds according to the invention can be used, so that degradable plastic compounds are ultimately obtained which may contain more than one transition ball.

The incorporation of the. Transition metal-containing polymers (component B ^ i or the incorporation of the 1,3-dicarbonyl groups tra- · lowing polymers and the transition metal compounds in the respective thermoplastic material for the purpose of manufacture " a transition metal-containing masterbatch or a transition metal-containing plastic composite according to the invention

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Setting takes place by mixing as homogeneously as possible, such as Extruding, compounding or rolling on the for this usual. Machines under the usual conditions for the thermoplastic used in each case. This is how it is done Mixing in a temperature range from a mixing time of 1 min. To 30 min.

Mix in a temperature range of 100 C to 350 C.

If one of the transition metal compounds mentioned is in the respective thermoplastic material incorporated together with or after the polymer bearing 1,3-dicarbonyl groups, so the compound can be incorporated either as a pure substance or in the form of a solution. In the latter case, will the solvent usually during the incorporation due to the high processing temperatures from the plastic composition removed. An extruder with a degassing zone can advantageously be used.

0.1 to 5.0 % by weight of other photodegradation-promoting substances, such as those mentioned, for example, in German Offenlegungsschrift No. 2,133,896, ie benzophenones such as benzophenone, arylalkyl ketones such as Acetophenone and propiophenone, anthraquinones, fluorenones and / or xanthones.

The plastic compositions according to the invention can contain the usual additives, such as blowing agents, pigments or fillers, Antistatic agents, lubricants or other aids can be added. You can, like all thermoplastics according to the known methods are processed on the usual machines to form molded parts, films, threads or fibers.

The following examples illustrate the invention without restricting it.

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example 1

200 g of an approximately 97% saponified copolymer of ethylene and vinyl acetate (mp 100-112 ° C.) with an OH content of approx. 7% were dissolved in chloroform and reacted at 60 ° C. with 70 g of diketene. The reaction mixture was stirred at 60 ° C. for a further 2 hours. The product was then precipitated in methanol. The polymer (melting point 100-1-15 ° C., freezing temperature 41-42 ° C.) was obtained in an almost quantitative yield (> 95%) as a fine, white powder.

Example 2

200 g of the saponified ethylene-vinyl acetate copolymer mentioned in Example 1 were dissolved in chloroform and ^{reacted at 60 °} C. with 73 g of mercaptoacetic acid. The reaction took place on a water separator and with p-toluenesulfonic acid catalysis. After the reaction had taken place, the catalyst was neutralized with sodium hydrogen carbonate and separated off. The product was reacted with 66 g of diketene at 60 ° C. in chloroform without further work-up. The reaction mixture was stirred for a further 2 hours at 60 ° C. and then precipitated in methanol. The polymer precipitated in about 75% yield based on the employed copolymer, as a white powder (mp 80 ⁰ C - 101 ⁰ C).

Example 3

52 g of polystyrene were dissolved in 1,2-dichloroethane at 40 ⁰ C and placed ₅ g of diketene at 21 to the reaction at this temperature in the presence of AlCl ^. The reaction mixture was stirred for a further 4 hours at 40 ° C. and finally poured onto ice / hydrochloric acid. The product was brought into a crystalline, easily isolable form by adding methanol. The polymer was obtained as a yellow powder (m.p. 140 ⁰ C - 145 ° C).

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Example 4 Ar

144 g of hydroxypropyl methacrylate were mixed with 1 g of triethylamine. 84 g of diketene were then added dropwise at 55 ° C. with stirring and the mixture was subsequently stirred at this temperature for 1 hour. 23 g of this reaction product of hydroxypropyl methacrylate with diketene were placed in toluene. At 110 ° C., 104 g of styrene, in which 3.5 g of dibenzoyl peroxide had been dissolved, were added dropwise over the course of 1 hour. The solution was stirred for a further 4 hours at this temperature and then precipitated in methanol. In about 90% yield a white polymer powder was obtained (mp 120 ⁰ C - 140 ⁰ C).

Example 5

23 g of the reaction product of hydroxypropyl methacrylate with diketene prepared in Example 4 were placed in toluene. At 110 ^° C., 100 g of methyl methacrylate, in which 3.5 g of dibenzoyl peroxide had been dissolved, were added dropwise over the course of 1 hour. The reaction mixture was stirred for a further 3 hours at 110 ° C. and then precipitated in methanol. The polymer precipitated as a white powder in approximately 95% yield (mp 141 ⁰ C 159 ° C).

Example 6

11.5 g of the reaction product of hydroxypropyl methacrylate with diketene prepared in Example -4 were initially introduced in toluene. At 11O ⁰ C for a further 103 g of this product were had been dissolved in 3.5 g of dibenzoyl peroxide was added dropwise within 1 h.. The solution was stirred for a further 3 hours at 110 ° C. and then precipitated in methanol. A slightly yellow-colored polymer powder was obtained in about 80% yield (mp 77 ° C. 85 ° C.).

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Example 7

200 g of the saponified ethylene-vinyl acetate copolymer from Example 1 were dissolved in chloroform and transesterified at 60 ° C. in the presence of catalytic amounts of p-toluenesulfonic acid with 160 g of ethyl acetoacetate. If the reaction is carried out in DMF or dioxane, ethanol can be distilled off continuously. In this 'case' only about 115 g of ethyl acetoacetate are required. The polymer was isolated after precipitation in methanol (melting point TOO ⁰ ° C.-113 ° C.).

Example 8

72 g of hydroxypropyl methacrylate were placed in toluene and transesterified with 65 g of ethyl acetoacetate in the presence of catalytic amounts of titanium tetrabutanolate. The resulting ethanol was continuously distilled off ,,. · After completion of the transesterification were performed at 110 ⁰ C 520 g of styrene, in the "17,5 g of dibenzoyl peroxide were dissolved were added dropwise over 3 hrs.. The reaction mixture was further 5 hrs. At 110 ^The mixture was stirred at 0 ° C. and then precipitated in methanol The polymer was obtained as a white powder (melting point 115 ° C.-140 ° C.).

Example 9

In each case 100 g of the 1,3-di carbonyl groups prepared in Example 1 Carrying polymers were suspended in ethanol and at room temperature with the desired amount of a transition metal compound offset. For this purpose, the transition metal compound was generally previously in a solvent, such as ethanol and / or water dissolved and then added dropwise. The reaction mixtures were for a further 30 minutes to 4 hours at room temperature touched. Finally, the transition metal-containing polymer was isolated by filtration. The table shows some of the after products manufactured using this process. Column 1 gives the

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transition metal compound used, column 2 the amount the transition metal compound used, column 3, the analytical determined amount of the transition metal in the polymer and column 4 the color of the transition metal-containing polymer.

Table 1 '

Transition metal compound

Transition metal quantity used, metal content

in polymer (ppm)

Coloring of the transition metal containing poly

meren

1 FeCl ₃ 0.15 g 510 Red 2 FeCl ^ 0.75 g 2550 Red 3 Fe stearate 1.30 g 800 Red 4th F e-naphthenate 3.00 g 1780 Red 5 Fe-ethylacetoace- did 1.20 g 1460 Red 6th Fe acetylacetonate 1.20 g 1750 Red 7th Mn stearate 1.70 g 1300 White 8th Co-octoate 2.00 g 1100 pink 9 CuCl ₂ 0.08 g 350 light green 10 CuCl ₂ 0.55 g 2500 light green 11 Cu stearate 3.90 g 3800 light green 12th Cu oleate 2.30 g 2230 light green 13th Cu naphthenate 2.00 g 1520 light green 14th NiCl ₉ 0.10 g 380 light green

As Fe-naphthenate, Co-octoate, Cumit 6 wt -.% Fe, 6 wt .- ^ Co and

Example 10

• naphthenate solutions 8 wt .-% Cu were used.

In each case 100 g of the 1,3-Dicarbony1 .Groups-bearing polymer prepared in Example 4 were dissolved in a toluene solution at 40 - 50 ⁰ C reacted with the desired amount of a transition metal compound. By introducing ammonia, the

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Solution neutralized. This was followed by the precipitation of the
transition metal-containing polymers in methanol. The products
were obtained as fine, mostly colored powders. The table shows some of the products made by this process.

Table 2

Transition metal compound

amount used

Transition metal content
in the polymer
(ppm)

Coloring of the transition metal containing Polymers

1 FeCl ₃ 8.5 g 19th 500 Red 2 FeCl ^ 2.0 g 6th 200 Red 3 Fe stearate 1.6 g 900 Red 4th Mn stearate 1.0 g 820 White' VJl CuCl ₂ 0.5 g 2 100 light green 6th Cu oleate 3.0 g 2 950 light green 7th / Ör (H ₂ O) ₆ _7cl ₃ 1.0 g 1 750 light green 8th ZnCl ₂ 0.5 g 2 100 White Example 11

The transition metal-containing polymers prepared in Example 9 were incorporated into polyethylene (Baylon V 22 H 864, manufacturer: Bayer AG, Leverkusen) in the amounts listed below, so that the total mixture resulted in 100 g in each case: 9.8 g of the iron-containing polymer (Tab . 1, line 1), 0.77 g of the manganese-containing polymer (Table 1, line 7), 2.72 g of the cobalt-containing polymer (Table 1, line 8), 1.33 g of the copper-containing
Polymers (Tab. 1, line 13), 2.63 g of the nickel-containing polymer (Tab. 1, line 14)

The products obtained in this way became foils of approx. 0.1 mm
Thickness produced and in the Xenon test (Atlas Weather-Ometer, 600
Watt emitter, spray cycle 102: 18) subjected to artificial weathering. At the same time was in a comparative experiment

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λ?

a film made of conventional polyethylene, i.e. Baylon

V 22 H 864 without the addition of a transition metal-containing polymer,

subjected to this test.

The degradation was determined by observing the appearance of the surface der Films "as well as by measuring the time it had to pass before vigorously double folding twice 180 degrees led to breakage of the foils.

The results of the xenon test are shown in Table 3

Table 3

Trial transition metal content (ppm)

1 50 12th Fe 2 10 Mn 3 30th Co 4th 20th Cu 5 10 Ni Comparison
attempt - example

Dark color
the surface
(by days) radiation time
until the break of the
Slide through dop
pelfalten (days; 8.5 12th 22nd 30th 17th 25th 22nd 31 30th 45

no observable changes during the entire duration of the test.

5 g of the metal-free, acetoacetylated copolymer prepared according to Example 1 were dissolved in 95 g of polyethylene (Baylon V 2.2
H 864, manufacturer: Bayer AG, Leverkusen). Then 0.8 g of iron acetoacetic ester were incorporated. · A masterbatch with 0.1% iron content was obtained. Joint extrusion of 200 g, 100 g, 50 g, 10 g of the masterbatch
with 800 g, 900 g, 950 g, 990 g of polyethylene each gave 1000 g of polyethylene with an iron content of 200, 100, 50, 10 ppm.
The results of the xenon test are summarized in Table 4.

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Example 15

5 g of the metal-free, acetoacetylated prepared according to Example 1 Copolymers were made together with 0.8 g of iron acetoacetic ester in 95 g of polyethylene (Baylon V 22 H 864, manufacturer: Bayer AG, Leverkusen) incorporated by extrusion. It was get a masterbatch with 0.1% iron content. Joint extrusion of 200 g, 100 g, 50-g, 1.0 g of this masterbatch with 800 g, 900 g, 950 g, 990 g polyethylene each yielded 1000 g polyethylene with an iron content of 200, 100, 50, 10 ppm. The results of the xenon test can be found in Table 4.

Example 14

The 0.8 g of iron acetoacetic ester from Example 12 were replaced by 1.62 g of iron stearate. In Table 4 are the results

of the xenon test.

Example 15

The 0.8 g of iron acetoacetic ester from Example 15 were replaced by 1.62 g of iron stearate. Table 4 shows the results of the xenon test. ·

Table 4

attempt

Iron content (ppm)

Dark color and the
surface
(by days)

Irradiation time until the film breaks due to double folding (days)

Ex. 12

200

100

50

TO

3.5

5.5

8 13 24

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3.5 5.5

6 8
9 13 14 24

3 4.5

4.5 6.5

7 11 11 22

3 4.5

4.5 6.5 '

7 11

11 '22

no observable changes during the entire duration of the test

5 g of the metal-free, acetoacetylated copolymer prepared according to Example 1 were extruded into 85 g of polyethylene (Baylon VH 86.4, manufacturer: Bayer AG, Leverkusen). At the same time, 1.62 g of iron stearate and 10 g of isopropylbenzophenone were incorporated. A masterbatch with 0.1 % iron content and 10% isopropylbenzophenone content was obtained. Joint extrusion of 100 g, 50 g of this masterbatch with 900 g, 950 g of polyethylene yielded 1000 g of polyethylene each with an iron and isopropylbenzophenone content of 100, 50 ppm and 1.0-0.5%, respectively. The results of the xenon test are summarized in Table 5.

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Ex. 13 200 100 50 10 Ex. 14 200 100 50 10 Ex. 15 200 100 50 10 Comparison
attempt - Example 16

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Table 5

attempt

Iron content ^ ppm)

Isopropyl

benzophe

non-content dark, irradiation time staining until breakage Fold the upper film through a double surface (days) (after Tgn.)

Ex. 16

Comparative experiment

100
50

1.0 0.5 3
5.5

5 8

no observable changes during the entire duration of the test

Example 17-19 . -

Instead of the polyethylene used in Examples 11, 13 and 15 now polypropylene (Hostalen PPH 1050, manufacturer: Farbwerke Hoechst, Frankfurt / M) was used. This corresponds to in the other procedure, Ex. 17 corresponds to Ex. 11 ″, Ex. 18 corresponds to Ex. 13 and Ex. 19 corresponds to Ex. 15. The Results of the xenon test are shown in Table 6.

Table 6

Test of iron content Darkening (ppm) of the surface (in days) Irradiation time until the film breaks due to double folds (days)

E.g. 17th 50 8th E.g. 18th 200 3 100 4.5 50 9 10 12th E.g. 19th 200 2.5 100 3.5 50 5.5 10 10 Comparison _ no B attempt rend de Le. - 21 - A 15 326

10

4.5 6.5 11 22

3.5

5.5 9

17.5 no observable changes during

5 0 9 8 19/0919

Example 20

5.13 g of the iron-containing polymer prepared according to Example 10, Tab. 2, line 1 were extruded into 95 g of polystyrene (143 E, manufacturer: BASF, Ludwigshafen). A masterbatch with 0.1% iron content is obtained in this way. Straight extrusion of 100 g, 50 g, 10 g of this masterbatch with 900 g, 950 g, 990 g polystyrene resulted in each case 1000 g polystyrene with an iron content of 100, 50, 10 ppm. Foils approx. 0.1 mm thick were produced from the products thus obtained and in the xenon test. (Atlas Weather-Ometer, 600 watt emitter, spray cycle. 102: 18) subjected to artificial weathering. At the same time, a film made of conventional polystyrene, ie of polystyrene 143 E without additives, was subjected to this test in a comparative test. The degradation was determined by observing the appearance of the surface of the films and by measuring the time it had to pass before the films could easily be ground into small particles or into a powder with the fingers (embrittlement of the films). The results of the xenon test are shown in the table.

Table 7 '

attempt

Iron content
(ppm)

Dark coloring
the surface
(by days)

Irradiation time until the film becomes brittle (days)

E.g. 20 100 50 10 Comparative
attempt - Example 21

2.5

7.5

5.5 7 16.5

no observable changes during the entire duration of the test

5 g of the iron-free copolymer described in Example 4 were extruded into 95 g of polystyrene (143 E, manufacturer: BASF, Ludwigshafen). Then 80 mg of iron acetoacetic ester were added incorporated. A masterbatch with an iron content of 100 ppm was obtained. Joint extrusion of 500 g, 100 g this masterbatch with 500 g, 900 g polystyrene each resulted in 1000 g polystyrene with an iron content of. 50, 10 ppm. the Results of the xenon test are summarized in Table 8.

Le A 15 326

- 22 509819/0919

33

Example 22

5 g of the iron-free copolymer described in Example 4 were together with 80 mg of iron acetoacetic ester in 95 g of polystyrene (143 E, manufacturer: BASF, Ludwigshafen) by extrusion incorporated. A masterbatch with an iron content of 100 ppm was obtained. Joint extrusion of 500 g, 100 g this masterbatch with 500 g, 900 g of polystyrene resulted in 1000 g of polystyrene with an iron content of 50, 10 ppm. the Results of the xenon test can be found in the table

Example 23

The 80 mg iron acetoacetic ester from Ex. 21 were replaced by 162 mg Replaced iron stearate. Table 8 shows the results of the xenon test.

Example 24

The 80 mg iron acetoacetic ester from Ex. 22 were replaced by 162 mg iron stearate. Table 8 shows the results of the Xenon tests.

Table 8 Iron content
(ppm) Darkening irradiation time up to
the surface becomes brittle
(by days) slide (days) 10 • attempt 50 5 - 17.5 Ex. 21 10 10 10 50 5 1.7.5- Ex. 22 10 10 8th - 50 5 16.5 Ex. 23 10 7.5 8th 50 5 16.5 Ex. 24 10 7.5 no observable changes
during the entire duration of the test - - 23 - Comparative
attempt Le A 15 326

50981 9/091

Example 25

45 g of the polymer bearing 1,3-dicarbony groups prepared in Example 3 were reacted with 4 g of FeCl 4. A brown-red powder with an iron content of 2.25 % was obtained; 4.44 g of this powder were extruded into 95.5 g of polystyrene (143 E, manufacturer: BASF, Ludwigshafen). A masterbatch with 0.1 % iron content was obtained in this way. Joint extrusion of 100 g, 50 g, 10 g of this masterbatch with 900 g, 950 g, 990 g polystyrene resulted in each 1000 g polystyrene with an iron content of 100, 50, 10 ppm. The results of the xenon test are shown in Table 9.

Table 9

attempt

Iron content (ppm)

Dark coloring the surface (after days)

Irradiation time until the Slide (days)

Ex. 25

100 50 10

Comparative experiment

6.5

19th

no observable changes during the entire duration of the test

Le A 15 326

- 24 -

509819/0919

Claims (7)

Claims 1) Plastic compositions consisting of a conventional thermoplastic plastic (A) and transition metal-containing polymeric compounds (B), which are the transition metal via 1,3-dicarbonyl groups attached to the polymer are contained in complex bound. 2) Plastic compositions according to claim 1, in which the Component (A) consists of polyolefins and / or polystyrene. 3) Plastic compositions according to claim 1 and 2, at which as transition metal in component (B) are the elements of the 4th period with atomic numbers 21 to 30, the 5th period with the ordinal numbers 39 to 48 and the 6th period with the ordinal numbers 57 to 79 are complexly bound to the polymer. 4) Plastic compositions according to claim 1, 2 and 3, at which the transition metal in component B in an amount of 0.1 ppm to 6 wt .-%, based on component B, complex is bound. 5) Plastic compositions according to claim 1 to 4, in which the transition metal-containing polymers (B) are added to the conventional thermoplastic material (A) in such an amount that transition metal-containing compositions with a metal content of 0.1 to 25,000 ppm arise. 6) Use of the plastic compositions according to claim to 5 as degradable plastics. 7) Process for the production of plastic compositions of claims 1 to 5, characterized in that components A and B, or component A, the 1,3-dicarbonyl group-containing polymer and the transition metal compound in a temperature range from 110 ⁰ C to 350 ' 1 min. To 30 min ·, can be mixed. Temperature range from 110 ⁰ C to 350 ⁰ C with a mixing time of Le A 15 326 - 25 - 509819/0919.