DE1769311C3 - Stabilizer mixture and stabilized polymer mass - Google Patents

Description

R "

R (S) _n CHCH ₂ CR '

where R is hydrogen, alkyl with 1 to 20 carbon atoms, Cycloalkyl with 5 to 8 carbon atoms, aryl with 6 to 24 carbon atoms or the remainder

R "" O

I Il

-CHCH ₂ CR "

R "and R""are hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 24 carbon atoms, R 'and R'" are hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 8 carbon atoms , Aryl with 6 to 24 carbon atoms, alkoxy with 1 to 20 carbon atoms, cycloalkoxy with 5 to 8 carbon atoms or aryloxy with 6 to 24 carbon atoms and π is an integer less than 3 (component B).

2. Stabilized polymer mass, consisting of polymers of the ^ .- olefins with 2 to 8 carbon atoms, Polystyrene and / or conventional modified polystyrene and a stabilizer combination the end

(a) 0.001 to 0.50 weight percent of an alkylated one Reaction product obtained by reacting dieyclopentadiene with phenol, p-cresol, o-cresol, mixed m / p-cresol or p-ethylphenol and subsequent alkylation of the phenol compound with a tertiary olefin of the group: isobutylene, tert-amylenes and tert-hexylenes, has been obtained (component A) and

(b) 0.001 to 0.50% by weight of a sulfur-containing compound of the general formula

R "O

I ii

R (S) _n CHCH ₂ CR '

wherein R is hydrogen, alkyl with 1 to 20 carbon atoms, cycloalkyl with 5 to 8 carbon atoms, Aryl with 6 to 24 carbon atoms or the rest

R "" O

I Il

-CHCH ₂ CR '"

R "and R" "hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, Aryl with 6 to 24 carbon atoms, R 'and R' "hydrogen, alkyl with 1 to 20 carbon atoms

atoms. Cycloalkyl with 5 to 8 carbon atoms, aryl with 6 to 24 carbon atoms, alkoxy with 1 to 20 carbon atoms, cycloalkoxy with 5 to 8 carbon atoms or aryloxy with 6 to 24 carbon atoms and η is an integer less than 3 (component B).

The invention relates to a stabilizer mixture and polymer compositions comprising the same and composed of polymers the -olefins with 2 to 8 carbon atoms, polystyrene and / or conventional modified polystyrene.

It is known that conventional rubbers such as butadiene-styrene copolymers, natural rubber, etc. against oxidative degradation can be stabilized by certain phenolic compounds. Usually however, amounts must range from about 0.75 to

> o 2.00 parts of antioxidant per 100 parts of rubber are used. It has been found that some of these phenolic antioxidants can also be used as stabilizers for relatively saturated polymers such as polyolefins and polystyrene. The effective amount of stabilizing agent is small compared to that for the conventional rubbers; it is about 0.25 parts of phenolic antioxidant per 100 parts by weight of polymer.
It would be useful to use even smaller amounts of this

m to use relatively expensive antioxidants and at the same time to protect the polyolefins effectively against oxidative degradation.

The invention is based on the object of a stabilizer mixture containing phenolic compounds

Γ) research and using the same to obtain stabilized, relatively saturated polymers that are resistant to oxidative degradation. the The amount of stabilizer should be very low. The provision of such stabilized polymers is essential likewise an object of the invention.

This object is achieved with a stabilizer mixture

(A) an alkylated reaction product obtained by reacting dieyclopentadiene with phenol, p-cresol,

o-cresol, mixed m / p-cresol or p-ethylphenol and then alkylating the phenolic compound with a tertiary olefin of the group: isobutylene, tert-amylenes and tert-hexylenes (Component A) and

(b) a sulfur-containing compound of the general formula

R "O

I Il

R (S) _n CHCH ₂ CR '

where R is hydrogen, alkyl with 1 to 20 carbon atoms, cycloalkyl with 5 to 8 carbon atoms, aryl with 6 to 24 carbon atoms or the remainder

R "" O

I Il

-CHCH ₂ CR "

R "and R" "hydrogen, alkyl with 1 to 20 carbon atoms, cycloalkyl with 5 to 8 carbon atoms, Aryl with 6 to 24 carbon atoms, R 'and R' "hydrogen, alkyl with 1 to 20 carbon atoms,

Cycloalkyl with 5 to 8 carbon atoms, aryl with 6 to 24 carbon atoms, alkoxy with 1 to 20 carbon atoms, cycloaikoxy with 5 to 8 carbon atoms or aryloxy having 6 to 24 carbon atoms and η is an integer less than 3 (component B).

The subject of the invention is also a stabilized polymer composition consisting of polymers of the -olefins with 2 to 8 carbon atoms, polystyrene and / or conventional modified polystyrene and a stabilizer combination the end

(a) 0.001 to 0.50% by weight of an alkylated reaction product obtained by reacting dicyclopentadiene with phenol, p-cresol, o-cresol, mixed m / p-cresol or p-ethylphenol and then alkylating the Phenolic compound with a tertiary olefin of the group: isobutylene, terL-amylenes and tert.-hexylenes has been produced (component A) and

(b) 0.001 to 0.50% by weight of a sulfur-containing compound of the general formula

20th

R "

Il

R (S) _n CHCH ₂ CR '

wherein R is hydrogen, alkyl having 1 to 20 carbon atoms. Cycloalkyl with 5 to 8 carbon atoms, aryl with 6 to 24 carbon atoms or the remainder

R "" O

I Il

-CHCH ₂ CR "

R "and R""are hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 24 carbon atoms, R 'and R'" j-, hydrogen, alkyl having 1 to 20 carbon atoms, cycloalkyl having 5 up to 8 carbon atoms, aryl with 6 to 24 carbon atoms, alkoxy with 1 to 20 carbon atoms, cycloaikoxy with 5 to 8 carbon atoms or aryloxy with 6 to 24 carbon atoms and η is an integer less than 3 (component B).

The alkylated reaction products are preferably prepared by adding (1) 1 mole of dicyclopentadiene and at least 1 mole of a phenolic product from the group: phenol, p-cresol, mixed 4> tes m / p-cresol and p-ethylphenol, in the presence of a Friedel-Crafts catalyst and then (2) the first Reaction product reacts with at least V2 mol of olefin of the group specified.

The amount of olefin used depends on the phenolic compound used and also on the Molar ratio of the phenolic compound to dicyclopentadiene in the reaction product. The product from Phenol and dicyclopentadiene react with more olefin than the product from p-cresol. The conversion product from phenol with a molar ratio of 2: 1 phenol / dicyclopentadiene reacts more strongly with the olefin than the 1: 1 product. Incompletely alkylated products also differ from non-alkylated products However, those products that exhibit superior antioxidant properties are preferred where the alkylation is practically complete. 1.0 to 2.0 is preferred in the finished alkylation product Moles of tertiary olefin per mole of dicyclopentadiftn when p-cresol, o-cresol, mixtures of m / p-cresol and b5 p-Ethylphenol can be reacted with dicyclopentadiene to form the product according to stage 1. the preferred proportions of reactants in the final alkylation product amount to 2.0 to 4.0 moles of terL-olefin per mole of dicyclopentadiene, when phenol is reacted with dicyclopentadiene to form the product after step 1. It will be in generally a small excess of alkylating agent applied to ensure that the desired amount is mixed with the product from step 1 is implemented. The conversion products produced by the process described above have proved to be much more effective as rubber antioxidants than those after stage 1 by reacting Dicyclopentadiene with phenol prepared reaction products, which in the core already with tert-hydrocarbon groups are substituted.

The reaction between dicyclopentadiene and the phenolic compound is effectively catalyzed by Friedel-Crafts catalysts and in particular the Friedel-Craft catalysts such as aluminum chloride, Zinc chloride, iron (II) and iron (III) chloride and boron trifluoride, as well as complexes based on boron trifluoride, preferably boron trifluoride and complexes Preferred catalysts for the first process stage are based on boron trifluoride. The second Process stage of the two-stage reaction process in which the product by reacting dicyclopentadiene and a phenol compound is obtained, is further alkylated with tert.-Clefin in the presence of an or several of the common acidic alkylation catalysts, such as sulfuric acid, benzenesulfonic acid, toluenesulfonic acid, Acid activated clays, boron trifluoride, zinc chloride, iron (II) and iron (III) halides, Aluminum halides and tin (N) and tin (IV) halides. Sulfuric acid, benzenesulfonic acid, toluenesulfonic acid and acid activated clay are preferred catalysts for the second stage process. the Catalysts are used in both the first and the second process stage in conventional catalytic Amounts used normally from 0.1% to 5.0% catalyst based on the total weight of the Implementation participants in the reaction to be catalyzed vary.

Thus, it is preferred to remove the boron trifluoride catalyst if it is used in the first stage reaction before performing the second or alkylation stage of the disclosed process. The boron trifluoride catalyst can be removed by using a base such as ammonia or a solution of sodium hydroxide or sodium carbonate. The boron trifluoride catalyst can optionally be removed by means of an excess of phenol compounds by heating the reaction mixture to a temperature of 100 to 160 ^° C. under vacuum. An additional method of the boron trifluoride catalyst for removing, which is applied in the first process step may be carried out by means of holding the coming from the first stage reaction mixture at reflux with a small amount of an inert organic solvent such as toluene, at a temperature of 150 to 16O ⁰ C .

The dicyclopentadiene is reacted with a phenolic compound at a temperature of 25 to 160 ° C. It is possible to carry out the reaction at slightly higher temperatures, but care must be taken that the decomposition temperature of the dicyclopentadiene, which is around 170 ^° C., is not reached or exceeded. Preferred reaction temperatures are between 80 and 150 ⁰ C. The reaction between dicyclopentadiene and a phenol

Connection can be started at room temperature and since the reaction is quite fast and is exothermic, the heat of reaction can be used to achieve the final reaction temperature will. If there are suitable cooling options, the reaction can be carried out continuously will.

The molar ratio of the phenolic compound to dicyclopentadiene which is present in the reaction mixture of step 1 used can be 1: 1 to 5 or higher. The amounts usually employed are 2: 1 to 4: 1 moles of phenolic compound per mole of dicyclopentadiene and a preferred ratio is 3: 1. The above preferred Amounts of reactants lead to a substantial excess of the phenolic compound over the Amount that actually reacts with the dicyclopentadiene. The molar amounts of phenolic compound with Dicyclopentadiene are made to react, usually vary from 1: 1 to 2: \ whereby the preferred molar ratio of the reaction participants in the product obtained by process stage 1 is obtained, amounts to 1.50 to 1.75 moles of phenolic compound per mole of dicyclopentadiene. In some In some cases, it may be useful to carry out process stage 1 in an inert organic solvent, such as benzene, Toluene, etc. to run. The use of a solvent is particularly useful when a relatively low ratio of phenolic compound to dicyclopentadiene is used. If that If the molar ratio of phenolic compound to dicyclopenadiene is 3: 1 or more, the excess is effective Phenol compound as an effective solvent, and no additional solvent needs to be applied will.

Process step 1 can be carried out by adding dicyclopentadiene to the mixture of the phenolic compound and catalyst are carried out, or the catalyst can be added in stages to the mixture of Phenolic compound and dicyclopentadiene are added, the first process stage being preferred. The speed with which the implementation participants are brought together can be controlled by a can vary over a wide range as long as the temperature is kept below 150 ° C.

The second process stage includes the alkylation of the product obtained from process stage 1. In carrying out the second step, the resinous product obtained from Step 1 is dissolved in an equal amount of an inert hydrocarbon solvent such as benzene, toluene, etc. The alkylation is carried out at a temperature between 20 and 100 ° C. A preferred temperature range is 60 to 80 ° C. If the tertiary olefin employed as the alkylating agent is a gas, it can be added to the reaction under pressure, but the pressures should ^{not exceed 2.1 kg / cm 2} if excess polymerization is to be avoided. In the second stage of the process it is also preferred to effect the alkylation as quickly as possible, but the time within which the reaction is complete depends on the activity of the alkylating agent used.

The chemical composition of the very complex reaction mixture, consisting of fairly high molecular weight Compounds cannot be precisely defined by a chemical formula. Furthermore were no pure compounds from the reaction product

isolated. Thus it is impossible to get a precise chemical Indicate the formula for the reaction mixture obtained or the same by expressions of the chemical Define standard nomenclature.

In preparing the alkylated reaction products, p-cresol and mixed m / p-cresol are preferred Phenolic products. The preferred olefin is isobutylene.

Typical examples of sulfur-containing compounds used in carrying out the process can be applied are

1 - (butylthio) heptanone-3,

1 - (Cyclohexylthio) -hexanone-3,

1- (3-methylphenylthio) octanone-3,

3- (hexylthio) -propanal, 3- (phenyldithio) -hexanal,

3- (Cyc! Ohexylthio) -butana !,

3- (4-methylphenylthio) octanal,

Octadecyl 3- (cyclohexythio) propanoate,

Dodecyl 3- (phenyldithio) propanoate,

3- (ethylthio) propanoic acid.

Preferred sulfur-containing compounds for the subject matter of the invention are esters of thiodipropionic acid, that of the formula

XOC-CH ₂ -CH ₂ -S-CH ₂ -CH ₂ -COY

correspond, in which X and Y are alkyl radicals having 1 to 20 carbon atoms. Are particularly preferred those that contain 8 to 18 K. carbon fatomes.

Characteristic compounds corresponding to the above formula are those in which X and Y the following are:

X Y methyl ethyl Propyl Butyl 40 pentyl Hexyl Pentyl Hcptyl Octyl Octadecyl Nonyl Hexadecyl Decyl Hexadecyl 45 monodecyl Pentadecyl Dodecyl Tetrahexyl Tridecyl Telradecyl Octyl Octyl Nonyl Nonyl so dodecyl Dodecyl Monodecyl Monodecyl Dodecyl Dodecy! Tridecyl Tridecyl Tetradecyl Tetradecyl 55 pentadecyl Pentadecyl Hexadecyl Hexadecyl Heptadecyl Heptadecyl Octadecyl Octadecyl 1-methylpropyI 2-methylpropyl bo 1-ethylhexyl 1-methylheptyl 1-ethylhexyl I-ethyl-3-methyipentyl

Didodecyl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate and dioctadecyl-3,3'-thiodipropionate are particularly characteristic.

The sulfur-containing compounds can can be prepared by any known method.

Polymers that can be stabilized by the stabilizer according to the invention are polystyrene, modified polystyrene and polymers of the «-olefins with 2 to 8 carbon atoms, such as polyethylene and Polypropylene.

The mixture proves to be particularly favorable when it is made of polypropylene and rurn ^ bilise Polvüiliy'en is applied. It is particularly cheap in the stabilization of polypropylene.

The one used according to the invention The amount of the phenolic component is from about 0.001 part to about 0.50 part by weight per 100 parts of the Polymers. The sulfur-containing compound used in the present invention amounts to about 0.001 part to about 0.50 part by weight per 100 parts of polymer. The ratio of the phenolic component to the sulfur-containing compound is about 10/1 to about 1/10.

Optionally, amounts greater than 0.50 parts of each component can be used, but amounts are over 0.50 parts of each component in combination normally not under ordinary conditions necessary.

The ability of polyethylene to withstand degradation is greater than that of polypropylene, Polystyrene and modified polystyrene, and thus require lesser amounts of stabilizer than these polymers need for an equivalent level of protection against degradation.

The stabilization system can employ any conventional arrangement for adding phenolic stabilizers can be added to polymers. Where the polymer is a polyolefin, that when dry is present, the stabilizer can be through conventional arrangements such as mixing on an open mill or by internal mixing as carried out in a Banbury mixer or physical mixing provided that the particle size is sufficiently small, or by solvent precipitation methods.

The components of the stabilizer mixture according to the invention are prepared in a customary manner Procedure:

Production example 1

330 g ρ cresol and 9.0 g phenol BF ₃ complex containing 26% BF _{3 are} heated to 100 ° C. and then 132 g dicyclopentadiene are added over a period of 3.5 hours. The excess p-cresol is removed by heating to a temperature of the acid of 150 ^° C. at 4 mm. This also removes the BF3 catalyst. A residue of 316 is obtained.

236 g of this product are dissolved in an equal weight of toluene and 4.0 g of H ₂ SO _{4 are} added. The solution is heated to 80 ° C. and 168 g of isobutene are added over a period of 1.75 hours. The mixture is heated for a further hour and The catalyst is then _{destroyed with a Na 2} CO ₃ LoSURg. Volatile and unreacted constituents are removed by heating to 175 ° C. at 30 mm. Catalyst residues are removed by filtration. The product is obtained in an amount of 313 g.

Production example 2

376 g of phenol and 9 g of a phenol-BFrKomplexes, of 26% BF ₃ includes heated to 9O ⁰ C 132 g of dicyclopentadiene is added in one hour at Einei temperature between 90 and 107 ° C, since! The mixture is kept at this temperature for several hours. Then it is turned on to ISOT at 15 mmh / i to remove BF ₃ and unreacted phenol. Mar obtained a yield of 291 g of a hard resin. There; The ratio of phenol to dicyclopentadiene is 1.69 to 1.

_{| ()} Preparation example 3

A 215 g portion of the product according to Example 2 is dissolved in 4½ ml of toluene. 6 g of concentrated H ₂ SO _{4 are} added. The mixture is heated to 55 ° C. and isobutylene is added in 3.5 hours or until nothing is absorbed. The catalyst is destroyed with 12 g of Na ₂ CO ₃ dissolved in 50 ml of H ₂ O. The volatile constituents are means of heating to 150 ⁰ C at atmospheric pressure removed, then, the remaining Anteii at the same temperature and melted 15 mm. 309 g of the product are obtained.

Production example 4

174 g of the reaction product are au; p-cresol and dicyclopentadiene, prepared as in Example 1, dissolved in 200 ml of toluene and 6 g of concentrated H ₂ SO ₄ added to the solution. The solution is heated aul 76 ° C and 100 g of 2-methyl-1-pentene was added in one hour, the mixture is maintained for 6 hours at the temperature of 60 to 70 ⁰ C. Of the

The catalyst is destroyed with 40 g of 25% strength Na2CO ₃ solution. The mixture is then mm to a final pot temperature of 150 ⁰ C at 15 under removal of the volatile constituents is heated. 235 g of the product are obtained.

Production example 5

401 g of p-ethylphenol and 10 g of phenol BF ₃ complex containing 26% BF _{3 are} heated to 84 ° C. and then 132 g of dicyclopentadiene are added over the course of 2.5 hours. The mixture is then heated to 19O ⁰ C (pot temperature) at 10 mm to BF ₃ unc excess p-Äthyiphenol to remove. The product yield is 331 g. The molar ratio: of p-ethylphenol to dicyclopentadiene is 1.63 zi

Production example 6

237 g of the product according to Example 5 are dissolved in 250 ml of toluene and 10 g of concentrated H ₂ SO ₄ are added

so added to the solution. The mixture is heated to 65 ° C. and isobutylene is added until no further reaction occurred. This took about 3 hours. 50 g of a 25% Na ₂ CO ₃ -Losung added to destroy the catalyst and the entire mixture is heated to 180 ⁰ C at 10 mm purpose "devolatilisation g The product is obtained in an amount of three hundred and first

Production example 7

There are 324 g of a mixed m / p-cresol with a 3 ° -Siedepunktsbereich and '9 g of BF ₃ phenol complex at 80 ⁰ C. and then 132 g of dicyclopentadiene added in two hours The mixture is maintained at 80 ⁰ C and a stirred for a further hour. The excess m / p-Kresoi and BF ₃ are then removed by heating to a vessel temperature of 190 ° C. at 10 mm

294 g. This corresponds to an internal 1.5 to 1 molar ratio of m / p-cresol to dicyclopentadiene.

Hersielluii ^ s'Dc ^ spicl 8

Is there 20ό g of the reaction products? dissolved in 250 ml of toluene after ^r> Example 7 and 10 g of concentrated H2SO4 to the solution was added. The mixture is heated to fiTG and 150 g of 2-methyl-1-butene are added in 2 hours. The genius is kept at 60'C for a further 4 hours. The catalyst is then destroyed and the volatile constituents removed as in the previous examples. The yield of the product is 263 g.

There are various attempts at stabilized with the inventive Stabilisierungssystein \ * performed> polypropylene. The same tests are carried out on non-stabilized polypropylene and on polypropylene stabilized with other than the system according to the invention. In particular, the yield strength and melt indices of non-aged and non-aged polypropylene, both stabilized and non-stabilized, were determined.

The polypropylene samples are prepared in the following manner: The phenolic compound is either dissolved in a suitable solvent such as hexane or acetone at a concentration of 1 to 5% and added to the polypropylene by dispersing the stabilizer solution in the powdered propylene using a Henschel mixer and stirring 2800 rpm are added and the propylene compound so is added directly to the polypropylene in a Henschel mixer

The sulfur-containing compound was added to the polypropylene in the mixer either directly or in solution. After 15 minutes, the typical batch temperature reaches 95 ° C. and an acceptable dispersion of the stabilizers is obtained. After 10 minutes only traces of the solvent remain where the stabilizer was added in solution. The stabilized polypropylene is then injection molded to form tensile bars that conform to ASTM-D-638-64T. The tensile bars are aged at a temperature of 140 ⁰ C in a forged Luflofen. The tensile load properties of the original and aged samples are measured on an Instron. A 11.4 cm jaw is used, the jaw separation speed was 2.54 cm per minute.

Melt index determinations are carried out on aged and non-aged tensile rods, which are shown in small pieces had been cut up. The melt index test is carried out according to ASTM-D-1238-62T, Condition L. As the polymer degrades, the molecular weight is reduced by chain scission. The melt index indicates the molecular weight reduction and is expressed in grams of des Polymers pressed out per unit of time.

As the molecular weight decreases due to degradation, the melt index increases.

The following examples 3 and 5 show the embodiment according to the invention.

Examples 1-3

A propylene polymer is stabilized according to the invention (Example 3). Examples 1 and 2 relate to polypropylene polymers containing the individual components of the system according to Example 3. the Samples are prepared, aged and tested in the manner described above. The yield point and the melt index values are shown in Table I.

Table I.

Examples 1

Butylated reaction product of 0.05 p-cresol and dicycolopentadiene (parts) ')
Dilauryl thiodipropionate (parts) -

0.25

0.05
0.25

Aging time (days)

1
3
5
7th
9

') Manufactured according to the procedure of the example

A - yield point (kg / cm ² ).

B - melt index expressed in grams of polymer expressed per 10 minutes.

+ - Failed

The above numerical values show the improvement, the phenolic compound (Example 1) between the fifth when applying the mixture according to the invention 65 and seventh day to fall. With the thiodipropionate

388 1.58 388 2.61 382 1.52 360 2.04 367 2.64 358 1.45 348 2.45 287 3.30 350 1.58 356 2.63 + + 360 1.81 204 + - - 361 2.12 42.7 - - - 354 2.16

(Example 3) in contrast to the application of the components of the mixture individually (Examples 1 and 2) is obtained. The yield point began at the

(Example 2) the yield point begins to drop between the first and third day. The yield point for the mixture began several days after the nine-day

as shown above. The effect of the mixture was thus greater than that of adding the individual components. The melt index for the blend (Example 3) was also superior to that of adding the individual components.

Examples 4 and 5

A polypropylene polymer is stabilized according to the invention (Example 5). Example 4 relates to a Polypropylene polymer made with a phenol / thiodipropionate mixture has been stabilized outside the scope of the invention. The latter stabilization system is applied in an amount sufficient for the Five times the amount of the stabilization system used in Example 5 is. The samples are in manufactured, aged and tested in the manner described above. The numerical values relating to the Yield strength are shown in Table II.

Table II

Stabilization system

Examples
4 5

2,6-diter-butyl-p-cresol (parts) 0.25 -

butylated reaction product ² ) and - 0.05 dicylopentadiene (parts)

Dilauryl thiodipropinate (parts) 0.25 0.05

Aging time
(Days)

stretch
(kg / cm ² )

389 370

357 360 3i2 357 354 357 362 362 370 370 360 360

358 358 350 351

fails 352 290 181

² ) Manufactured according to the procedure of Example 1.

The above numerical values show that the mixture according to the invention (Example 5) can be used in an amount Vs that of a commercially available mixture of phenol and a thiodipropionate (Example 4) and a superior stabilization is still achieved. The period of time until failure of the yield point in a product which has been protected by the ^r> mixture of the invention, is approximately 39 days, while the time to failure of the product has been protected by five times the amount of the other mixture, 27 days amounts to.

ίο The examples above show the effectiveness of the isobutylated reaction product of p-cresol and dicyclopentadiene with dilauryl-3,3'-thiodipropionate. Other phenolic compounds that fall within the scope of the invention and by the two-stage process

n ren have been produced (i.e. the reaction of the Phenolic compound and dicyclopentadiene and subsequent alkylation step), which are also according to the invention are effective when applied and tested in the same way as described in the examples are: the isobutylated reaction product of phenol and dicyclopentadiene, the isobutylated reaction product from o-cresol and dicyclopentadiene, the isobutylated reaction product from mixed m / p-cresol and dicyclopentadiene. the isobutylated

Reaction product of p-ethylphenol and dicyclopentadiene, the tert-amylated reaction product of p-cresol and dicyclopentadiene, the tert-amylated Reaction product of o-cresol and dicyclopentadiene, the tert-amylated reaction product from ge

jo mixed m / p-cresol and dicyclopentadiene, the tert-amylated Reaction product of p-ethylphenol and dicyclopentadiene, the tert-hexylated reaction product from phenol and dicyclopentadiene, the tert-hexylated reaction product of p-cresol and dicyclopentadiene, the tert-hexylated reaction product of o-cresol and dicyclopentadiene, the tert-hexylated one Reaction product of mixed m / p-cresol and dicyclopentadiene and the tert-hexylated reaction product of p-ethylphenol and dicyclopentadiene. It any of the isomers of the tertiary amylenes or hexylenes can be used.

Other sulfur-containing compounds that are within the scope of the invention and are also effective are, if they are specified, applied and tested in the same way as in the examples, are those defined by the structural formulas given above.

The stabilizers of the present invention are similarly effective in stabilizing of modified styrene, polystyrene and polyethylene.

The numerical values show that extremely small amounts of certain are used in the practice of the invention phenolic stabilizers can be applied to prevent oxidative degradation in polyolefins to stabilize effectively.

Claims (1)

Patent claims: 1. Stabilizer mixture off (A) an alkylated reaction product, which by Reaction of dieyclopentadiene with phenol, p-cresol, o-cresol, mixed m / p-cresol or p-ethylphenol and then alkylating the phenolic compound with a tertiary olefin of the group: Isobutylene, tert-amylenes and tert-hexylenes has been (component A) ur.d (b) a sulfur-containing compound of the general formula