DE2505071A1 - STABILIZING COMPOSITION AND STABILIZED POLYOLEFIN COMPOSITION - Google Patents

Description

Air .. 'j. Γ6, Feb. Ϊ975

DS- '- ■ - ^urF

623 Γ · Γ:. * · .Ϊ; ^; "." ■ '■' -i Αλλ /.'AiVi-HUu-HSf

Our no. 19 681

Exxon Research and Engineering Company Linden, N.J., V.St.A.

Stabilizing composition and stabilized polyolefin composition

It is generally believed that the best thermal stability of polyolefins, such as polypropylene, is obtained by using an agent such as a phenol or a imine-adds, which stops free radical chains. It can do it give off a hydrogen radical to the polymeric free radical and stop the chain reaction. The phenol or amine is generally substituted so that that from the phenol or the radical resulting from the amine is relatively stable.

2. In addition to the chain-stopping agents, stabilizers are often used

catalysts such as thiodipropionates, which act according to a mechanism in which no free radicals occur, peroxides and hydro - "-"

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ORIGINAL INSPECTED

destroy peroxides, used. The two types of stabilizers often react synergistically and result in extremely effective stabilizing systems.

The invention relates to polyolefin compositions that resist degradation by. Oxidation and UV rays are stabilized, because they contain effective amounts of a new polycarbonate made by a new process.

In particular, the invention relates to new compositions which act as antioxidants and light stabilizers. this means an improvement over U.S. Patent 3,510,507, in who described the use of polycarbonate condensation products as particularly effective stabilizers for polyolefins is.

The invention relates to compositions of the following structural formula ι

R '

Uli

f ti

tlll

X-J.

R ¹

R ¹

O i -τΖ If C-

whati * i mean:

1.) X a) -S- or

R ι

b) -Οι

RlIlIl

in which: R and R ^{IIMI are} hydrogen, a C ^ -C | g-alkyl radical and an aryl radical,

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Il

c) -θα) -CC- and
e) -CAC-

where: A is a C.-C.g-alkylene radical and an arylene radical,

2) R ¹ tertiary C to Cp-alkyl radicals ^{un (} * secondary C, to C, ~ -
Alkyl radicals,

R ¹ 'is hydrogen

R ¹¹ 'is hydrogen and a C ^ -Cc -alkyl radical,

R ¹ " ^{1 is} hydrogen and a Cj-Cg-alkyl radical, -

3) Y hydrogen, carbophenoxy and substituted carbophenoxy radicals,

Zf) -Z a) phenoxy radicals

b) substituted phenoxy radicals and

c),

where: B, R ¹ , R- ", R" ¹ , R ' ¹ "and X, as indicated above and

5) η is a number from 1 to 10.

In preferred compositions for stabilizing polyolefins as polypropylene mean:

a) X R

-σι

RlIfIl

509 833/106 5

it

b) Y <()> - OCO-

c) η 4 to 8 and

d) R, R ¹ , R ″, R ¹¹¹ , R ¹ ″ ¹ , R ^ltllf and Z as indicated above.

The compositions of the invention are as good or better than known stabilizers, provided they have thermal or oxidation stability result. Compared to known stabilizers, however, they are in terms of their function as light stabilizers think. In addition, they have numerous advantages over known stabilizers with important properties, particularly over those in U.S. Patent 3,510,507 polycarbonate stabilizers described. The advantages are that, according to the invention, the ends of the polymer chains are closed can be, resulting in a material that has little or no free hydroxyl groups associated with the aromatic rings are connected.

The compositions according to the invention are notable for the fact that they do not require any free hydroxyl groups which are im essential as 1: 1 substitutes for the mostly used serve hindered phenols. Another indication that the compositions of the invention are capable of being hindered Phenols act in stabilizing polyolefins against heat is the fact that the compositions are synergistic interact with diesters of thiodipropionic acid and thereby result in excellent oxidation stability in the case of polyolefins.

The ability of the compositions of the invention that do not contain free hydroxyl groups., Hindered phenols, the free Replacing hydroxyl groups containing hydroxyl groups is not only surprising but also gives several important advantages · One major one The disadvantage of hindered phenols or aromatic amines is that they are often because of the reaction

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free hydroxyl group with oxygen, acids or bases or metal ions discoloration of the stabilized materials occurs, usually goes with the color development because of this Reactions also lost the stabilizing effect.

Since the compositions according to the invention are in the form of let produce that no free hydroxyl groups are present these problems are avoided. In some applications it is desirable to maintain a completely neutral medium, because acidic or basic additives such as hindered phenols or aromatic amines catalyze undesired reactions can be. The compositions of the invention can be prepared in such a way that they are completely neutral and thus avoid such problems.

When the compositions according to the invention are added to polyolefins, they have stabilizers known to them the advantages that the polymers have better color, improved stability and better odor. Compared to known Stabilizers for polyolefins have the additives of the present invention significantly reduced volatility and are suitable therefore for high temperature applications. Polyolefins, which contain the stabilizers according to the invention can be used for the production of films, shells, car parts and the like be used.

The compositions according to the invention are particularly advantageous for stabilizing polyolefins, especially those using catalysts of the Ziegler type Use polyolefins made from alpha olefins, as the stabilizers are excellently soluble in the polyolefins and are compatible with the polyolefins. In addition, the stabilizers according to the invention do not combine with the metal residues in the polyolefins. The compositions according to the invention are mostly crystalline white or colorless solids, which can be easily powdered and are therefore

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especially advantageous to add in a dry stabilizer additive system.

The invention also relates to a method of production of the compositions according to the invention. The compositions are obtained as condensation products by the reaction of a bisphenol with phosgene or diphenyl carbonate. "The Condensation products are a mixture of the products according to the invention and have molecular weights which depend on the molar ratio of the starting products, the presence of monofunctional Chain stopping and closing materials and the degree of condensation (or degree of polymerization) up to which the reaction occurs by removing one of the reaction products, depend.

The aim is to produce a product that does not contain free hydroxyl groups by mixing the ends of those to be capped Polycarbonate chains with aryloxy groups are used in the manufacture of the compositions according to the invention Procedure extremely beneficial.

When the bisphenols react with phosgene, the chain ends can however, by adding a monofunctional phenol to the reaction mixture after the polymerization is complete before the product is processed. It is also possible to polymerize between the bisphenol and to carry out phosgene directly in the presence of the monofunctional phenol. In the latter case, the desired Production of a closed chain with free hydroxyl groups also has the advantage that the molecular weight is very high can be easily regulated.

The preferred reaction of bisphenols with diphenyl carbonate provides for the use of excess diphenyl carbonate compared to the bisphenol that all chain ends are closed, In addition, the molecular weight of the product can through

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Regulating the ratio of excess diphenyl carbonate to bisphenol can be easily regulated. The opposite of the compositions U.S. Patent 3,510,507 improved color is also a consequence of the use of excess diphenyl carbonate as the color-forming side reaction is of the Kolbe-Schmitt type this is prevented. Bisphenol and diphenyl carbonate can be used in a molar ratio of about 1: 2 to about 1: 1 can be reacted. Preferably the molar ratio is about 10-11.

Examples of phenols that can be used for the condensation reactions are: i ^, V-butylidenebis (3-methyl-6-t-butyl-phenol); 4,4'-methylenebis (3-methyl-6-t-butylphenol); Jf, V-thiobis (3-methyl-6-t-butylphenol); 4,4 · -Methylene bis (3-methyl-6-t-butylphenol); 4 ^ ^f -I ^so P ^ro Pyli ^den ki ^s Pk ^en ° l >>4'-Isopropylidenebis(2-isopropylphenol);4>4'-methylenebis (2-methyl-6-t-butylphenol). Other 4,4'-bisphenols that can be used are the reaction products of substituted phenols and aldehydes or ketones.

The monofunctional ones that can be used to close the chain ends Phenols are very numerous. For example: phenol, 2,4-di-t-butylphenol and p-cresol are suitable.

When the condensation reaction between a bisphenol and phosgene is carried out, at least one equivalent of a suitable weak base such as pyridine is used. This reaction can in an inert solvent such as dichloromethane with a slight Excess of a weak base can be carried out. Alternatively, this reaction can be carried out using a weak base such as Pyridine run as a solvent, one of which Excess is used.

When the condensation reaction using the bisphenol and diphenyl carbonate is made, it is advantageous to use a basic catalyst. Suitable catalysts are

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the alkali metals, sodium, potassium or lithium, also tetran-butylammonium hydroxide, Sodium hydroxide, potassium t-butoxide, sodium methoxide, lithium hydride and the like. The basic one Catalyst is used in effective amounts of from about 0.001 to about 0.05 percent by weight based on the total amount of that used Reaction components used.

According to one embodiment of the invention in which diphenyl carbonate is used, a mixture of the new products is obtained under conditions under which the condensation reaction is completed by removing the phenol. Accordingly, conditions for the condensation reaction range from above 182 ° C at atmospheric pressure (the boiling point of the phenol) to a temperature at which the phenol or the phenolic type reaction product forms in a vacuum of about 1 to 2 mm Hg. Since the phenol or the reaction product of the phenolic type cannot simply be separated from the starting material, temperatures of about 160 to about 200 ^° C. are preferred and the reactor in which the reaction takes place is evacuated. Suitable conditions for carrying out the reaction are from about 18O ⁰ C and a vacuum of about 1 mm Hg.

That obtained by condensing a bisphenol with diphenyl carbonate Mixture of the new compositions is a clear glass that can easily be pulverized to a white solid. In this form, the solid mixture can be used as a stabilizer which gives excellent results. It can jedocjj also cleaning procedures are carried out to remove odor and to improve color. The preferred cleaning method is by slurrying the powder in methanol and stirring the mixture for a short time at room temperature. The product can then be filtered off. An odorless and colorless solid is obtained.

The invention is illustrated in more detail by the following examples.

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25 Q 5,071

example 1

A solution of 9.52 g (0.028 mol) of 2,2-bis- (ifhydroxy-3-t-butylphenyl) propane in 175 ml pyridine filled. 5 S (0.051 mol) of phosgene were slowly passed in at room temperature over the course of 30 minutes. The reaction mixture was then stirred for an additional 90 minutes and then poured into water. An oily semi-solid mass was obtained by decanting the liquid layer. The oily product was dissolved in dichloromethane and the resulting solution was extracted with 5 percent strength aqueous hydrochloric acid. It was then washed with water until a neutral washing solution was obtained. The dichloromethane was then evaporated under reduced pressure. 10, 1 + 5 S of a solid product were obtained. This product was pulverized, slurried in methanol and filtered. / f if2 210 g of the product as a fine white powder and dried, mp. 214 ° C.

Example 2

The procedure described in Example 1 was followed, but the reaction mixture was quenched by adding 50 ml of methanol before pouring into water. 11.25 S of a brown powder were obtained. M.p. 166 to 172 ^° C.

Example 3

The procedure described in Example 1 was followed, but 165 g (0.008 mol) of 2,2f-di-t-butylphenol were added to the reaction mixture before the addition of the phosgene. 11.15 g of a brown powder, melting point 185 ^° C. were obtained.

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Example ^

120.27 g (0.31 mol) of Zf, Zf'-butylidenebis (3-methyl-6-t-butylphenol) were dissolved in 1000 ml of dichloromethane. Then 59.75 g (0.75 mol) of pyridine was added and the solution was placed in a 2000 ml 3-necked flask equipped with a mechanical stirrer, a gas inlet tube and a condenser. 31.10 g (0.31 mol) of phosgene were passed in over the course of 4 hours. During this time the temperature was kept ^{between 25 and 29 0 C with an ice bath.} After complete addition of the phosgene, the solution 1 was χ with 10 percent aqueous hydrochloric acid extracted and washed h χ with distilled water. The last wash solution was neutral and chloride free. The solution was concentrated to 600 ml and dropped into methanol. 110 g of a slightly gray-white precipitate were obtained. Mp 155 -. 170 ⁰ C, molecular weight if 120th

Example 5

The procedure described in Example 2 was followed, but 10? g (0.028 mol) of Zf, V ~ butylidenebis (3-methyl-6-t-butylphenol) used.

Example 6

47.82 g (0.125 mol) of Z _ff Zf «-Butylidenebis (3-methyl-6-t-butylphenol) and TO, 32 g (0.050 mol) 2, ^ - di-t-butylphenol were in 650 ml of dry pyridine dissolved and reacted with phosgene at room temperature until a reddish color formed in the reaction mixture. Then the reaction mixture was poured into water. The gummy mass that formed was obtained by decanting the aqueous layer. The gummy mass was then rubbed several times with distilled water until a solid powder formed. The powder was filtered off,

50 9 8 33/1065

washed again with water and dried. A light brown powder with a molecular weight of 1075 was obtained. The analysis showed 79.74 % carbon, 9.06 % hydrogen and 11.20 % oxygen (the percentages are amounts by weight).

Example 7

In a 500 ml round bottom flask, 20.20 g (0.053 mol) of 4 »4 ^f -butylidenebis (3-methyl-6-t-butylphenol), 17.13 S (0.080 mol) diphenyl carbonate, and 0.001 g lithium hydride were mixed. The flask was attached to an all-glass rotary evaporator with the flask itself remaining in an oil bath. At a pressure of 15-20 Torr in the flask was heated oil bath at IZf5 ⁰ C. Once the flask contents formed a clear melt, the vacuum was increased and the temperature is raised until the the oil bath temperature 180-190 ⁰ C reached and the pressure was less than 1 Torr. After one hour the vacuum was released and the components not involved in the reaction were removed. The reaction mixture had lost 9.05 g substance and increased the receiving flask on the rotary evaporator to 9.05 S. The material collected in the receiving flask was 95 % phenol (as determined by NMV). Upon cooling to room temperature, the material in the reaction flask solidified and formed a clear glass. The glass could easily be powdered and yielded 28.4 g of a pure white powder, mp 105 FCI 110 ⁰ C. (Softening range 58-70 ⁰ C) Molecular Weight 680.

Example 8

The procedure described in Example 7 was followed, but 15.24 g (0.071 mol) of diphenyl carbonate were used. 8.38 grams of phenol was collected. The product formed a clear glass. After pulverization, -27.2 g of a white powder was obtained. M.p. 161 ⁰ C (softening range 78 to 95 ⁰ C) ^ MoIe-

5 0 9 8 3 3/1065

weight 850.

Example 9

The procedure described in Example 7 was followed, however, H, 21 g (0.066 mol) of diphenyl carbonate is used. Caught became 8.54-S phenol. The product made a clear one Glass. After pulverizing, it became 25.9% of a white powder obtain. M.p. 217 ° C (softening range 107 to 127 ° C), molecular weight 935

Example 10

The procedure described in Example 7 was followed, except that 13.7 g (0.064 mol) of diphenyl carbonate were used. 10.02 grams of phenol was collected. The product formed a clear glass. After pulverization, 24.0 g of a white powder was obtained. Melting point 240 ^° C. (softening point 131 to 152 ^° C.).

Example 11

The procedure described in Example 7 was followed, except that 50.0 g (0.23 mol) of diphenyl carbonate and 81.2 g (0.21 mol) of 4,4 ^f -Butylidenbis- (3-methyl-6-t- butylphenol) used * The product lost 38.48 g of phenol. The clear glass was pulverized to give a white powder which was slurried in methanol for one hour, then filtered and dried. The product obtained had a mp. Of 255 ° C (softening at 150 ⁰ C) and a molecular weight from 1952.

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Example 12

The procedure described in Example 11 was followed, however 5 ^, 8 g (0.26 mol) of diphenyl carbonate used. That Product lost 38.92 g of phenol. After pulverizing and slurrying with methanol, a white powder was obtained. M.p. 2if8 ° C (softening at H5 ° C), molecular weight 1650.

In the examples described above, several methods of making the compositions of the present invention are illustrated. It should be noted, however, that after each process a "mixture" of the compositions of the invention is formed. The term “mixture” is understood to mean that the products of the examples described above contain compositions according to the invention which differ only in the number of repeating groups and thus in molecular weight. In addition, these processes are used to produce "mixtures" in which one composition according to the invention differs from the other composition in terms of its end group. The mixtures produced appear to arise in a probable distribution. As shown in the examples, the products change depending on the conditions, for example the use of excess phenol or condensing agent. The distribution in the "mixtures" is reproducible. The individual compositions according to the invention can be separated from the "mixtures" by known processes. However, the products according to the invention are also effective stabilizers when used as a "mixture". The average molecular weights obtained by these processes are between 600 and 8,000 or greater. Average molecular weights between about 800 and 3,000 are preferred for the stabilizers of the invention.

The compositions according to the invention are suitable as stabilizers to inhibit the thermal, oxidative and photochemical

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oxidative degradation of fats, hydrocarbons and high molecular weight polyolefins. The stabilizers according to the invention are the materials to be stabilized in amounts of about 0.01 to about 1.5 weight percent added. The compositions of the invention are in high molecular weight solid polyolefins particularly effective when dialkyl sulfide co-stabilizers are also added may be added, for example dilauryl thiodipropionate, distearyl thiodipropionate and diabietyl thiodipropionate. It has been found that when used together with the invention Compositions and dialkyl sulfides have a synergistic stabilizing effect in high molecular weight solid polyolefins occurs.

The compositions according to the invention inhibit the photochemical Degradation of high molecular weight polyolefins is particularly effective when used in combination with dialkyl sulfides. Additional stabilization in the direction of the ultraviolet can be achieved by adding an organic phosphite to the above Combination can be obtained. Suitable organic phosphites are, for example, tris (alkylated phenyl) phosphites, such as Tris (nonylphenyl) phosphite or a dialkyl pentaerythritol diphosphite, such as didodecyl pentaerythritol diphosphite.

When using the compositions according to the invention as stabilizers for high molecular weight polyolefins, they are in Amounts from about 0.01 to. about 1 percent by weight, based on the polymer used. The polymers are preferably with Stabilized amounts of from about 0.05 to about 0.20 weight percent. The dialkyl sulfides are used in amounts of about 0.05 to about 1.0 percent by weight, preferably about 0.1 to about 0.5 percent by weight, used. The organic phosphites are used in amounts of about 0.01 to about 1.0 percent by weight, preferably about 0.05 to about 0.20 weight percent, used.

The polyolefin polymers stabilized according to the invention can be produced by known methods. For example

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can they be carried out according to the polymerisation method \ roni Ziegler type, be manufactured by the high pressure or low pressure process. Examples of suitable polyolefin polymers are polymers of λ-olefins with 2 to 8 carbon atoms in the molecule, e.g. polyethylene, polypropylene, ethylene-propylene copolymers, Ethylene-butene-1 copolymers, ethylene-pentene-1 copolymers and like that. They have molecular weights in the range from about 10,000 to about 1,000,000. Those according to the invention as examples The polymers employed were made by polymerizing the corresponding olefins using polymerization catalysts of the Ziegler type.

The addition of the compositions according to the invention can be expedient be carried out in such a way that the polyolefin is a solution of the compositions in an aromatic hydrocarbon clogs. The solution can be sprayed over the granules or particles of the polyolefin. The mixture obtained in this way can then extruded using suitable extrusion equipment to produce a homogeneous mixture. The invention Compositions can also be added as dry solids when in this form. After adding the compositions of the invention to the Polymer particles can be used to produce the mixture obtained a homogeneous mixture of these components are ground, extruded or passed through other mixing devices. In the same Dialkyl sulfides and organic phosphites can also be added to the polymer particles.

About the stabilizing effect of the compositions according to the invention To illustrate, they have been incorporated into polypropylene. The samples were prepared by dry blending the compositions of the invention with polypropylene powder, the one small amount (0.0 / f - 0.06 weight percent) of the processing stabilizer BHT. The mixes were then extruded and granulated.

09-8 3 3/106

To illustrate that the compositions according to the invention are useful as stabilizers against thermal oxidation, the granules of the mixtures were compression molded into 1.27 mm (50 mil) samples and according to ASTM method D 3012-72 for determining the thermal oxidation stability of propylene plastics aged in a Freas oven with air blower. The samples were kept at a temperature of 150 ^° C. and the days were determined which elapsed until errors occurred in the samples. Any visually recognizable localized discoloration or flaking of any part of the samples directly exposed to the air stream were considered to be defects.

To illustrate that the compositions of the present invention are useful as anti-ultraviolet light detrimental stabilizers, the granules of the mixtures were extruded into a 0.15 mm (6 mil) monofilament and prepared according to ASTM Method D-2565-70, Method B , aged in an Atlas Xenon Are-type weathering knife. Defects were defined as the number of hours that were required to reduce the tensile strength to 50 % of the original value.

The values for the thermal oxidative stability achieved with the compositions according to the invention for polypropylene are in Tables I, II and III included. In Table I the effectiveness of the compositions according to the invention is illustrated, if they are used together with a second stabilizer or co-stabilizer, the combination being a synergistic effect results. The co-stabilizer used in this experiment was distearyl thiodipropionate (DSTDP). Farther Table I are values for a comparison of the combination of the composition according to the invention and DSTDP with two commercially available phenolic stabilizers can be found.

The values in Table II show what effect the increase in the molecular weight of the compositions according to the invention

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Has subsidence. The effectiveness as an oxidation stabilizer increases with increasing molecular weight (Example 7 to 11).

The values in Table III show the effects of the end groups of the compositions according to the invention on stabilization. The values show that the end group 2,4-di-t-butylphenol (No. kk ^ S and Vf27) is more effective than no end group (No. if431 and 2fi6 ^) ". And that methanol is the end group (No. . Jj432 and kW55) is disadvantageous for the stabilizing effect of the composition.

The values in Table IV show that the invention Compositions give polypropylene excellent stability against photodegradation.

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Table I.

Thermally oxidative stability of stabilized polypropylene

Stabilizer system weight percent

oxidative

stability

Days

CD CXJ CO CO

not stabilized distearyl thiodipropionate (DSTDP) 4,4'-butylidene-bis- (3-methyl-6-t-butylphenol) Tris (3,5-di-t-butyl-Zf-hydroxy * benzyl) isocyanurate Pentaerythryl-1 etra-3,5 ~ di-t-butyl-Zf-hydrocinnamate

example

DSTDP, 4, V-butylidene-bis- (3-methyl-6-t-butyl-phenol) DSTDP, Tr'is- (3,5-di-t-butyl-Zf-hydroxy-benzyl) isocyanurate

DSTDP, pentaarythryl-1etra-3,5-di-t-butyl-Zf-hydroxyhydrocine namat

DSTDP, example

0.25 1 Oo 250507 0.10 1 ¹ 0.10 2 0.10 35 0.10 1 0.25, 0.10 15th 0.25, 0.10 108 0.25, 0.10 126 0.25, 0.10 131

Table II

Thermal oxidative stability of polypropylene

Sample no. Stabilizing system Weight percent 0.10 oxidative
stability
Days 4546 DSTBP, example 7 0.25, 0.10 51 4547 DSTDP, example 8 0.25, 0.10 67 4548 DSTDP, example 9 0.25, 0.10 98 4566 DSTDP, example 10 0.25, 0.10 - 118 4654 DSTDP, example 11 0.25, 131

Table III

Thermal oxidative stability of polypropylene

Sample no. Stabilizing system Weight percent 0.10 oxidative
stability
Days 4431 DSTDP, example 1 0.25, 0.10 108 4432 DSTDP, example 2 0.25, 0.10 17th 4429 DSTDP, example 3 0.25, 0.10 112 4164 DSTDP, example I ₊ 0.25, 0.10 93 4435 DSTDP, example 5 0.25, 0.10 ¹ O 4427 DSTDP, example 6 0.25, 108

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Table IV

Photochemical stability of polypropylene

Sample no,

Stabilizing system

Weight percent hours ^ to the original tensile strength
% is decreased

O CO CO

3580 4705 4707 4706

4708

not stabilized DSTDP, example DSTDP, example

0.30, 0.10 0.30, 0.10

DSTDP, Example 8, 0.30, 0.10, 0.10

Distearyl pentaerythritol

diphosphite

DSTDP, Example 11, 0.30, 0.10, 0.10

DLstearyl-pentaerythril »·

diphosphite 250
10 ^ 0
1100
1100

1200

Claims (1)

Claims 'Composition of the following structural formula: where mean: DX a)
b) -S- R ι -Οι RItMl where: R and R ¹ " ^{11 are} hydrogen, a Cj-Cq alkyl radical and an aryl radical, ο 2 -C- d) -C-C- and e) -C-A-C- wherein: A is a C.-C.g-alkylene radical and a Arylene radical, 2) R ^f tertiary C. to C. ^ - alkyl radicals and secondary C ^ -C ₁ alkyl radicals, 509833/1065 R "hydrogen, R ¹ "is hydrogen and a Cj-C ₍ _-alkyl radical, R ¹ " ^{1 is} hydrogen and a (L-Cp-alkyl radical, 3) Y hydrogen, carbophenoxy and substituted carbophenoxy radicals, Zj.) Z a) phenoxy radicals, b) substituted phenoxy radicals and c) ζ ¹ " r ß""· wherein: R ¹ , R ", R ¹ ", R ¹¹ "and X are as before specified and 5) η is a number from 1 to 10. 2. Stabilizing mixture made by reacting a 4,4 ^f -Bisphenol with an equimolar amount or an excess of diphenyl carbonate in the presence of a basic catalyst, the phenol formed is continuously removed and the reaction conditions are regulated in such a way that the average molecular weight of the stabilizing mixture obtained is between 600 and 8,000 This average molecular weight depends in part on the excess of diphenyl carbonate present during the reaction. 3. Stabilizing mixture, prepared according to claim 2, characterized in that the stabilizing obtained Mixture has an average molecular weight of 800 owns up to 3,000. 509833/1065 Zf. Stabilizing mixture after. Claim 2, characterized in that it that the 4, Zf * -bisphenol if, if '-Butyliden-bis ~ (3-methyl-6-t-butylphenol) is. 5. Stabilizing mixture prepared by reacting a Zf, Zf'-bisphenol with phosgene in the presence of a basic one Catalyst and a monophenol, the reaction conditions being controlled so that the stabilizing mixture obtained has an average molecular weight owns between 800 and 3,000. 6. Stabilizing mixture according to claim 5> characterized in that the if, if '-Bisphenol Zf, Zf «-Butylidene-bis- (3-methyl-6-t-butylphenol) and the monophenol is phenol. 7. Stabilizing mixture prepared by reacting an if, if'-bisphenol with phosgene in the presence of a basic one Catalyst and immediately thereafter reacting the polymer obtained with a monophenol, with all Reaction conditions are chosen so that the resulting stabilizing mixture has an average molecular weight between 800 and 3,000. 8. Stabilizing mixture according to claim 7 »characterized in that that the if, if'-bisphenol if, if -Butyliden-bis- (3-methyl-6-t-butylphenol) and the monophenol is phenol. 9. Composition containing a hydrocarbon and a Stabilizing amount of a composition having the structural formula given in claim 1. 10. The composition of claim 9, containing a synergistic Amount of an ELester of thiodipropionic acid or another dialkyl sulfide. 11. Composition according to claim 10, characterized in that the hydrocarbon is a polyolefin. 509833 / 106b 12. Composition according to claim IJ, characterized in that that the polyolefin is polypropylene. ] $ ' Composition containing a hydrocarbon and. a stabilizing amount of a mixture prepared according to claim 2. T / f. Composition according to claim 13, containing a synergistic Amount of a diester of thiodipropionic acid or a dialkyl sulfide. 15. Composition according to claim lif, characterized in that that the hydrocarbon is a polyolefin. 16. Composition according to claim 15, characterized in that that the polyolefin is polypropylene. 17. The composition according to claim 16, characterized in that the bisphenol k, k '-butylidene-bis- (3-methyl-6-t-butylphenol) and the diester of thiodipropionic acid is distearyl thiodipropionate. 8. Polyolefin composition with improved stability against the decomposition by light, characterized in that it an olefin polymer and a stabilizing amount of one Composition of structural formula according to claim 1 contains. 19 · Polyolefin composition with improved stability against the decomposition by light, characterized in that it "contains an olefin polymer and a stabilizing amount of a mixture prepared according to claim 2. 20. Polyolefin composition according to claim 19, containing polypropylene and about 0.01 % to about 5.0%, based on the polypropylene, of the stabilizer produced according to claim 2 509 8337106b mixture in which the bisphenol is if, 1; - ^: -ButylI 6-t-butylphenol). 21. Polyolefin composition according to claim 20, characterized in that it contains about 0.01 % to about 5, ο % of a diester of thiodipropionic acid. 22. The polyolefin composition of claim 21 containing from about 0.01 to about 5.0 % of a phosphite. For: Exxon Research and Engineering Company Linden, N.J., V.St.A. . Dr.H. $ no. At 1 Lawyer 5 0 9833/106 5