DE2143362A1 - Vinyl ester polymers with sterically hindered phenol groups - Google Patents

Description

CIBA-GEIGY AG, Basel / Switzerland

yinyl ester polymers with sterically hindered phenol groups

Preventing various organic materials from being oxidized is an important industrial task. Therefore is added to a large number of technical products which are usually subject to oxidative decomposition, such as synthetic polymers, as given below, to oils, plastics, etc., antioxidants.

The mechanism of action of sterically hindered phenolic compounds as antioxidants is not exactly known. However, one takes suggest that the sterically hindered phenols act as chain terminators serve for the free radical chain mechanism in the oxidation and that they are either hydrogen or a Electron donated to the free radical that occurs during the oxidation process or that the free radical with the aromatic Ring of the antioxidant reacts, either by direct addition or by the formation of a ^ complex.

It is generally believed that free radicals, which are necessary for the polymerization of vinyl and related monomers,

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are borrowed by the antioxidants as sterically hindered Phenols. Because of this, the polymerization of vinyl monomers containing a phenol group or contain a hindered phenolic group, stepwise carried out. In this process the following • stages are carried out: a) esterification of the phenol group,

b) the polymerization of the vinyl group by free radicals and

c) hydrolysis of the ester group to obtain the desired polymeric antioxidant. This procedure is supported by S.N. Ushakov et al. In the USSR patent No. 149 888 as follows.

CH ₃ = CH-

OCOCH.

OCOCH.

G. Manecke and G. Bourwieg, Makromolekulare Chemie, 99 (1966) 175 - 185, describe this procedure as follows:

CH ₂ = CH

CH ₂ = CH

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CH ₃ CO

Eb has now been found that monomers containing sterically hindered phenol groups can be released directly by free alkyl or aryl radicals can be polymerized, the polymeric antioxidants desired according to the invention being formed.

The present invention relates to new vinyl ester homopolymers or copolymers which contain sterically hindered phenol groups in the recurring polymeric units, and the invention also relates to a method of manufacture these polymers. The invention also relates to organic materials and especially synthetic materials Polymers, such as polyolefins, which protect against oxidative and thermal decomposition by incorporating the new novel Polymers are stabilized.

In the process according to the invention, the desired polymeric antioxidants produced by under polymerization conditions a) a monomer compound that differs from derived from a vinyl ester and contains a sterically hindered phenol group and b) an initiator that delivers free radicals, uitoelat. The initiator is a compound that is in a Can dissociate alkyl or aryl radical. Therefore, a one-step process is used in the method according to the invention Production of the desired polymeric antioxidants and can avoid the known multi-step processes.

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BATH ORIGINAL

A key reactant "in the manufacture of the polymeric antioxidants according to the invention is an initiator., which is reacted with the antioxidant monomers and where one receives the desired polymeric antioxidants directly in one step. Included among the initiators are aisqnitriles and azo derivatives in. Alkyl or aryl radicals at temperatures which are suitable for the polymerization, dissociate. The example of an azonitrile that is best known is 2,2'-azobisisobirfcyronitrile and the dissociation that is desired Delivers alkyl radicals is represented as follows:

CH.

CH.

NC-C-N = N-C-CN

CH.

CH.

CH.

2 NC-C.

CH.

+ N,

Other azonitriles and azo derivatives that one can use to make to react them with the aforementioned antioxidant monomers, the desired products according to the invention being obtained, are by J. Brandrup and E.H. Immergut, Polymer Handbook (John Wiley & Sons) 1965, pages II-3 to 11-14 and include for example:

2-cyano-2-propyl-azo-formamide

2,2'-azo-bis-isobutyronitrile

2,2'- ■ A-zo-bis-2-methylpropionitrile

1,1'-azo-bis-i-cyclobutane-nitrile; .- "

2,2'-azo-bis-2-meth.ylbutyronitrile 4,4'-azo-bis-4-cyanovaleric acid

., 1'-azo-bis-i-cycloirentane-nitrile

2.2 '- ■ A-zo-bis-2-methylvaleronitrile 2,2'-azo-bis-2-cyclobutylpropionitrile 1,1'-azo-bis-i-cyelohexan-nitrile 2,2 ^f- azo-bis-2, 4-dimethylvaleronitrile

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_ 5 -

2,2'-azo-bis-2,4-, 4'-trimethylvaleronitrile 2,2'-azo-Ms-2-benzylpropionitrile 1,1'-azo-bis-i-cyclodecane nitrile Azo-bis- (i-carbometlioxy-3-me1; hylpropane) Phenyl azo diphenyl methane

Phenyl-azo-triphenylinethane

Azo-bis-diphenylmethane

3-tolyl-azo-triphenylmethane

Certain peroxide initiators are similarly valuable for manufacture of the polymeric antioxidants according to the invention. The useful peroxide initiators are those that decompose instantly to alkyl or aryl radicals. The alkyl or aryl radicals either by spontaneous decomposition or by rearrangement reaction of the primary decomposition products of the Peroxide compound. Of the peroxides, the aliphatic ones are • Ayl peroxides most useful. Most preferred

Peroxide is acetyl peroxide. The decomposition of this compound in alkyl radicals can be represented as follows:

I II

CH ₃ COO-OCOCH ₃ ? 2CH ₃ COO *:> 2CH * ₃ + 2CO ₂

Implementation II immediately follows implementation I. In the presence of iodine, only CH, I is isolated, which is evidence for the immediate formation of the methyl raccal is. Additionally lauroyl peroxide and decanoyl peroxide also belong to acetyl peroxide preferred. Other aliphatic ayl peroxides up to Containing 18 carbon atoms are used as initiators for the Polymerization of antioxidant monomers also useful. Such peroxide compounds include propionyl peroxide, Butyryl peroxide, isobutyry peroxide, cyclobutane acetyl peroxide, Heptanoyl peroxide, caprylyl peroxide, cyclohexane acetyl peroxide, nonanoyl peroxide, myristoyl peroxide, stearyl peroxide and the like.

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Although the above-mentioned peroxides are preferred, ketone peroxides are and aldehyde peroxides are also useful. It was found that only part of the antioxidant monomer polymerized, if the peroxides just mentioned were used, which indicates that during the decomposition sofoj't formed alkyl radicals became. However, the ketone peroxides and the aldehyde peroxides generally provide lower yields and are sometimes maintained yellow-colored polymers, which indicates that, in addition to the polymerization, an oxidation of the sterically hindered phenol groups also occurs.

Monomers that are used for the preparation of the polymers according to the invention Can use antioxidants are compounds of the formula:

CH ₂ = C (R) -O-A

i adrigalkyl

Lower alkyl

where R is a hydrogen atom or a methyl group, preferably a hydrogen atom,

| A -C _n ^ n "' ^{n =} ^ ** ^is 6» straight-chain or branched, preferably O or 2 or O to 2,

-C HpjjjO-, m = 1 to 6, preferably 1 or 2.

Lower alkyl groups up to and including 6 carbon atoms are for example the following: methyl, ethyl, n-propyl, isopropyl, η-butyl, t-butyl and hexyl.

These groups are substituents on the phenolic group. An alkyl substituent; in o-position to the hydroxyl group and a second alkyl group is either a) in the other o-position to the hydroxy group or b) in the - m-position to the hydroxy group and in p-position to the first Alkyl group. The dialkyl-4-hydroxyphenyl groups are preferred

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- Ί -

pen in which the alley groups are branched groups, such as Isopropyl, t-butyl, or t-hexyl. However, others can Arrangements "can be used, such as the i> -t-butyl-6-methyl-4 ~ liydroxyphenylgruppe, the 3,5-di-isopropyl-4-hydroxyphenylgruppe, the 3,4-di-t-hexyl-4-hydroxyphenyl group, the 3,5-D methyl-4-hydroxyphenyl group or the 3,5-di-n-hexyl-4-hydroxyphenyl group.

The corresponding polymers according to the invention of the Mono mers are those that have recurring units of the formula

i e d rigalkyl

have, wherein R and A have the meanings given above and χ is at least 2.

General methods for preparation of the AntioxydansmonoRieren, which can be used for the preparation of the novel polymeric antioxidants include those procedures which can kyl-- in general for the preparation of Ij and used Arylvinylestern as

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- 8 a) the direct reaction of acetylene with an acid

CHsCH + Ηθά-Λ - ^) -

-.Lower alkyl, lower alkyl

CII ^ CHOC-A- ^ - OH

Me dr ig alkyl Lower alkyl

b) the acid hydrolysis of vinyl acetate or isopropenyl acetate

! Lower alkyl lieurigalkyl

OO r— (. O , - (

CH ₂ = CH-OCCH ₃ + KOC-Zi- (Q) -OH -> CH ₂ = CIIOC-A- / r ^) \ - OH

I ■.

Lower alkyl lower alkyl

Lower alkyl Ni edrig ^ alkyl

OO i - / O / - (

= C (CH ₃₎ -OCCH ₃ + HOC-A- / 1QYOH -> CH ₂ = C (CH ₃₎ -O-Z (T) X-OH

Lower alkyl 'lower alkyl

like them from CE. Schildknecht, Vinyl and Related Polymers, pp. 323-385, (J. Wiley & Sons, Inc., New York 1952).

The preferred method is method b) if mai ·. the Svntliese carried out on a laboratory scale. This procedure is detailed in Example 1 for the preparation of vinyl 3- (3,5-ti-t-4-hydroxyphenyl) propionate described.

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Process for the preparation of acids that are sterically hindered Containing phenolic groups are "known. The synthesis of these acids comprises the conversion of the alkali metal salts of one alkylated phenol with methyl acrylate, the reaction of alkali metal salts of alkylated phenols with esters of Cx -halogenalkanecarboxylic acids, the reaction of alkylhydroxybenzyl chlorides with alkali metal cyanides, whereby one alkylhydroxyphenylacetonitrile receives, with subsequent hydrolysis of the Acids.

If esters are obtained in the processes described above, so one can use the free acids by hydrolysis of the esters Represent sodium hydroxide. The manufacture of some of the Acids used herein are described in U.S. Patent ITr. "3,249,632.

The new vinyl ester polymers, the sterically hindered phenolic ones Groups containing are useful antioxidants for organic materials that are oxidative or thermal Subject to decomposition. These polymers are particularly useful as antioxidants for polyolefins, such as for polypropylene dull polyethylene. Other synthetic polymers which can be stabilized with the polymeric antioxidants according to the invention are polystyrene, polyvinyl chloride, nylon and other polyamides, polyesters, cellulose materials, polyacetals, Polyurethanes, petroleum and wood resins, mineral oils, animal and vegetable fats, waxes, rubbers, such as styrene-butadiene rubber (SBH), acrylonitrile-butadiene-styrene rubber (ABS), olefin copolymers, ethylene-vinyl acetate copolymers, Polycarbonates, polyacrylonitrile, poly (4-methylpentene (1) polymers, Polyoxymethylene and similar substances. It has been found that the polymeric antioxidant, if the polymer, which is to be protected against oxidative decomposition, is a solid material, such as a polypropylene, polyethylene, Nylon, polyacetal, polyurethane, styrene-butadiene rubber, acrylonitrile-butadiene-styrene rubber, and the like should have a relatively low molecular weight, i.

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-it should be an oligomeric compound, -th. a polymer with a molecular weight between about 400 and about 6000. The best and cheapest antioxidant activities are obtained, when using oligomers which have a molecular weight between about 500 and about 1500. Polymers Antioxidants that have a higher degree of polymerization, are incompatible with high molecular weight polymers and therefore less effective with compounds of this type.

Y / it has been found that the polymeric antioxidant if the polymeric material that is to be protected against oxidative decomposition is not a solid, but a liquid or a semi-liquid, such as an oil or wax, should have a higher molecular weight, e. a Molecular weight that is higher than about 6000. With one higher degrees of polymerization often achieve further goals or advantages. This is how polymeric antioxidants work, for example with high molecular weight at the same time as thickening agent and as a viscosity index improver.

As noted earlier, polymeric antioxidants are useful as additives in various polymeric systems. It is also possible to use a small amount of an antioxidant monomer in amounts between about 0.05 and about 5 # and preferably from about 0.1 to about 2 i <> with other monomers that form the polymers that must be protected against oxidative decomposition, form, mix-polymerize. In such a case, the antioxidant monomer part forms an integral part of the polymer system. Small amounts of antioxidant monomers can therefore be mispolymerized with monomers which form polymers which must be protected against oxidative decomposition, such as ethylene, propylene, isobutylene and vinyl halides. Thus, depending on the end use, antioxidant monomer units can form part of an oligomeric polymer system or a high molecular weight polymer system.

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If the antioxidant monomer part is not a copolymerized part of the polymer, the antioxidant polymers can be incorporated into the polymers using known methods. For example, the polymeric antioxidants can be incorporated into the material to be stabilized according to suitable devices, such as by rolling the antioxidants on hot or cold rollers or by mixing using a Banbury mixer or other well-known devices of this type, or the antioxidant can be processed with the polyolefin material in the form of a pre-powdered or it can be processed during the spraying or before the Spraying or working in during a spraying process The antioxidant itself can be incorporated into a solution of the polyolefin material, which solution can then be used for the formation of films, for the wet or dry spinning of fibers, uonofilaments and the like.

It should be noted that the polymers according to the invention . Homopolymers of the new antioxidant monomers and copolymers with other ethylenically unsaturated Include monomers. Comsnomers are in the process of synthesis oligomeric and polymeric antioxidants are important for various reasons. A) It is well known that vinyl esters are present in the generally polymerize less easily with increasing length of the ester group and that a mixture of oligomereEk and unreacted monomer. With certain Gomonomers, however, such as with puma rates or haleates, occurs polymerization easily and high conversions are obtained. B) Gomonoinere can show the physical properties of the polymeric antioxidants, such as the solubility properties, especially the properties in the solid state, modify and the compatibility of the polymeric antioxidants with the Polymers that are to be protected improve and therefore wix'd increase the activity of antioxidants «

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In general, the new vinyl esters show the sterically hindered ones contain phenolic groups, the same behavior during copolymerization as alkyl and ary! vinyl esters, as detailed, for example, by C.E. Schildknecht, Vinyl and Related Polymers, 323-385, (John Wiley & Sons, New New York (1965)). Preferred comonomers, which form slightly alternating copolymers with the new vinyl esters are:

Maleate, Fumerate, Citraconate, Mesaconate, Itaconate and Aconitates with alkyl groups of 1 to 18 carbon atoms; Maleic anhydride, citraconic anhydride and itaconic anhydride; Maleic acid imides, citraconimides and itaconimides with alkyl groups of up to 1 to 18 carbon atoms. * ~

Other monomers with the new vinyl esters. mixed primers, are:

Acrylates and methacrylates with alkyl groups of 1 to 18 carbon atoms; Ethylene and chlorine, fluorine and cyano derivatives of ethylene, such as vinyl chloride, vinylidene chloride, vinyl fluoride, Vinylidene fluoride, acrylonitrile, methacrylonitrile and higher chlorinated and fluorinated ethylene.

Also of importance as comonomers are

Alkyl and aryl vinyl esters, preferably those that are short Contain ester groups, such as vinyl acetate, isopropenyl acetate, vinyl benzoate, vinyl propionate, vinyl butyrate, vinyl diethyl acetate and vinyl trimethyl acetate.

In addition to ethylene, olefins such as propylene and isobutylene can be used as comonomers. Also useful as tomonomers are alkyl esters of crotonic and cinnamic acids having 1 to 18 carbon atoms in the ester groups. Other useful comonomers are cx "ß ^un 6 ^it ättigte esters containing steriscli hindered phenol groups and the German in the patent

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are described, which of the patent application 2? 19 31 4-52.4-. is equivalent to*

The copolymers prepared as described above ent- keep . repeating units of vinyl ester monomers, which have been described above and of ethylenically unsaturated comonomers which have also been described above.

The polymerization of the monomers can be carried out in bulk, in solution, in suspension or emulsion according to known processes. A preferred polymerization process is a solution polymerization process, in which one Lb'sungs-. agents such as benzene, toluene, xylene and other aromatic solvents or chlorinated solvents such as chloroform, tetrachlorethylene and the like, and the initiators described above in amounts which vary between 0 * 10 $> and 2 $, calculated on the weight of the monomers , used. The polymerization temperatures depend on the initiator used and are generally between 40 and 100.degree.

It has also been found when carrying out the polymerization that the use of a solvent is advantageous can be replaced by either distearyl thiodipropionate or dilauryl thiodipropionate. These connections will referred to as "synergistic agents" because they have the activity or increase the effect of the polymeric antioxidants according to the invention. The aforementioned synergistic substances are used in amounts equivalent to approximately 3 parts of synergistic compound to 1 part of antioxidant. If one uses either distearyl thiodipropionate or dilauryl thiodipropionate as a solvent in the polymerization of When using antioxidant monomers, one obtains two main advantages: 1.) It is not necessary after the polymerization to distill off the solvent and 2.) the mixture of antioxidant polymer and synergistic compound It solidifies at room temperature after polymerisation and a white mass is obtained which is slightly pulverized

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. can. Sole powders are preferred additives in comparison with extremely high or solid polymers,

The following examples illustrate the invention without it • however, to be limited.

example 1

Production of vinyl 3- (3 * 5 - di-t-butyl-4-hydroxypheny: L) -propionate

A solution containing 13.9 g (0.05 mol) of 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid and 43.0 g (0.50 mol) of freshly distilled vinyl acetate was added 0.2 g of mercury (II) -aeetat under stirring at 50 ⁰ C treated. After 15 minutes, 0.02 ial 100% sulfuric acid was added and the reaction mixture was refluxed in a sticky atmosphere for 3 hours. The reaction mixture was cooled and neutralized with 0.5 g of Ifatritunaeetat (Ha ^ PpH-Op · 3ΗρΟ '). The solution was decanted from the insoluble solids and then the volatiles were distilled off, leaving 16.5 g of residue. The residue was dissolved in 50 ml of benzene and passed through a bed of 1.44 g of aluminum oxide (Woelm, neutral, activity II). The aluminum oxide was washed with a further 200 ml of benzene. Removal of the solvent yielded 12.7 g (83.5 ° yield) of a product which spontaneously crystallized to a colorless solid with a melting point of 70 to 74 ° C. The product was crystallized from 50 ml of hexane with cooling in an ice bath, giving 9.2 g of material. Mp 71 to 74 ⁰ C was obtained. An analytical sample was obtained by subliming 1.05 g at 100 ° C / 0.05 mm. 1.00 g ($ 95 recovery) of a sublimate with a melting point of IZ to 75 ° C. and whose KivIR ~ confirmed the assumed structure were obtained.

Analysis: C ^ gH ₂₈ O,.

calculated: G 74.96 H 9.27 "p

Found: C 75.12 H 9.17 ° / <> 209822/0970

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According to the method described in Example 1, the following vinyl ester from vinyl acetate or isopropenyl acetate and the respected acids containing sterically hindered phenolic groups:

Table I
Examples .. vinyl ester

9 9 r- ^ 9  rP

CH ₂ = CrIOCCH ₃ + HOC O OH> CH ₂ = CHOC <£ ^ OH

9 U

CH ₂ = CHOCCH ₃ + HOC Ώ) OH> CH ₂ = CHOC (T)) OH

C H- HO (U CH ₂ CIi ₂₂ ^

O O · / O /

CH ₂ = CHOCCH ₃ + HOCCH ₂

δ
CH ₂ = C (CH ₃ ) OCCH ₃ + HOCCH ₂ CH ₂ (Q) -OE-) CII ₂ = C (CII ₃ )

y O

CH ₂ = CHOCCH ₃ +

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Table I continued

Examples. TinyIester

O O /

= C (CH ₃ ) OCCH ₃ + HOCCH ₂ CH ₂ -O-OH- /

O /

O O _ / O /

it · »ι - / _Λ * - · ΐ / ~ ΖΖ \

/ -ITT - / ^ T τ Λ \ / ^ / ^ τ τ JL TTf ^ f ^ TJ OtJ «/» ν »liT-T- ΐ ι ^ ΤΤ ■ -f ~ * VT O Γ" * ^ TT ι M // Λ-

2 3 ZJ. V- / ^ d /. £ \ jz /

O O ^ -A O,

. CH. = CH0CCH _o + HOC (CH ₀ ), - (O) -OH- v CH ₀ = CHOC (CH ₀ ) ί - {θ) -OH Δ 3 2 6 V- ^ 2 2 6

In Table I above are the substituents on the phenyl ring defined as follows:

(a straight line) means an ethyl group

\. means an isopropyl group *

-Ar '

means a tert-buty group

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Examples 9 Ms 13

The Wert.e for the copolymerization of a representative Antioxidant seomonomers, yinyl-3- (3,5-di-t-butyl-4-hydroxy ~ phenyl) propionate (Example 1) and maleic anhydride with various initiators, whereby the corresponding alternating copolymers are formed, are shown in Table II given below. The polymerization was carried out

-3 -5

by adding 2 χ 10 moles of each monomer and 8x5 moles of the Initiator dissolved in chloroform. The amount of chloroform used was twice the total weights of the monomers. The polymerization was carried out under nitrogen with man the temperatures and times given in Table II were used. Under these conditions the polymerization terminated after 1.5 half-lives of each initiator. The yield of copolymer is determined by entering the Polymer solution poured twenty times the amount by weight of hexane and the colorless, brittle polymer dried.

Table II

At initiators Polymerization Polymerisaspiels (0.02 mol / moltation time monomer ) temperature (C) (hrs.)

Yield of alternating copolymer

9 2,2-azo-bis
isobutyro
nitrile * 85 19.5 82.9 io 10 1,1-azo-bis-
1-cyclohexane
carbo-nitrile 60 19.5 80.8 io 11 Decaiioyl peroxide 60 18th 70.0 io 12th lauroyl peroxide 100 18th 72.2 io 13th Methyl-
ethyl-
ket ο np eroxyd 21st 43.5 ° / o

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-The alternating copolymer of the vinyl ester clay game T and maleic anhydride polymerized with azo-bisisobutylnitrile, as described in Example 9, had the following physical property:

Molecular Weight (^ _n ) * 6 130

Freezing temperature (I, DIA): 103 ° C

Melting point (T _n , DTA): 145 ⁰ C

Examples 14 Ms 16

The following examples explain the synthesis of copolymers of the yinyl ester from Example 1 and various comonomers, using azo-bis-isobutyronitrile as initiator. 20 parts of the Vinylesters of Example 1, 80 parts of the comonomers indicated in Table III, 1 part of azobisisobutyronitrile and 100 parts of benzene were melted in a vial under nitrogen and polymerized at 8O ⁰ C for 16 hours. The polymer solutions were diluted to 20% solutions with benzene and precipitated into twenty times the amount of hexane by single eating. The precipitated copolymers were dried and had the properties given in Table III.

Table III

In the case of antioxidant comonomers, the appearance of the molecular

mirror monomers wt .- $ * mixed polymer! - weight

Ie example T sats ^

Weight fo *

14th 31 ,8th vinyl
acetate
68.2 white, brittle
powder 7th 680 Ί 5 36 , 0 Vinyl-
benzoate
64.0 white, brittle
powder 6th 460 16 15th , 0 n-butyl
acrylate
85.0 colorless high
viscous oil 42 000

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* Ratio of anti-oxide monomer to comonomer determined through elemental analysis.

Examples 17 Ms 19

The following examples show the synthesis of alternating copolymers of the vinyl ester from Example 1 and from Di-n-octyl fumarate, azo-bis-isobutyronitrile being used as initiator and n-octyl mercaptan as a chain transfer agent for regulation the molecular weight used.

100 parts of equimolar amounts of the yinyl ester of Example 1 and Di-n-octy.lfumarate, 1 part azo-bis-isobutyroiiitrile, 100 parts Chloroform and n-octyl mercaptan. in those given in Table IV Ratios .wurden melted in an ampoule under nitrogen and polymerized for 16 hours at 80 ° C. The resulting polymer solutions were either in a high vacuum dried or diluted with chloroform to 20% solutions and the twenty-fold amount of methanol precipitated. The dried copolymers have the properties given in Table IV.

At- mol mercaptan is prO KoI vinyl ester Ie. and dioctyl fumarate

Table IV

Molecular weight of polymer calculated: found.

Appearance of the polymer

17th 1 791 886 D. clear, viscous
oil 18th 0.66 1114 1112 ¹ ) clear, viscous
oil 13th no 232OO 2) colorless
something sticky
Polymer

1) Molecular weight calculated from S analysis

2) Molecular weight (M _n ) determined by osmometry

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Examples 20 Ms 21

Example 18 was repeated, but instead of n-octylmei'captan n-dodecyl mercaptan and n-hexadecyl mercaptan were used. Products similar to those in Example 18 were obtained.

Examples 22 to jO

100 parts of equimolar amounts of the vinyl esters of Examples 2 to 10 and di-n-octyl fumarate, 100 parts of chloroform and 1 part of azobis-isobutyronitrile were sealed in an ampoule under nitrogen and polymerized ^{at 80 ° C. for 16 hours.} The polymer solutions were then diluted to 20% solutions with chloroform and precipitated with twenty times the amount of bioethanol. The / precipitated and dried polymers show a similar appearance to the polymer of Example 19 with molecular weights in the range from 16 to 34,000.

Example 51

Homopolymer of vinyl 5- (5 _t 5-di-t-butyl-4-hydroxypheriyl) propionate

100 parts of the vinyl ester from Example 1 and 2 parts of azo-bisisobutyronitrile were melted in an ampoule under nitrogen and polymerized at 80 ° C. for 22 hours. A mixture of unreacted monomer plus a polymer was obtained. After removing the unreacted monomer by high vacuum sublimation at 100 ^° C., 27.6 parts of a v / oak white polymer were obtained. The IR spectrum confirmed the structure.

Analysisi _N (C ₁ 9 H ₂₈ O ₃₎ C. 74, 96 H 9, 27 calculated: C. 75 34 H 8th, 95 found:

The result, i.e. a low conversion in the case of homopolymerization of a vinyl ester derived from a high molecular weight acid is not surprising and

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• - 21 -

is consistent with the general behavior τοη vinyl esters ^ which are derived from higher aliphatic acids (see. C.E. Schildknecht, Vinyl and Related Polymers, p. 377,. John Wiley & Sons, Inc., New York, 1952).

"Example 32

Two experiments were carried out with the materials given in the tables below, using a tube furnace and operating with an air flow of 120 m / minute (400 feet per minute) and an oven temperature of 150 ^{° C.} The oven aging time is given in hours. The term "failure" denotes the first signs of decomposition of the polymer.

Unstabilized polypropylene powder was used to prepare the test samples good with the stated polymeric antioxidant mixed. The mixed material is then placed on a two roll mixer mixed at a temperature of 182 ° C for 6 minutes and then the stabilized polypropylene in the form of pollen taken from the roller and allowed to cool. The polypropylene film that contains the stabilizer, is then cut into small pieces and placed on a hydraulic press at 218 ° C and 12.4 kg / cm (174 pounds per square inch) pressure pressed. The nascent lOlie, the one Thickness of 0.635 mm (25 mils) is then used for its toughness against accelerated aging in the tubular furnace described above.

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- 22 Table V

Investigation of the antioxidant copolymers in polypropylene (0.635 mm (25 mil), tubular oven, 150 ° C

Examples hours to failure.

Table IV) "- ^:

0.25 fo antioxidant + 0.1 56 antioxidant + 0.5 fo ÜV-2 "ν 0.5 # W-2 + _ολ

^} 0.3 %> DSTDl? ^}

17 525 500

18 50 280

19 <2O <20

1) UV-2 '= an ultraviolet absorber 2- (3,5-di-t-butyl-2 ~

hydroxyphenyl) -5-ö.ichlorb'enzo tri azole

2) DSTDP = distearyl thiodipropionate, technical synergist for

Antioxidants

If no antioxidant is added to the polypropylene in the oven aging test mentioned above, then the "hours until the author say "less than 5 hours.

Table VI

Testing of antioxidant homopolymers in polypropylene (0.635 mm (25 mil), tubular oven, 150 ° C

Example hours to failure

0.5 ^ antioxidant $ 0.1 antioxidant +

0.4 ^c ß> -OSTD?

31 * 405 575

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Similar results to those given in Tables V and VI are obtained by using the antioxidants of the two

, - on page 13

Play 17, 18 and 21 together with the / indicated synergistic substances and ultraviolet absorbers used.

Example 33

Production of vinyl ~ 3,5-di-tert-biityl-4-hydroxybenzoate

100 g of 3,5-di-tert-butyl-4- hydr oxy benzo e acid. The mixture was stirred and heated to 60 ⁰ G and then added to 100 ml Äthylendiehlorid added. After stirring for 90 hours at 60 ⁰ C, e Rea was d. '. ^V tion mixture cooled and filtered to give 72.5 g of unreacted starting material to be removed. The filtrate was distilled mm at 4O ⁰ C / 15, and was obtained as a crude product 65 "2 g of a syrup. The syrup was dissolved in 600 ml of benzene and extracted with 2N sodium hydroxide (1 × 200 ml, 6 × 125 ml) until no more starting acid was removed. The organic solution was washed successively with water and saturated sodium chloride solution, then dried over sodium sulfate. Removal of the desiccant and solvent gave 23.3 g of the product in essentially pure form as examined by TLC (silica gel plates, 4/1 CgHg / HeOH, developed with an iodine detector). The product was purified by dissolving it in 175 ml of 95% ethanol, treating it with 1.2 g of animal charcoal, filtering it hot and then adding 80 ml of water. Filtration and drying to constant weight at 40 ° C / 0.1 mm gave 18.5 g of product, m.p. 88 to 90 ⁰ C.

Analysis ; C ^ Hp ^ O,

Calculated: C 73.88 H 8.75 1. Found: C 74.00 H 8.55 fi

The NIüR spectrum confirmed the assumed structure.

2098 22/0970 BAD ORIGINAL

Type of - 24 - -Number of
Protons 2143362 O (PP ^m ) Siiiglett Signals 18th Assignment 1.42 Doublet
Doublet ) 1
) 1 (t-butyl) X 2 4.58
4.95 Singlet of doublets
of doublets 1 · = CH ₂ ■ 5.67 Doublet 1 OH 7.4 Singlet of doublets 2 C-O-CH = O 7.88 aromatic

Example 34 '\ ···

Homopolymer of vinyl (3,5-di-t-butyl ~ 4 ~ hydro: kybenzoate)

100 parts vinyl (3,5 ~ di-t-butyl-4-hydroxy) ~ benzoate, 100 parts Benzene and 2 parts of azo-bis-isobutyronitrile were in one The ampoule was sealed under nitrogen and polymerized at 70 ° C. for 19 hours diluted with a 25 # strength benzene solution and the polymer was increased by adding the diluted solution z.u / forty-fold Amount of hexane precipitated. The precipitated polymer was filtered, washed well with hexane and dried in a high vacuum. In this way, 55 parts of homopolymer were obtained as colorless brittle powder. with a melting range from 195 to

235 C. (C ₁₇ H ₂₄ 0 ₃ ) _n C. 73 , 88 II 8th , 75 Analysis: calculated: C. 73 f 54 Ή 8th , 97 found:

The molecular weight (K _n ) was -10,910.

2 09 822/0970

2U3362

Example 35

-Mix polymer of vinyl (3,5-di-t-butyl-4-hydroxybenzoate) with di-ri-octylfiunara t

100 parts of equivalent amounts of vinyl * (3,5-di-t-butyl-4-hydroxy) benzoate and di-n-octyl fumarate, 1 part of azo-bis-isobutyronitrile and 100 parts of chloroform were placed in an ampoule Melted nitrogen and ^{polymerized at 7O 0} C for 19 hours. The resulting mixed polymer solution was diluted to a 20% solution with chloroform and the mixed polymer was precipitated by adding twenty times the amount of methanol. The supernatant solution was decanted and
the copolymer was washed several times with methanol. After drying under high vacuum, 46 parts of copolymer was obtained in the form of an amorphous colorless solid with a SchineXzbereich 98-145 ⁰ C.

Analysis : (° 37 ^H 6O ° 7 ^ n

Calculated: C 72.04 H $ 9.80>
found: C 71.82 H 9.87 1 °

The molecular weight (M _n ) was 20,120.

Example 36

A P olymerisat of vinyl (3,5-di-t-butyl-4-hydrpxy benzaat) _i with low molecular weight _i n-octyl mercaptan as Kettc oi übortrar; ungsmittel -

100 parts of vinyl (3,5-d: i.-t-butyl-4-hydroxy) benzoate, 100 parts of benzene, 2 parts of azo-bis-isobutyronitrile and 13 parts of n-octyl mercaptan (0.25 mol per mol of vinyl benzoate ) were in a
A.mpu? -Le tilter nitrogen melted down and ^{polymerized at 7O 0} C for 18.5 hours. The resulting solution was diluted with benzene to a 25% solution and the polymer was precipitated by adding the solution to twenty times the amount of hexane. The precipitated polymer was filtered off _t

209822/0970

BATH ORIGINAL

-good washed with hexane and vacuum dried ira high "In this way, 37 parts of polymer was obtained as a white powder with a Schmelzbei calibration from 180 to 21G ⁰ C.

- Analysis : ( ^G 76 ^H 1H ^O 12 ^S ^

Calculated: C 72.93 H 9.18 S 2.56 f ° Found: C 72.72 H 8.69 S 0.00 fa

The molecular weight (M _n ) was 1790.

70 parts of one were obtained from the benzoin-hexane mother-longs viscous oil. The sulfur analysis thereof showed a Sdivrefel content from $ 3.85.

Example 37

Ootelomer of vinyl (3 _< 5 - di-t-outyl-4-hydroxybeny.Oat) with Mn-octylf ^ marate with n-Qctylhr-ercaptan as chain transfer agent

100 parts of equimolar amounts of vinyl (3,5-di-t-butyl ~ 4-hydroxy) benzoate and di-n-octyl fumarate, 1 part of azo-bis-isobutyronitrile, 100 parts of chloroform and 16 parts of n- Octylaiercaptan (0.66 moles per mole of vinyl benzoate) were sealed under nitrogen in an ampoule and polymerized at 70 ⁰ C for 18 hours. The resulting cotelomer solution was mil; Chloroform was diluted to 20 io and then the processed solution was filtered and the coteloraere was isolated by removing the volatile materials in a high vacuum. In this way, 116 parts of cotelomer were obtained as a viscous oil.

Analysis : ( ^C 127 ^ 126 ° 21 ^S 2 ^

Calculated: C 71.16 H 10.16 S 2.99? ί found: C 71.07 H 10.02 S $ 3.04>

The molecular weight O-L) was 609.

209822/0970

Claims (23)

_27_ 2H3362 P at en "tan claims Ζ /. Polymer, with repeating ^ units of the structure CH ₂ - C (R) Low- U)] alkyl l ^ JJ ^ _Kle arigallcyl OH where R is a hydrogen atom or a methyl group, A -C _n H ^, with η is 0 to 6, or - ^c _m ^H 2 _m ~ ° "» ^{with m} is 1 to 6, and χ is 2 or more. 2. Polymer according to claim 1, characterized in that R is a hydrogen atom, A -C Hp, where η is 0 to 2, Lower alkyl is tert-butyl and χ is 2 or more. 3. Polymer according to claim 1, characterized in that the lower Alkylg.ru.ppen are tert-butyl groups and both groups in o-position to the hydroxyl group stand. 4. Polymer according to claim 1, characterized in that A is -CH ₉ -, in which η is 0 or 2. 209822/0970 5. Polymer according to claim 1, characterized in that
that AC EU -0- denotes, in which m represents 1 or 2. 6. Copolymer of a monomer of the formula CH ₂ = C (R) -O C = O
ι Nxedrig-v ! alkyl Lower alkyl wherein R is a hydrogen atom or the methyl group and
A -C Hp _n -, where η is 0 to 6 or G ₁₁₁ Hp _1n -O-,
wherein m is 1 to 6, and an ethylenically unsaturated comonomer. 7. Copolymer according to claim 6, characterized j that the comonomer is vinyl acetate. 8. Copolymer according to claim 6, characterized in that that the comonomer is vinyl benzoate. 9. Copolymer according to claim 6, characterized in that that the comonomer is n-butyl acrylate. 10. Copolymer according to claim 6, characterized in that that the comonomer is di-n-octyl fumarate. 11. Polymer according to claim 1, characterized in that it is a homopolymer of vinyl-3- (3,5-di-t · ^
butyl-4-hydroxyphenyl) propionate. 209822/0970 2U33.62 12. Copolymer according to claim 6, characterized in that that it is a copolymer of vinyl 3- (3, 5 ~ di-t-baityl-4-hydroxyphenyl) propionate and is di-n-octyl fumarate. ". 13 »Copolymer according to claim 6, characterized in that it is a copolymer of vinyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and is vinyl acetate. 14. Copolymer according to claim 6, characterized in that that it is a copolymer of vinyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and is vinyl benzoate. 15 * copolymer according to claim 6, characterized in that that it is a copolymer of vinyl 3- (3,5-di ~ t-butyl-4-hydroxyphenyl) ~ propionate and is n-butyl acrylate. 16. The use of a polymer according to claim 1 for Stabilization of organic material that is subject to oxidative or thermal decomposition. ■ 17. The use of a copolymer according to claim 6, to stabilize organic material that is subject to oxidative or thermal decomposition. 18. The use according to claim 16, characterized in that the organic material "is a polyolefin. 19. The use according to claim 16, characterized in that that the organic material is polypropylene. 20. The use according to claim 17, characterized in that the organic material is a polyolefin. 21. The use according to claim 17, characterized in that that the organic material is polypropylene. 209822/0970 22. Compounds of the formula 0 CH ₀ = C (R) -OC-A .Lower alkyl in which R is a hydrogen atom or the methyl group ", A -C _n IJp _n * in which η is 0 to 6, straight-chain or branched, or -CLH _2n , ⁰ is in which m is 1 to 6" 23. Compounds according to claim 1, wherein RY / ass only off, A - ° _n ^H 2n ""' ⁿ ° ^ ¹ * ^{3 2 and} ^ ie ^ igaiky ¹ mean tert-butyl. ' 209822/0970