DE1931452A1 - Polymeric antioxidants and methods of making them - Google Patents

Description

The invention relates to new compounds that act as antioxidants for organic materials and especially as antioxidants for synthetic polymers, especially polypropylene, polyethylene, Polyst3 * Tol, polyvinyl chloride, nylon and other polyamides, Polyesters, cellulose plastics, polyacetals, polyurethanes, petroleum and tree resins, mineral oils, animal and vegetable Greases, V / axle, rubbers, such as styrene / butadiene rubber (SBR), Acrylonitrile / butadiene / styrene rubber (ABS), olefin copolymers, Ethyl en / Yinylac etat-Mi sclipolymeri sate, polycarbonate, Polyacrylonitrile, poly (4-methyl-pentene-1) polymers, polyoxymethylene and the like, are usable.

The invention also relates to a method of production of these new connections.

Preventing the oxidation of various organic materials is apparently a primary industrial concern and therefore antioxidants are used in a great number of different technical products, such as synthetic polymers of the type specified above, oils, plastics, etc., which are normally subject to oxidative decomposition turns or added to them.

909882/1633

The mechanism of action of a sterically hindered phenolic compound as an antioxidant is not yet fully understood, however it is believed that the sterically hindered phenol as a chain terminator for the free radical chain mechanism of oxidation either by releasing hydrogen or by Donation of an electron to one generated in the oxidation process free radical or by combining a free radical Radical acts with the aromatic ring of the antioxidant either by direct addition or by forming an ir complex.

Since it is generally believed that free radicals are necessary for the polymerization of vinyl and related monomers are, by antioxidants, such as sterically hindered phenols, intercepted, polymerizations of Viny? _raonoineren, which is a phenol group or a sterically hindered phenol group carry, in a succession of stages / w elbe "the esterification the phenol group, free radical polymerization of the vinyl group and subsequent hydrolysis of the ester group to produce the desired polymeric antioxidant. This method is described in USSR patent specification 149 as follows

CH ₂ = CH-

CH ₂ = CH-

CH ₂ - QH

OCOCH,

and by G. Hanecke and G. Bourwieg, Makromolekulare Chemie, 29 (1966), pages 175 to 185 as follows:

909882/1633

ßAD ORIGINAL

CH R. ₂ = CH HO ' IpX ^ R

CH ₂ = CH

CII ₃ COO

OCOCH,

- CII ₂ -CH + I Jn

R X J

CH ₂ -CH-

ΟΗ, σο

OH

It has now been found that monomers that are sterically hindered Contain phenol groups, directly through free alkyl or aryl radicals can be polymerized to form the desired polymeric antioxidants according to the invention.

According to the inventive method, the desired polymeric antioxidants made by

(a) One of a cc, ß-unsaturated acid which is a sterically contains gel-relieved phenol group, derived monomeric compound and

(b) a free radical initiator

polymerizing conditions. The initiator is one Compound that can dissociate into an alkyl or aryl redical. Accordingly, according to the present invention, in manufacturing of the desired polymeric antioxidants in a one-step process applied, thereby din the above, previously known Avoid multi-stage procedures.

Thus, an important Reaktioiicteilnehner in the preparation of polymeric antioxidants erfindungscrnässen an initiator, which may react with the antioxidant-IIonomerRn with direct formation, ie in a stux ^- *, the polymeric frewüiiRchten Antiooxydantien. Rooms: These initiators include azonitriles and Asoderi \ ^ ate, you br-i to the polymer sationsreakti pn .-- common TeraT3 ° rntiiren 5.n Al ^- UyI- od dissociate "aryl radicals The most known ^!?.. An example of an asonitrile is 2,2'-Arso-bj ε-isobutvroiiitri 1 and which provide the required Al 1 ^ rI radical ""

909 8 82/1633

SAD ORJOtNAL

- * - 193U52

The dissociation takes place as follows:

H- OH- OH,

3 ι 3 j 3

ITC-C-IT = IT-C-CIT -> 2 NC-C. + Ed

CH

CH ₅ CH,

Other azonitriles and azo derivatives that react with the above-mentioned Ahtioxydans monomers aur to produce the desired products according to the invention can be used, are by J. Brandrup and E.H. Immergut, Polymer Handbook (John Wiley & Sons), 1965, pages II-3 to 11-14 and related thereto belong for example

2-Gyano-2-propyl-azo-formaTnid 2.2 ^f -Azo-bis-isobutyronitrile 2,2'-Aso-bis-2-methylpropionitrile 1,1'-Azo-bis-1-cyclobutane-nitrile 2.2 '-Azo-bis-2-ynethylbutyronitrile 4,4'-azo-bis-4-cyanopentane-carboxylic acid 1,1'-AzG-bis-i-cyclopentane-nitrile 2,2'-azo-bis-2-methylvaleronitrile 2 , 2 ^l -azo-bis-2-cyclobutylpropionitrile 1,1'-azo-bis-1-cyclohexanonitrile 2,2'-azo-bis-2,4,4-trimethylvaleronitrile 2,2'-azo-bis- 2, A-dimethylvaleronitrile 2,2'-azo-bis-2-benzylpropionitrile 1,1'-azo-bis-i-cyclodecane nitrile azo-bis- (1-carbomethoxy-3-methylprouane) phenylrazo-diphenylmethane phenyl-azo triphenylmethane azo-bis-diphenylmethane 3-tolyl-azo-triphenylmethane

909882/1633

BATH ORIGINAL

Certain peroxide initiators can be used in the same way in the preparation of the desired inventions polymeric antioxidant products, the useful or useful peroxide initiators being those which are instantly incorporated into Know how to decompose alkyl or aryl radicals. The alkyl or aryl radical is produced either by immediate decomposition or by a storage reaction of the primary decomposition products of the peroxide compound obtain. Among the peroxides, for example, the aliphatic acyl peroxides are the most useful and one the preferred aliphatic peroxide is acetyl peroxide. The decomposition this compound into alkyl radicals can be achieved by the following Scheme are shown:

I II · CH ₃ GOO-OCOGH ₃ - > 2GH ₃ GOO '> 2CH ₃ ' + 2CO ₂

Reaction II immediately follows reaction I. In the presence of iodine, only CH ₃ I is isolated, proof of the immediate formation of the methyl radical. "Besides acetyl peroxide, lauroyl peroxide and decanoyl peroxide, the preferred peroxides, other aliphatic acyl peroxides containing up to 18 carbon atoms can also be used as initiators for the polymerization of the antioxidant monomers , Caprylyl peroxide, cyclohexanaoetyl peroxide, nonanoyl peroxide, hyristoyl peroxide, stearyl peroxide and the like.

Aromatic acyl peroxides such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and the like have also been examined. However, no polymerization occurred because of the intermediate benzoyloxy radicals do not immediately decompose into phenyl radicals, but rather "the hydroxyl group of the antioxidant hydrogen revoke.

909882/1633

BATH ORIGINAL

193U52

Dialkyl peroxides and especially di-tert-butyl peroxide were also examined as possible polymerization initiators. In the equivalent of antioxidant monomers, however, it was found that that the tert-butyl alcohol was the main decomposition product, which indicates that the alkoxy radical is more likely to be hydrogen withdraws from the double bond of the antioxidant monomer to accumulate. Peresters have also been studied, but these compounds have been found to be the antioxidant monomers oxidize, but not polymerize. Another group of Compounds that have been investigated for their potential use as polymerization initiators have been the hydroperoxides and a typical example was tertiary butyl hydroperyl. It was found, however, that this latter compound in the implementation with an antioxidant monomer, none Polymerization resulted in no alkyl radicals at the same time were formed during the decomposition. It is assumed that the other hydroperoxides behave similarly.

Another group of compounds examined were the ketone peroxides and aldehyde peroxides. It was found that only partial polymerization when using the above peroxides of the antioxidant monomers occurred, indicating that the alkyl radicals formed instantly during the decomposition became. The etone peroxides and aldehyde peroxides gave Jedoeh. in the generally lower yields of antioxidant polymers and sometimes yellow-colored polymers were obtained Indication that in addition to the polymerization, oxidation of the sterically hindered phenol group also occurred.

Some of the polymers used to make the polymers of the invention Monomers used in antioxidants are among the following. Connection classes:

BATH ORIGINAL

909882/1633

-.022222SiL

Ester. Thioesters and amides of acrylic and methacrylic acid

Esters »thioesters and amides of maleic acid (R. = H, ice) fumaric acid (R ₁ = H, trans) citraconic acid (R ₁ = CH ,, ice)

Mesaconic acid (R ₁ = CH ,, -, trans)

ι j

Imides of citraconic acid and maleic acid

CH ₂ = G (R ₁ ) -COX-AR

COX-A-R

COX-A-R

IT-A-R

Esters, thioesters and anides of itaconic acid

Esters, thioesters and anides of crotonic and cinnamic acids

CH ₂ = C-COX-AR

CH ₂ -COX-AR

CH ₅ -CH = CH-COX-AR C ₆ H ₅ -CH = CH-COX-AR

where R

(Lower) alkyl

(ITlower) alkyl and preferably

. (Hi edrifO alkyl

(lower) alkyl

R .. hydrogen or _X 0-, -S -.'- KH-; -

- \ md

-Ch ₀ GH ₀ XCOGH ₀ CH ₀ - ', -0, H ₀ - ( c. <L ad Hl cXH

m 2ra * ** n. * 2a

η 0 Ms f, non-branched or branched, m 1 to 6, non-branched or branched, ο 1 to 3 .. * ■■■■; ■■■?: - {:> a, ±

mean.

^ 909882/1633 "and before

βΑΟ ORIGINAL

193U52

The term lower alkyl as used herein includes alkyl groups containing "up to and including 6 carbon atoms, and examples thereof are methyl, ethyl, n-propyl, isopropyl, η-butyl, tert-butyl, hexyl and the like.

The corresponding polymers of the monomers according to the invention are those with repeating units of

CII ₂ -O (R ₁ ) -J- CO-XAR

/It

Esters, thioesters and amides [of acrylic and methacrylic \ acid

-CH-

■ 9 (& i

CO-X-A-R CO-X-A-R

CH-

CO

CH,

C (R. CO

,! ΤΑ
R.

-el

/ from left

CO-X-A-R

H ₂ -CO-XAR

/ Esters, thioesters and amides from Haiein-, Fumar-, Citracon-I and mesacona acid

/ Iraiden of maleic and I citraconic acid

/ Esters, thioesters and j I amides of itaconic acid /

--CH (CH, - or -Cv-Hc) -CH-- f esters, thioesters and amides] ■ * '' ⁷ \ J \ of crotonic and cinnamic acids j

CO-XAR \ y

v / orin R, R., -X- and -A- have the meanings given above. .

Of the various classes of monomers given above
the preferred groups of monomers are the esters, shioesters and amides of acrylic, hethaeryl, fumaric and itaconic acids.

909882/1633

SAD ORiGiNAt

Examples of specific monomers of the above-mentioned groups of antioxidant monomers which are used for the preparation of the polymeric antioxidants according to the invention are
the following:

structure

3,5-di-tert-butyl-4-CH ₂ = OH-COO-R

hydroxyphenyl-acryl at

3,5-Dt-tert. -bu tyl-4-hydr oxy CH ₂ = C (^) ₂

phenyl methaorylate ^

3- (3,5-Di-1 ert. -Butvl ^ -hydroxy-CH ₂ = O (CH ^) -COO (CH ₉ ) -R ₂
phenyl) propyl methaerylate - ^J * ~

2- (3,5-di-tert-butyl-4-

hydroxyljenzoyloxy) -ethyl- CH ₉ = C (CH,) - COO (CH ₀ ) ₉ 0C0-R _o

methacrylate "' * - 0 ά <ld

2- (3,5-Di-te.rt .- "butyl-4-

hydroxyphenylacetosT) -ethyl- CH ₉ = C (CH,) - COO (CH ₉ ) ₉ OCOCH ₉ -R ₉

methacrylate ^ ·> ^ά * * ^ά

2- [3- (3,5-di-tert-butyl-4-

hydroxyphenyl) propionyloxy] - CH ₉ = C (CH -) - COO (CII ₉ ) _o 0C0 (CH ₉ ) ₉ -R ₉

ethyl methacrylate "" ^d . > ^{ά fc Δ ά ά}

2- [3- (3,5-D.t-t ert. -Butyl-4-

hydroxyphfinyl) -pronionyloxy] - CH ₉ = CH-COO (CH ₉ ) ₉ OCO (CH ₉ ) _O -R ₉

ethyl acrylate " ^ά ά ά. ά d ί

2- [3- (3. ^ - di-tert-butyl-4-

hy (iroxyphenyl) -propionyloxyl- CH ₉ = CH-COO-CHpCH (CH ^) OCO (CHp) PR

propyl acylate " °

2- [3- (3,5-I) i-tert. ~ L> utyl-4-

hydroxyohenyl) propionyloxy] - CH ₂ = C (CH -) - COOCH ₂ CH (GH-) OCO (CR) ₂

propyl methacrylate '■

Bis- (3,5-di-tert-butyl ~ 4-hydr ο xyph enyl) fumarate

Bis {2- [3- (3,5-di-tert-bu.tyl- H COO (CHp) «000 (CHp) ₂ -H ₂ ■ 4-hydrox ^ -r> hpnyl) - nropionyloxy3- \ ^
ethyl funarat

909882/1633

SAO ORK3INAU

1331452

n-Sutyl-2- [3- (3'.5-cU -tert. -.

biitvl ^ -hydroxyphenylj

oxyl propyl mateate

Bis (3,5-di-tert-butyl-4-hydroxyphenyl) itaconate

3,5-di-tert-butyl-4-hydroxyphenyl crotonate

3,5-di-tert. -butyl-4-hydroxyphenyl-c innamat

H-3,5-di-tert-butyl - * - / ^ hydroxyben ^ yl-acrylamide ^

GOOCH ₂ CH (CH _g ) OCO (CH) ^ - T

GH ₂ = C-COOR, CH ₂ COOR

CH_-CH = CH-C00R _o 3 2

C ₆ H ₅ CH = CH-COOR ₂ CH ₂ = CH-COIJHCh ₂ -R ₂

^ ⁷ described in the French. U.S. Patent 1,457,152

, G (CH,).

where R,

C (CH ₃ ) ₃

means.

Of the antioxidant ionic acids listed above, the preferred are Monomers the acrylates and methacrylates «

The three general methods of making the antioxidant » Monomers that are used for the preparation of the polymers according to the invention Antioxidants applied are the following;

ΐ £ ίί £ ί2ΐ £: Β_ ^ one mole of the alcohol given in Table I below, which is dissolved in 5 times the amount of pyridine, is 1 mol of the given in Table I below ^{with vigorous stirring at 5 to 10 ° C} Acid chloride in the form of a

n solution added, the temperature below 25 "C-" The reaction mixture will be held for 1 to 2 hours slightly stirred at Paum temperature. The precipitated hydrochloride is filtered off, the solvent and the excess pyridine

909882/1633

BM) ORSGlNAL

are evaporated and the residue is v / ird after the addition of "fcher washed with 2N hydrochloric acid and then with Yfesser. the separated ether layer is dried over lithium sulfate, filtered and evaporated., The residue is then, as in the Table I below indicates either church HochvaV.xiura distillation or purified by recrystallization. The yields are very high, i.e. they range from about $ 70 to $ 95.

Method B - Equimolar acidity and alcohol are used (as indicated in Table I below) in twofold Amount of Bensol or Eoluene for 12 to 36 hours, "under-reflux boiled (refluxing is stopped when the conversion, such as by gas chromatography or thin layer chromatography is found to be high genup: is). Then it will be the hesktiojisiainchung with a 2N potassium bicarbonate solution and then washed with kegs. The organic layer is over ITaiacIuiasulfat rretdry and after the evaporation of the solvent the crude product, as indicated in the following table I, either by high vacuum distillation or by recrystallization purified * The yields are in the range 65 and $ 85.

-.S alcohol is converted into 3 to 5 moles of the acid

dissolved and refluxed for 1 to 3 hours (The refluxing is stopped when the conversion, as by gas chromatography or thin layer chromatography is determined to be Tollständig). The excess at Acid chloride is then removed by distillation and after Wash the powdery residue with hexane or heptane to remove it the last traces of the acid chloride is the residue, As stated in table I * purified by recrystallization. The bulges are excellent and vary between 80 and

suletEt is the preferred method in the A look at the short reaction time, ... the very high yields and the simple work-up procedure when the excess is on

908882/1633

8AO

f »β β«

. ■■■■■ "■ ■■" - ¹² -.

Acid chloride, as in the case of acrylyl chloride, methaerylyl chloride, crotonyl chloride, cinnamoyl chloride ,. etc., easily

♦ ■■■ - ■ ■ can be removed. If the boiling point of the acid chloride is too high, procedure 0 described above is carried out using a solvent such as benzene ',, lolupl,

The starting materials used to make the antioxidant monomers and "the properties of these monomers are given in the following label I. In the last column the table shows the synthesis method used and attention is drawn to the procedures listed above.

909882/1633

(O OO ÖD

ϊ ¹ . (C). El era en tar anal.

Moiioroeres appearance (fcristalli- Kp (C) "Ter ~~" ^ e? "~" S5ürechlorTd "" ITvrt5ö ~, proced-

5,5-Di-tert, - white 102,5 ^ 105,5 -— 0 73,88 73,95 Acrylyl- 2,6-Di - fcert, -

t) ütvi-il-.liv'drö3ry- Eristalle (heptane) H 8.75 8.95 chloride butylhydro- A

phetyl acrylate quinone

-weisge 137 -137 * 5 0 74.44 74.15 methacrylyl 2,6-di-tert, -

^ yy- crystals (heptane) H 9 * 03 8.73 chloride butylhydro- A

phenyl- ■ "". quinone toethaorylate

^ (^. ^^ Bi ^ tei-t * - yi oleo sea / ^ 6O 157 0 75.86 75.63 Methacrylyl 3- (3> 5 ~ Di-tert.-

putyi-4 * hydroxy- 01, yer-, (0.1inm) H 9.70 9.83 chloride butyl-4-hydroxy- A

pheriyl) -propyl ~ strengthens,. ■ ', ■ phenyl) -1-pro

methacrylate itself n * d * panol

2- (33-M "tert * - weispe ■■" 71.5-72 069.5869.74. 3,5-di-tert.- 2-hydroxyethyl-

butyl * 4-hydroxy crystals (heptane) H 8.34 8.54 butyl 4-methacrylate A

benzoyloxy), hydroxy

ethyl ethyl acetate benzoyichloride

2- (3.5-m-tftrt, - v / eiBse 54.5-56 174 O 70.18 70.16 3.5-IÜ-tert.- 2-hydroxyethyl-

Taut2 '"i-4-hyaro3c \ r crystals (heptane) (0.2mm) H 8.57 8.41 butyl-4-hy- methacrylate A

phenyi-aceto5cy) ^ ■ droxyphenyl-.

ethyl methacrylate. acetyl chloride

2- [3- (3.5 ^ 3- colorless .—- 196 0 70.74 70.54 3- (3 ^ 5-Dl- 2-hydroxyethyl-

tert. ⁱ -butyl-4-viscoses (0.1mm) H 8 * 70 8.66 -tert.-butyl methacrylate A

) - Oil '4 ^ yCIrOXy-

ppyy], phenyl) -pro-

ethyl methacrylate pionyl chloride

5L ^ -S-S-ILiUL .--- I (continued)

J *. ( ⁰ C) elementary al. Ausgan ^ Rmatieri al Syn

Monoraeres' appearance (crystalline Kp (O) _χ ~ Τ ~~~ 7 ~ Ι ~ ί ~~~ acid chloride ~ "Il? Oil" ~ "" ~ "

i ^ L ISI fill S! il -ΞΐΞ?! -_ ° -ϋ: _ "_-_ -

2- [3- (3,5-Di- colorless - 181, C 70.18 69.8Q 3- (3,5-Si-? -Hydr <oxy-

te ^ t .- "Dutyl-4 · '- ViBkoses (0.1ram) H 8.57 8.60 tGi-t. ^ butyl-ethylt-acrylate A

hydroxyphenyl) * · oil 4-hyd "rox7-

PrOPiOnViOXyI * - '"- phenyl) -pro-

ethyl aerylate '' ■■ pionyl chloride

»« [.3- (3, 5-M- colorless - 181 0 70.74 70.60 3- (^, 5-Di - 2-hydroxy-

ttA viscous (0.2mm) H 8.78 S, 57 tert.-hutjri-propyl- Δ

y) ~ oil · _; .. "4-» hydroxy acrylate

yi ox «rl-. phenj ^ iy-pro-

l-acryl at pioiiylchiorid

2 * - [3- (5,5-di- colorless --- 178 C 71.25 71.26 3- (3.5-Ώί.- 2-hydroxy-

teit.-butyl - ^ - viscous (0.05 H 8.97 8.89 tert.-butyl-propyl-, Δ

hydroxyphenyl) oil .mm) 4-hydroxy methacrylate

prop ioiiyl 03ry] - phenyl) -pro-

propyl methacrylate. ' pi onyl chi orid

Bis- (3 ^ -dT.- yellow 205-205.5 - »- C 73.25 73.49 Fiitnaryl- 2.6-di-tert.-

t6ft> -butyl-4-crystals (heptane / H 8.45 8.40 chloride butyl-hydro- B

hyrlroX7 / pher) yl) - ■. Benzene) 'quinone

■ fwn & ff & t ■ " . ·. .- '■' ■ ■ ', ■. ■,:. ■ ■. ■ .; ■'''. ■ ■. ■ .. ■■. '■ ■■■■■"'.'■■' ■■ .. ■ ': ■ ..' ■ '. . . . ■ ■■ -. "'■

lisi2- [3 '- (3.5- white 99.5 ^ 100.5 ---- 0 69.58 · 69.52 Pu.maryl- 3- (3,5-Di-'

Öite1ibtl- ■ Crystals · '(Hexane) H 8.34 8.'50 chloride tert-butyl-4-B

ypyl) - hydroxyphenyl) -

pnyl oxy] * - 2-hydro3cyät> jyl-

} fiit © ^: J ^

.: ■ ■■ '■' ■■ -vi

T AB E I IJ! I (continued)

• Monomers

Look

( ⁰ C)

: SLial Eleraentaranal. Aias gan material

n-? Butvl-2- [3 «colorless (^, 'i-'di-tcft, - viscous "buty3-4 ~ hyflrox3r · - · oil phenyl) -prdpionyl-

oil

white crystals

- white -4-hydroxy- crystals ltt

rnnlent

«Ο '

⁴ ^ t he t.-3iy4rox
M & taconate

3 _f 5 ~ white "butyl-4-hydro253r- crystals phenyi-cinnamate

IT-3,5-di-tert-white ■ butyl 4-hydroxy crystals t> enzylacrylaraid

iff ::

fÜf! L

228-230 0 68.54 68.74 3- (3,5-Bi- hydroxy- (0,6πηβ) Η 8.63 8.33 tert-butyl-propyl-n- '

butyi-inaleat

145-146 (heptane)

80.5-81.5 (heptane)

125-126 (heptane)

114-116 (ethanol / water) C 73.57 73.59
H 8.61 8.61

phenyl) propionyl chloride

Itaconyl chloride

G 74.44 74 * 39 Crotonylr « K 9.03 9.23 calorid '*

G 78.37
H 8.01

Ciiinainoyl Chloride

2,6-di-tert. »

butyl hydro

Ghinon

2,6-Di-1 er t.

butylhydro-

cliinon

2,6-di-tert, -

butylliydroquinone

French patent 1,457

-ie- If 31452

CzI ■ ■■ ^; ■> ^: ■ -

^ This alcohol. -Was-made by the following procedure: The ester of % 5-di-tert-butyl-4-hydro: xyphenyl-propionyl chloride and ethylene glycol was made using "Procedure A above and a 20%" Molar excess of ethylene glycol. The product was purified (using the work-up procedure described in Method A above) by column chromatography using neutral Alox I and further purified by recrystallization from heptane. The product was given in form obtained white crystals which melt between 87.5 and 88.5 ° 0

calc .: 70.77 f 9.38? δ ^Γ

found : 70.81 ~ f> 9

90 9 882/1633

BAÖ ORiGlNAL

It has been found that if that is against oxidative decomposition polymer to be protected is a pesticide ", e.g. a polypropylene, polyethylene, ITylon, polyacetal, polyurethane, Styrene / butadiene rubber, acrylonitrile / butadxene / styrene rubber school and the like, the polymeric antioxidant is a relatively should have a low molecular weight, i.e. it should be an oligomeric Substance, i.e. a polymer with a molecular weight between about 400 and about 6000. The "most useful and highest antioxidant activities are obtained when using oligomers which have a molecular weight between about 500 and have about 1500. Polymeric antioxidants with a higher level Degrees of polymerization are not compatible with high molecular weight polymers and are therefore less effective with substances this guy.

It has also been found that if this is against oxidative decomposition The polymeric material to be protected is not a solid, but rather a liquid or a semi-solid substance, such as an oil or a wax, the polymeric antioxidants have a higher molecular weight, i.e., molecular weights above about 6000. At -a higher degree of polymerization sometimes occur secondary results or benefits that can be achieved. In oils, for example, polymeric antioxidants with a high molecular weight also act as thickeners and agents to improve the viscosity index.

¥ The ones already mentioned above, polymeric antioxidants can be used as additives to various polymeric systems. However, it is also possible to copolymerize smaller amounts of an antioxidant monomer in amounts which vary between about 0.05 and about 5 % and preferably between about 0.1 and about 2% with other monomers which form polymers, which require protection against oxidative decomposition. In such a case, the AntioxidanR monomer fraction forms an integral part of the polymer system. ¹ Small amounts of antioxidant monomers can therefore be used as butadiene / styrene, aeryl nitrile / butadiene /

§09882 / 1633

■; ^ _::; : ^ ii- _: SAOORfGiNAL

Styrene, ethylene and other monomers are copolymerized, the Polymerinn.te Ml, which require a solrate against oxy dative decomposition. So depending on the end use ..Antioxydans-IInnornerantoil ρ a part of a ?! oligomeric or high molecular weight. Polyme? '.'IGats; rBtenis

If the anti-cyclic monomer component is not a copolymerized part of the polymer which requires protection against oxidative decomposition, the anti-cyclic polymers can be incorporated into polymers using more methods. At game's ^SWEi: e are .the erfindnngsgemässen polymeric antioxidants in dan zu.stabilisierende material by any suitable means ·, be? For example, by grinding the antioxidant on hot or cold roller mills, by mixing it in using a Banbury mixer or other known devices of this type, or the antioxidant can be incorporated with the polyolefin material in the form of a molding powder 'mixed around during the extrusion or before the extrusion or during the injection: essens incorporated. The antioxidant can even be incorporated into a solution of the polyolefin material. which solution can then be used for the production of films, for wet or dry spinning of fibers, threads and the like.

It should be noted that the polymers according to the invention are homopolymers of the new antioxidant conomers and their copolymers with other äthylenir.eh unsaturated Include monomers. The polymerization of the monomers can-in Mass, in solution, in suspension or emulsion carried out according to methods known to the person skilled in the art .. The preferred Pop.ymeri The solution polymerisation process is the solution polymerisation process using solvents such as benzene, toluene, Xylene, and other aromatic or chlorinated solvents Solvents such as 3. Chloroform, tetrachlorethylene, and the like, and the initiators described above in amounts between 0.01 and 2? <, based on the weight of the monomers.

- .-> _f ^ a 909882/1633

.- 19 -

vary. The .Polymerisationsteraperatures depend on the initiator used and usually ran between 40 and 100 ° Ö. - "■ / '■

It was also found that when the polymerization was carried out the solvent advantageously through the use of either distearyl thiodipropionate or dilauryl thiodipropionate can be replaced. These connections are called “Synergists” denotes since they increase the activity or the effect of the polymeric antiorydants according to the invention. the The above mentioned synergists are used in proportions of about 3 Share Synei'g is used on 1 part antioxidant. Besides that can by using either distearyl thiodipropionate or dilauryl thiodipropionate as a solvent in the polymerizations the antioxidant monomers achieve two significant advantages:

(1) the prelude to the stripping ?, the solvent after the Polymerization is avoided and

(2) the antio ^ .rclpjispolyroerisat-Synergist-Hischen solidified after polymerization at room temperature to a v / e, i.Rsen Hate that can be easily pulverized. These powders are additives compared to highly viscous or solid polymers preferred. ■.

The following examples explain the processes used to prepare the polymeric antioxidants according to the invention and also explain the various tests which were carried out with these polymeric antioxidants. These examples are merely to illustrate the present invention without, however, limiting it.

In Table II below is the homopolymerization of representative representatives of the Antio ^ Na & ns-i.ionoraeren, i.e. of 2- [3- (3,5 ~ di-tert-butyl- ^ hydro ^ phenyl) -propionyloxyl-ethyl-baethaerylate and 3,5-di-tert-bu-tArl-A-hydroicyphenyl methacrylate, with different initiators to form the corresponding

V-. '<■■ "' 0.09882 / 1633; ■ ·.

internal antioxidants. The polymerization will

_ "5 ■■■■ '-, carried out by, for example, 4x10 moles of the monomer

- ■ - _5 -. ■■■ .-. "■■" - ■ - .. ■■■ - ■■ -.- "■■ and 8x10 mol of the initiator is dissolved in three times the amount of benzene. The polymerization is carried out under nitrogen and carried out using the temperature and time given in Table 2. Under these conditions, the polymerization is terminated after 1.5 times the life of each initiator.

TABLE II

Initiators Polym. Polym. Yield to Yield to (0.0? Mol / mol Expensive. Time HomoOolTTn. HomoTvolym. Monomeric} ^ Hours} ί · "'1 Φ ifil Φ 2-cyano-2-r> ropyl- azoformamide 100 23 88.8 75.6 2,2'-azo-bis-iso- butyronitrile 65 19.5 86.7 84.5 1.1 -Azo-bip-1- cyclohexane earbo 85 19.5 91.9 84.8 nitrile. Acetyl peroxide 67.5 18th 70.8 69.5 Decanoylpero ^ rvd 60 18th 70.5 - = 75.4 Lauryl neroxide 60 18th 88.9 84.5 ' 2,4-dichloro benzoyl peroxide 52 ' 19.5 no no Benzoyl peroxide 70 19.5 no no He thyläthyIkeΐοη- peroxide 100 21 54.2 35.0 tert-butyl peroxide 125 19.5 no no CumylT> ernxyd 115 18th no noFi tert-but ^ l-hydro- - peroxide 160 43.5 no no Cumene Hydro Animal Oxide 155 19.5 no . no tert-3utyl peracetate 100 19.5 no no tert-butyl perpivalat 52 19.5 no no tert-butyl - perbenzoate 105 19.5 1 tbsp. ixe Vein θ

90988 2/1633

BAO ORfGlJMAL

^ 2- [3- (3, S-di-tert-butyl ^ -hydroxyphenyl) propionyloxy] ethyl methacrylate - "..-.'.- '

^ 3,5-Di-tert-butyl-4-hydroxyphenyl methaerylate

From the above results it can be seen that only when using the initiator compounds indicated as being useful the polymerization can be effected.

The following Table III explains the homopolymerization of the preferred acrylate and methacrylate antioxidant monomers. In the polymerizations indicated, 10 parts of monomer, 20 parts of chloroform and 0.2 part of 2.2 ^l -azo-bis-isobutyronitrile are used, the process is carried out under nitrogen and the mixture is ^{polymerized at 80 °} C. for 16 hours. . ·

TABELI. E III

Monomer

Thermal differential yield in G-ew .- $ analysis

3,5-Dl-tert-butyl-4-hydroxy-phenyl-acrylate

3,5-di-tert-butyl-4-hydroxyphenyl methacrylate

3- (3,5-Di-tert-butyl-4-hydroxynhenyl) -prooyl methacrylate

2- (3,5-di-tert-butyl-4-hydroxybenzoyloxy) -ethyl-. methacrylate

2- (3, 5-Di - +. Ert. -Butvl-4-hydroxvphei ^ lacetoxy) -. äthy ¹ -Ft e thaoryl at

2- [3- (3.5-Di-tert-butyl-4-hydroxyphenyl) -oropionyloxy] -ethyl-methaerylate

2- [3- (3,5-di-tert-butyl -4-

hyd ^ oxyphenyl) propiony1.oxy] ethyl acrylate

909882/1633

79 blurred 60 +148 76.3 blurred +178 65.8 +55 "Ms 63 our.harf 82 +111 30th +125 92.5 +58 to +95 " 81.2 +29 to BAB +100 97.4
3 3 +24 +70 to
80 ORIGINAL

(Continuation)

, Thermal differential job analysis

2- [3- (3,5-Di-tert- "butyl-4-nyrtroxyphpnyl) -proOionyloxy propyl acryate

2 [3 (3.5Ditert.buty34
hydroxyphenyl) -proi> ionyloxy1 Oropvl-methacrjrlat ""

y
hydroxj ^ benzyl acryiamide

74-, 2 +7
75, B +42
79.45 +138

. + 42

+57 "to

58 ■.

: +172

In all! Cases, the polymeric antioxidants are in shape of a white powder. At Yerv / endunp of B ° nzoyl peroxide no polymerization occurs as an initiator.

The following table IV explains the production of horopolymers, for example oligonucleotides and high molecular weight polymers of 3,5-di-tert.-hutyl-4-hy < ^: oxvphenyl-inethacrylate. In the preparation of these Hoiaopol products, 1 mole of the above-mentioned monomer (and the octylraercaptan in the proportions given) and 0.01 col.2 ₅ 2'-azobisisobutyronitrile are dissolved in twice the volume of chlorine forra. The polymerization is carried out under nitrogen at a temperature of 80 ° C. for 16 hours; carried out. The erhaltp-πρ ■ nol-Tner: Product is not fractionated, but obtained by evaporation of the solvent. The molecular weight is determined by osmometry or vapor pressure osmometry.

ORIGINAL BATHROOM

909882/1633

IV

Appearance
of the poly Mole mercatttan /
Moles of monomer Average
Molecular Weight 935 ΠΊγγΐ f fl Λ
AlU I ^ y J white,
crumbly
powder 1/2 727 1176 +55 Il 1/3 1017 1336 +66 Il 1/4 1307 1888 +72 Il 1/6 1888 81400 +83 Il none ___ + 178

It should be noted that "in the preparation of oligomers, i.e. from antioxidants with a low molecular weight, the polymerization usually takes place in the presence of chain transfer pn, such as mercaptans, is carried out. Examples of such chain carrier products are alkyl mercaptans, such as n-octyl · ·, n-dodecyV. n-He?: adeoyl - nerca-ntane etc.

Comonomers are important in the synthesis of oligomeric and polymeric antioxidants insofar as they can modify the physical properties of the polymeric antioxidant, i.e. the solubility properties and the solid properties of the polymeric antioxidant can be influenced, and the use of Modified expensive antioxidant monomers or replaced by using cheap co-monomers.

The copolymerization behavior of the antioxidant monomer can be determined in advance by the corresponding Moncra class, that is, an antioxidant ionic acid of the acrylate or methacrylate type behaves in the same way as an alkyloerylate or an alkyl methacrylate.

909882/1633

1331452

acrylate. An antioxidant monomer of the fumarate type behaves also similar to an alkyl fumarate in a copolymerization. Comonomers that are used in co-polymerization with acrylates, meth- / acrylates, s'lryroles, fumarates and itaconates can be used ^ are known to the person skilled in the art and, for example, in detail by O.E. Schildknecht in "Vinyl and Related Polymers" (John Wiley & Sons, New York, 1952). . -

When using acrylate and methacrylate antioxidant monomers Bind the preferred comonomers to alkyl (1 to 24 carbon atoms) acrylates and methacrylates, styrenes, vinyl esters, butadiene and isoprene are essentially chlorinated or fluorinated derivatives daA ^ on. When using Pumarat and. Itaconate and related Diester antioxidant monomers are the preferred comonomers Vinyl ethers, vinyl esters, fv-olefins, styrenes and. H-vinyl monomers.

In the following table V i ^ t the production of alternating copolymers:? sowing a representative sample of comonomers with antioxidant fumarates or ilaleateh explained. The polymerization is carried out using equimolar! ■ steer the lionomers, which are dissolved in equal amounts of chloroform and polymerized using 2 # 2,2'-azo-bis-isobutyronitrile. The polymerization is carried out at a temperature of BO ⁰ C for 16 hours under nitrogen.

BATH
909882/16 3 3

TABEL

co co OO OO to

Antioxidant Monomer

Comonomeric thermal
Differential Analysis Appearance Te: ( ⁰ G) Tm. ( ⁰ G)

Elemental analysis

BI β {2- [3- (3,5-dimethylethylt ert. -butyl ^ -hydroxy- ether phenyl) -propionyloxy] -

ethyl fumarate

n-Butyl-2- [3- (3,5-di-vinyl acetate ■ teTt. - ■ butyl-4-hydroxy-oxyhenyl) -propionyloxy-propyl maleate yellowish +30 to
Powder 37

white,
sticky polymer

+ 5G

C 69.02 H 8.50

C 66.64 H 8.82

69, '14 8.67

66.21 B,

co co to

Methyl vinyl ether white, +29

crumbly

Polymer

+69

67.85 8.82

68.61 8.63

The elemental analysis is calculated for an alternating 1: 1 copolymer.

_ - 26 -

The copolymerization of representative antioxidant honeyomers with styrene is illustrated in Table VI below. In this : Copolymerization 10% by weight of the antioxidant monomer and 90% styrene ground in twice the amount of Benaol (using the "first two monomers in Table VI below) or chloroform (using the last two monomers Table VI below) dissolved Di "polymerization is in the presence of 2 $ 2,2'-Az;.. o-bis-i durchgeführt- sobutyronitril and at a temperature of 80 ⁰ C for 16 hours under nitrogen, then the polymer solution is with Chloroform diluted to a 10% strength by weight solution and precipitated in 20 times the amount of methanol. The precipitated polymer is filtered and dried under high vacuum. The yields vary between 91 and 95% by weight. All polymers are white, crumbly Powder.

T A B E L L E VI

; Antioxidant Monomer ίi ^ i

Styrene l

5,5-di-tert-butyl-4-hydroxyphenyl crotonate 10.2

3,5-di-tert-butyl-4-hydroxyphenyl cinnamate 11.3

Bis (3,5-di-tert-butyl-4-hydroxyphenyl) fumarate 13.9

Bis- (3,5-di-tert-butyl-4-hydroxyphenyl) itaconate 14.5

89.8 88.2

86, p

85.4-

Mol elcu lar gev / i cht (determined by osmometry)

12 080

14 300

15 600

16 700

Most polymers are oxidized at ambient temperatures so slowly, even in the absence of antioxidants, that

909882/1633

8ADORJGtNAL

the study of the effects of the antioxidants must be carried out at high temperatures in order to obtain results within a reasonable time. The. with those listed in the following tables materials were tests conducted in a tube furnace with an air flow of 400 1 per minute conducted at a furnace temperature of 150 ⁰ C. The aging time in the oven is given in hours. The term "failure" indicates the first sign of polymer degradation.

To prepare the test sample, unstabilized polypropylene powder is carefully mixed with the specified polymeric antioxidant. The mixed material is then on. sheeted on a two roll mill at a temperature of 132 ⁰ C for 6 minutes, then the stabilized polypropylene in the form of a film from the mill is removed and allowed to cool. The rolled polypropylene film that has been stabilized is then cut into small pieces and pressed for 7 minutes on a hydraulic press at 218 ° C and a pressure of 12.3 kg / cm (174 psl). The resulting 0.0635 cm (25 mil) thick film is then tested for resistance to accelerated aging in the oven described above.

909882/1633

Oven aging strength of PoXypropylene films with an inner board of 0.0635 cw (25 mil), the different thickness nolvifiere wrid'.olipoinpre Ant-5 contain oxidants. ·

Pnlyrnerinte

with honey molecular

to

, 25 "< Anti $ 0.1 antioxidant

(ο

'»■■. ■' ■■. *" "

po?, 5-di-tert .-- 'biityl-4-

'fo · hvdroTynhenyl-raethacrylat

Ca »

yyyXy) -J-! thylmei-hacryl.at , '"

2- Γ 3- ( τ> 5-di.-Tert-butyl-4-

2-r>(>5; «5
hy (1 fn * xryoli
• nropyl-aoryT at

JT- ¹⁷ J, 5 ~ Mt ert. - "butyl-4-

y i onyloxy] -

25th
¹ <S ■ 1B

145

4B5 120

260 270

Oligomers ^^ (pentamers)

0, 2 * & Anti o: cvflans

525

790

595 140

O, Vf antioxidant. + 0.3 ^ DSTDP

1075

633

1240

950 260

Where in the above oven aging test no antioxidant added to that Polypropylene is added, the time to failure is less than 5 hours.

^ The synthesis of high molecular weight polymers is described in Table III above. -

^ The antioxidant monomers and n-dodecyl mercaptan listed in the table above in a molar ratio of 5: 1 and 1 wt .- $ 2.2 ^! -Azo-bis-isobutyronitrile (based on the monomer) v / ground in twice the amount of chloroform, dissolved and melted under nitrogen. 16-fold stündlger polymerization at 80 ⁰ C the solvent is evaporated and the oligoraere antioxidant is dried under Hochvalaram. In all examples the yield is quantitative, ie about $ 100.

^ Distearyl thiodipropionate.

The following Table YIII gives the results of oven aging tests on polypropylene films 0.0635 cm (25 mils) thick containing oligomers made with various mercaptans of 2- [3 ~ (3,5-di-tert-butyl- 4-hydroxyphenyl J-propionjrloxy] ethyl methacrylate., The method used comprises dissolving a mixture of the above monomer and the mercaptan (mixed in the molar ratios given in Table VIII) and 1 wt .- ^ 2.2 ^f azo-bis-isobutyronitrile (based on the monomers) in three times the amount of benzene and melting down under nitrogen. Hach 16 hours of polymerization at 70 ⁰ C the solvent is evaporated, and the oligomeric antioxidant is dried under high vacuum. the yields are in in all cases quantitative, ie 100 ^.

909882/1633

. I A B 'τ? LI, E VIII

Mercaptan appearance §ilI2-SS_] 2i2_ ^ HIB ~ Y £? £ 2. £: §S_

(Mol / Hol Honoraeres) o ?? «- onr- _P n ° ' ²⁵ ''^ * ¹ "°' ¹ ^ ^Αη ^ ° * ^ -

u ± i. _: omexen _OXV cUms + 0.Ts T) Sl ¹ DP

n-octyl mercaptan. . _ ...

"(0,4) 'ses Polyra. 970' 1435

white n-octylmeroaptan,

(0.2 j weak 800 1325 ■ ■ ■■. Sticky

Polymer

n-dodecyl mercaptan hoohvisko-

(0,4) "ses oil 845 1315

n-Dodec ^ imercaptan white, ■ -

(0,2) "■. ■ weak 790 ^ 124-0

. sticky -

. Polymer

n-Hexadecy] .mercaT »tan highly viscous

(0,4) ses oil 1040 1215

n-Hexadecvlmerca-otan v / eisses,

(0.2) sticky 725 1225

Polymer

Where in the above oven aging test no antioxidant added to that Polypropylene is added, the time to failure is less than 5 hours.

In the following table IX the brgebnips of the under Use of copolymer seeds of 2- [3- (3v5-M-tert-biityl-4-hydroxyphenyl) propionyloxy] ethyl methacrylate and various OoEionomers specified oven aging tests carried out * The copolymers given in this table are used of the VftrtXhtfene given in Table VIII above produced, with the exception that 50% by weight of the monomer through the Coraono beers listed in Table IX below be replaced.

BADORiGlNAL

909 8 82/1633

T_ A_B_2_T._ Ti_lR IX

Comonoroeres Appearance of the Hour Mr ^ un Betrayed (50% by weight of the Oli ^ oraeren ö ~ ^ ~ "7 ~ 7 ~ T ~ 7 ^ ~ 7 ~~

no high viscosity,

colorless oil 845 1315

Methyl methacrylate colorless,

. sticky 450 435 polymer

n-octyl methaorylate colorless,

high viscosity 850 949 oil

n-dodecyl

methacrylate "1040-1075

n-octadecyl

rnethnorylat "995 1020

Styrene ir 430 830

1-vinylnaphthalene schvmch ^ eI-

bee, high- 83 558 viscous oil

N-Vinylcarba.ssöl rail chi ^ eP,

sticky '800 875 polymer.

In general, the 01ip; oaers themselves showed failure in the oven only a curdled color change / ?. However, if there is no anti ^ - oxydans sugeeeben, time to failure was never less than 5 hours.

In the following Table X the results of the tests with oligors of 3r5-di-tert.-butyl-4-hydrox? 7p ^nen " ^l ' ^r - ~ ^rae ^ ^{lac: r} y"' lat and n -Dod ^ cyl-nercaptan aiiriegen. The polymerization is carried out by adding a mixture of the above-mentioned monomer and n-dodr'cyl-mercaptan (in the molar ratios given in the table) and 1 wt. 2.2 ^l; -A?; O-bis-isobutvronitrile was dissolved in twice the amount of chloroform. ITacii the meltdown under nitrogen and after 16 hours of polymerization

909882/1633

BATH

7O ⁰ C the solvent is evaporated and the oligomer dried under high vacuum. The yields are quantitative.

TABLE X

Molar ratio Mole weight Appearance of the Hours to for sewing Mercaptan /
Monomer d. Anti
oxydans Oligomers 0.25 <£ anti $ 0.1 antiox. 1/2 793 white, high-
viscous oil 930 1270 1 / 2.5 925 white, sticky
riges poly
merisat 940 1600 ■ 1 / 3.3 1165 white,
solid poly
merisat 800 1415 1/5 1654 white,
crumbly
Polymer 525 1075 1/10 3106 white,
crumbles
Polymer 330 490

It was found -dans even after packaging in the oven no discoloration occurred. If no antioxidant has been used, the time to failure was less than 5 hours.

8ADORSGiNAL

909882/1633

Claims (7)

«3.H52 1. Process for the preparation of a polymeric antioxidant compound, that of an α, ß-unsaturated acid, which is at least contains a sterically hindered phenol group, contains derived monomer units, characterized in that / a) a monomer compound derived from an oc, ß- _{unsaturated, f} £ j acid which contains a sterically hindered phenol group and b) a free-radical initiator is selected from the group of a Azonitrils, an azo derivative, an aliphatic Acylperoxyds, a Ketonperoxyds Uend ^j a Aldehydperoxyds Subjected to polymerization conditions. 2. The method according to claim 1, characterized in that the monomer used is a "monomer from the group of esters, iDhioesters and amides of acrylic and methacrylic acid j der Ister, iDhioesters and amides of maleic, fumaric, orraconic and mesaconic acids; the imides of maleic and citraconic acids; the ester, thio- * esters and amides of itaconic acid; the esters, iDhioesters and amides of orotonic and cinnamic acid 1st. \; 3. The method according to claim 1, characterized in that the azonitrile used is 2.2 ^t -azo-bis-isobutyronitrile. 4. The method according to claim 1, characterized in that as aliphatic acyl peroxide iiauroyl peroxide or decanoyl peroxide oxide is used. . . ν 5. The method according to claim 1, characterized in that a gomonomer compound is added to the polymer aation reaction. j will. - ■ ■ 6.- The method according to claim 5, characterized in that, ss 'a / ls comonomer compound is a compound from the group of. ; 9Q98g2 / 1ß33 i - 34- 3931452 Alkyl acrylates and methacrylates, styrenes, vinylenter, butadiene and Iaoprenes and chlorinated and fluorinated derivatives thereof is used and that all monomers acrylates or methacrylates are used. 7. The method according to claim 1, characterized in that the polymerization in the presence of a chain transferring agent is carried out. 90 9 882/16 33 BATH