DE1264051B - Stabilization of polyolefins or styrene polymers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

C08f

German class: 39b ^ 22/04

Number: 1264 051

File number: G 32032IV c / 39 b

Filing date: April 11, 1961

Open date: March 21, 1968

The invention relates to stabilizing polyolefins, particularly polypropylene, as well Styrene polymers with the aid of substituted triazines.

The invention thus relates to the use of small amounts of a triazine compound of the following general formulas

N N

R ₃ -ZA _n ^) - YR ₂

(a)

(R ₁ and R ₂ are, independently of one another, alkyl, cycloalkyl, phenyl, alkylphenyl, alkylhydroxyphenyl, alkylhydroxybenzyl, cyanoalkyl, alkylmercaptoalkyl, carbalkoxyalkyl, carbalkoxyphenyl groups, R ₃ = hydroxyphenyl, alkylhydroxyphenyl or alkylhydroxyphenyl, phenylhydroxyphenyl groups , Y and Z are independent of one another - S -, - O-, a stabilization of polyolefins or styrene polymers

Applicant:

J. R. Geigy A. G., Basel (Switzerland)

Representative:

Dr. F. Zumstein, Dr. E. Assmann and Dr. R. Koenigsberger, patent attorneys, 8000 Munich 2, Bräuhausstr. 4th

Named as inventor:

Martin Dexter, White Plains, N.Y .; Martin Knell, Ossining, N. Y .; Eric A. Roskin, Bronx, N.Y. (V. St. A.)

Claimed priority:

V. St. v. America of April 12, 1960 (21 604), of August 3, 1960 (47 159), dated February 21, 1961 (87 520)

- N - benzyl, - Ν -
lower alkyl

or - NH - group)

Cl

R ₅

30 alkyl radicals with 1 to 18 carbon atoms) or

R12
X

N N

N N

^3S

_14th

(R ₅ = a hydroxyphenylamino, alkylhydroxyphenylamino, or alkylmercapto and R ₆ = an alkylhydroxyphenylamino group)

C = O

(R ₁₂ and R ₁₃ are independently alkyl groups with 1 to 18 carbon atoms, R ₁₄ = an alkyl hydroxyphenyl group, R = an alkyl group and X and Y are independently - S -, - O -,

45 one

N N

N N

(c)

R ₉

₅ o - N - benzyl, - Ν - lower alkyl

or - NH - group) to stabilize polyolefins or styrene poly-

(R ₈ , R ₉ , R ₁₀ and R ₁₁ are, independently of one another, merizates against oxidation.

809 519/708

3 4

Stabilizers of the formula a) are, for example, substance atoms, the hydroxyphenyl or the phenyl compounds of the formula given denote hydroxyphenyl radical.

Another valuable subclass of Stabilisato-Ri Ren of the formula a) includes triazines of the formula

I 5

/ \ ο

NN

wherein R ₁ and R ₂ are independently ³ ^ N ^ ²

Alkyl radical with 1 to 18 carbon atoms, one

Cycloalkyl radical with 5 to 6 carbon atoms, a 15 in which R ₁ and R ₂ independently of one another the phenyl-alkylphenyl radical with 7 to 24 carbon atoms, radical or an alkylhydroxyphenyl radical with 7 to

z. B. a methylphenyl, dimethylphenyl, ethyl 24 carbon atoms and R _{3 is} an alkylhydroxyphenyl, propylphenyl, butylphenyl, dibutylphenyl, phenyl radical with 7 to 24 carbon atoms.

Dioctylphenyl, Octadecylphenylgruppe, an alkyl group Another valuable subclass of stabilizers

Hydroxyphenyl with preferably 7 to 24 carbon gates of the formula a) includes the dioxy-substituted atoms or alkylhydroxybenzyl radical with 8 to 25 carbon triazines of the formula lenstoffatomen, z. B. a methyl substituted hydroxy

benzyl-, ethyl-substituted hydroxybenzyl-, dimethyl- R ₁

substituted hydroxybenzyl-, butyl-substituted Hy- |

droxybenzyl-, dibutyl-substituted hydroxybenzyl-25 O

group, a cyanoalkyl radical with 2 to 7 carbon I

atoms, e.g. B. a cyanomethyl, cyanoethyl, cyan

propyl, cyanobutyl, cyanhexyl group, an alkyl N N

mercaptoalkyl radical with 2 to 10 carbon atoms, _{R ς} [IJ _n "

z. B. a methylthiomethyl, ethylthiomethyl, octyl 30 ³ ~~ ^ N ^ ~ ^{υ Ka}

thioethyl group, a carbalkoxyalkyl radical with 3 to

15 carbon atoms, e.g. B. a Carbomethoxyme- in which R ₁ and R _{2 are} independently a ethyl, Carbäthoxymethyl-, Carbäthoxyäthyl, Carbo- Alkylhydroxyphenylrest with 7 to 24 carbon butoxymethyl, Carbobutoxyäthyl, Carbolauryloxy- atoms and R _{3 is} an alkyl radical with 1 to 18 carbon methyl groups, or a carbalkoxyphenyl radical with 35 material atoms.

8 to 19 carbon atoms, e.g. B. a carbomethoxy- Finally, one last valuable sub-

phenyl, carbobutoxyphenyl, carbolauryloxyphenyl class of stabilizers of the formula a) triazine group, an alkylhydroxyphenyl radical having 7 to compounds of the formula 24 carbon atoms, e.g. B. a'Methylhydroxyphe-

nyl-, dimethylhydroxyphenyl-, ethylhydroxyphenyl-, 4 ° R ₁

Butylhydroxyphenyl, dibutylhydroxyphenyl, octyl |

hydroxyphenyl, octadecyl hydroxyphenyl, or
denote an alkylhydroxybenzyl radical with 8 to 25 carbon atoms and X, Y and Z as under formula a)
are defined. 45 NN

A particularly valuable subclass of Stabilisa- "q | J ς, "

gates of the formula a) includes the dithio-substituted ³ ^ N ^ ²

Triazines of the formula

wherein R ₁ and R ₂ independently of one another are an alkyl

R ₁ 50 radical with 1 to 18 carbon atoms or one

I alkyl mercaptoalkyl radical with 2 to 10 carbon

atoms and R ₃ denotes the hydroxyphenyl radical or an alkylhydroxyphenyl radical having 7 to 24 carbon atoms.

NN 55 stabilizers of the formula b) are for example

ρ _XT TT Il I _c r, compounds of the formula given

^Λ 3 ^iNrl V [Sj ' ¹ ^ ^ 2

Cl

wherein R ₁ and R ₂ independently of one another are one

Alkyl radical with 1 to 18 carbon atoms, a 60 / V.

Cycloalkyl radical with 5 to 6 carbon atoms, an N N

Alkylphenyl radical with 7 to 24 carbon atoms, _ || J "

the phenyl radical, a cyanoalkyl radical with 2 to 7 Koh- ^ ~ ^^^ ~~ ^K 5

lenstoffatomen, an alkyl mercaptoalkyl radical with 2 to

10 carbon atoms, a carbalkoxyalkyl radical with 65 in which R _{5 is} an alkylhydroxyphenylamino radical with 7 3 to 15 carbon atoms or a carbalkoxy radical with up to 24 carbon atoms, e.g. B. a methylhydroxyphenyl radical with 8 to 19 carbon atoms and phenylamino, ethylhydroxyphenylamino, propyl R ₃ an alkylhydroxyphenyl radical with 7 to 24 carbons hydroxyphenylamino, butylhydroxyphenylamino,

Octylhydroxyphenylamino, octadecylhydroxyphenylamino, dimethylhydroxyphenylamino, dibutylhydroxyphenylamino, or an alkyl mercapto radical with 1 to 18 carbon atoms, ζ. Β. a methyl mercapto, ethyl mercapto, propyl mercapto, butyl mercapto, octyl mercapto, dodecyl mercapto, octadecyl mercapto group, and R _{6 is} an alkyl hydroxyphenylamino radical having 7 to 24 carbon atoms, e.g. B. a methylhydroxyphenylamino ^ ethylhydroxyphenylamino, propylhydroxyphenylamino, butyl ίο hydroxyphenylamino, octylhydroxyphenylamino, octadecylhydroxyphenylamino, dimethylhydroxyphenylamino, dibutylhydroxyphenylamino, mean.

Stabilizers of the formula c) are, for example, compounds of the formula given

Rn-S-

N _v 0v /

^s "

N N

N N

20th

SR ₉

wherein R ₈ , R ₉ , R ₁₀ and R ₁₁ independently of one another, for. B. mean a methyl, ethyl, propyl, butyl, octyl, dodecyl, octadecyl group.

Stabilizers of the formula) are, for example, compounds of the formula given

N N

- N-

Y-R

■ 13

35

40

wherein R ₁₂ and R ₁₃ independently of one another, for. B. a methyl, ethyl, propyl, butyl, octyl, dodecyl, octadecyl group, R _{14 is} an alkyl hydroxyphenyl radical having 7 to 24 carbon atoms, e.g. B. a methylhydroxyphenyl, ethylhydroxyphenyl, propylhydroxyphenyl, butylhydroxyphenyl, octylhydroxyphenyl, dodecylhydroxyphenyl, octadecylhydroxyphenyl, dimethylhydroxyphenyl, dibutylhydroxyphenyl, dibutylhydroxyphenyl, one carbon, 1 bis. B. a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl, decyl, undecyl group, and X and Y are as defined under formula d), but preferably - S - mean.

Examples of compounds which can be used in the present invention are the following called:

6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bis- (ethylthio) -l, 3,5-triazine, F. 89 or 90 ⁰ C;

6- (4-Hydroxy-3,5-di-t-butylanilino) -2,4-bis (cyclohexylthio) -1, 3,5-triazine, M.p. 171 to 172 ° C;

6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bis (octadecylthio) -l, 3,5-triazine, F. 86 to 88 ⁰ C;

65 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bis-

(p-t-butylphenylthio) -1, 3,5-triazine, m.p. 87 ° C; 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bis-

(t-butylthio) -1, 3,5-triazine, mp 169-170 ° C; 4,6-bis- (4-hydroxy-3,5-di-t-butylanilino-

2-n-octylthio-1,3,5-triazine, F.95 to 100 ⁰ C; 4,6-bis- (4-hydroxy-3,5-di-t-butylanilino) -2-chloro-

1,3,5-triazine, m.p. 304 ^° C;
6- (4-hydroxy-3,5-di-t-butylanilino) -4-n-octyl-

thio-2-chloro-1,3,5-triazine, m.p. 119 to 12O ⁰ C; 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bis-

(anilino) -1,3,5-triazine, m.p. 192 to 194 ° C; 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bis-

(n-octylamino) -1, 3,5-triazine, mp 42-45 ° C; 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bis-

(phenoxy) -1,3,5-triazine, mp 160 to 161 ° C; 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bis-

(ethoxy) -l, 3,5-triazine, F. 54 ⁰ C; 2,4,6-tris (4-hydroxy-3,5-di-t-butylbenzylthio) -

1,3,5-triazine, m.p. 96 to 98 ° C; 6- (2-Hydroxy-3-t-butyl-5-methylanilino) -2,4-bis-

(n-octylthio) -1,3,5-triazine, viscous; 6- (4-hydroxy-3,5-di-isopropylanilino) -2,4-bis-

(n-octylthio) -1, 3,5-triazine, viscous; 6- (4-Hydroxy-3-methyl-5-t-butylanilino) -2,4-bis-

(n-octylthio) -1, 3,5-triazine, viscous; 6- (4-hydroxyanilino) -2,4-bis- (n-octylthio) -

1,3,5-triazine, m.p. 62 to 63 ° C; 6- (4-hydroxy-3,5-dimethylanilino) -2,4-bis-

(n-octylthio) -1, 3,5-triazine, mp 70 to 71 ° C; 6- (4-Hydroxy-3,5-di-t-butylanilino) -2,4-bis (n-octylthioethylthio) -1, 3,5-triazine, F. 67

up to 69 ° C;
6- (4-hydroxy-3,5-di-t-butyl-N-benzylanilino) -

2,4-bis (n-octylthio) -1,3,5-triazine, mp 36 ° C; 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bis-

(cyanoethylthio) -l, 3,5-triazine, mp 100 to 103 ° C; 6- (4-Hydroxy-3,5-di-t-butylanilino) -2,4-bis- (4-t-butylphenoxy) -1, 3,5-triazine, F. 119

up to 121 ° C;
6- (4-Hydroxy-3,5-di-t-butylanilino) -2,4-bis- (4-t-octylphenoxy) -1,3,5-triazine, m.p. 99 bis

101 ° C;
6- (4-Hydroxy-3,5-di-t-butylanilino) -2,4-bis (carbo-n-dodecyloxyethylthio) -1, 3,5-triazine,

viscous;
6- (4-Hydroxy-3,5-di-t-butylanilino) -2,4-bis- (carbo-n-decyloxymethylthio) -1, 3,5-triazine,

viscous;
6- (4-Hydroxy-3,5-di-t-butylanilino) -2,4-bis- (carbo-n-decyloxyethylthio) -l, 3,5-triazine,

viscous;
6- (4-Hydroxy-3,5-di-t-butylanilino) -2,4-bis- (carbo-n-dodecyloxymethylthio) -1,3,5-triazine,

viscous;
6- (4-Hydroxy-3,5-di-t-butylanilino) -2,4-bis- (2-carbo-n-lauryloxyphenylthio) -1,3,5-triazine,

viscous;
6- (4-hydroxy-5-methylanilino) -2,4-bis (n-octyl-

thio) -l, 3,5-triazine, m.p. 67 to 68 ⁰ C; 6- (2-hydroxy-5-methylanilino) -2,4-bis (n-octyl-

thio) -l, 3,5-triazine, m.p. 99 to 101 ⁰ C; 6- (3-hydroxyanilino) -2,4-bis (n-octylthio) -

1,3,5-triazine, m.p. 55 to 57 ° C; 6- (4-Hydroxy-N-methylanilino) -2,4-bis (n-octyl-

thio) -1, 3,5-triazine, m.p. 55 to 57 ° G; 6- (2-hydroxyanilino) -2,4-bis- (n-octylthio) -1,3,5-triazine, 103 ° C .;

6- (4-Hydroxy-5-t-butylanilino) -2.4-bis (n-octyl- ■ thio) -1, 3,5-triazine, m.p. 75 "C;
6- (4-hydroxy-2,6-dimethylanilino) -2,4-bis-

(n-octylthio) -1,3,5-triazine, mp 122 to 123 ° C; 6- (2-hydroxy-3,5-di-t-butylanilino) -2,4-bis-

(n-octylthio) -1, 3,5-triazine, mp 74 ° C; 6- (2-Hydroxy-3,5-di-t-butyl-6-methylanilino) -

2,4-bis (n-octylthio) -1,3,5-triazine, viscous; 6- (2-Hydroxy-5-t-butylanilino) -2,4-bis- (n-octyl-

thio) -1, 3,5-triazine, m.p. 101 ⁰ C; 6- (4-hydroxy-3,5-di-t-butylphenylthio) -2,4-bis-

(n-octylthio) -1, 3,5-triazine, viscous; 6- (4-hydroxy-3,5-dimethylphenylthio) -2,4-bis-

(n-octylthio) -1, 3,5-triazine, viscous; 6- (4-Hydroxy-3,5-di-t-butylanilino) -2,4-bis- (2,3-dimethylphenylthio) -1, 3,5-triazine,

viscous;
6- (4-hydroxy-3,5-di-t-butylphenoxy) -2,4-bis-

(n-octylthio) -1, 3,5-triazine, viscous; 1,4-phenylene-bis- [2-oxy-4,6-bis- (n-octylthio) -

1,3,5-triazine], m.p. 98 ° C;
6- (4-hydroxyphenoxy) -2,4-bis (n-octylthio) -

1,3,5-triazine, m.p. 79 to 80 ^° C; 6- (4-hydroxy-3,5-di-t-butylbenzylthio) -

1,3,5-triazine, viscous;
4,6-bis (4-hydroxy-3,5-di-t-butylphenoxy) -

2- (n-octylthio) -1, 3,5-triazine, mp 133-135 ° C; 2,4-bis (4-hydroxy-3-t-butylphenoxy) -

6- (n-octylthio) -1, 3,5-triazine, viscous; 6- (4-Hydroxy-3,5-di-t-butylanilino) -2- (n-octylthio) -4- (phenylthio) -1, 3,5-triazine, F. 83

up to 85 ° C;
6- (4-hydroxy-3,5-di-t-butylanilino) -2- (n-octylthio) -4- (4-hydroxy-3,5-di-t-butylphenoxy) -

1,3,5-triazine, m.p. 182-183 ° C; 6- (4-hydroxy-3,5-di-t-butylphenoxy) -2,4-bis-

(phenoxy) -1,3,5-triazine, mp 145 to 147 ° C; 2,4,6-tris (4-hydroxy-3,5-di-t-butylphenoxy) -

1,3,5-triazine, m.p. 298 ° C;
2,4,6-tris (4-hydroxy-3-t-butylphenoxy) -

1,3,5-triazine, m.p. 130 ^° C;
6- (4-hydroxy-3,5-di-t-butylphenoxy) -2,4-bis-

(n-octylthioäthylthio) -1, 3,5-triazine, viscous; 6- (N-acetyl-4-hydroxy-3,5-di-t-butylanilino) -2,4-bis- (n-octylthio) -1,3,5-triazine, viscous.

To date, the use of the specified substituted triazines for stabilizing polymers, such as B. polypropylene, not known, surprisingly has now been found that polyolefins against oxidative decomposition by incorporating a of the substituted triazines defined above are very well stabilized.

From the laid out documents of the Belgian patents 563 210 and 583 316 are triazole stabilizers known for polyolefins. The benzotriazole compounds described there are however, they are typical UV absorbers, i.e. stabilizers against light and not against oxidation. These compounds are ineffective as antioxidants for polyolefins and therefore because of them different effect not comparable with the stabilizers used according to the invention.

According to the invention, polyolefins, such as. B. polyethylene, polypropylene, but also polystyrene, as well as mixed polymers of butadiene and styrene. The polyolefins are said to be beneficial have a high molecular weight, say from one thousand to the hundred thousand. That for them The most suitable stabilization polymer is polypropylene.

The triazine stabilizers used according to the invention are based on known methods from cyanuric chloride.

The following example illustrates the invention. The parts therein mean parts by weight, and the Temperatures are given in degrees Celsius.

example

Unstabilized powdered, isotactic polypropylene with a molecular weight of approximately 300,000, the specific gravity of 0.905 and a crystal melting point of 167 °, is 0.5 weight percent 6 - (4 - Hydroxy -3,5-di-t-butylanilino) -2,4-bis (n-octylthio) -1, 3,5-triazine (mp 92 to 95 °) intimately mixed. The mixture is then ground on a two-roll mill at 182 ° for 10 minutes and then pulled out into a foil.

The stabilized polypropylene film is cut into small pieces and placed in a hydraulic press pressed at 218 ° and at a pressure of about 140 atmospheres. The 0.60 mm thick film is now at 149 ° Tested for resistance in an air-circulating oven that accelerates aging. That stabilized After a treatment in the oven for 370 hours, polypropylene still shows no signs of aging; on the other hand, an unstabilized blank made of polypropylene is among the same Conditions changed significantly after just 3 hours. Stable polypropylene blends are also produced in the same way obtained with the aid of 0.5 percent by weight of one of the compounds listed below. This can be seen from the following figures, which in the aging test described above, the time measured by eye-visible decomposition.

4,6-bis- (4-hydroxy-3,5-di-t-butylphenoxy) -2- (n-octylthio) -1,3,5-triazine (F. 133 °):

270 hours;

6- (4-Hydroxy-3,5-di-t-butylphenoxy) -2,4-bis- (n-octylthioethylthio) -1,3,5-triazine

(resinous oil): 1100 hours; 6- (4-Hydroxy-3,5-di-t-butylanilino) -2-chloro-4-n-octylthio-1,3,5-triazine (F. 119 to 120 °):

205 hours;
4,6-bis- (4-hydroxy-3,5-di-t-butylanilino) -2-chloro-

1,3,5-triazine (mp 304 °): 350 hours; 1,4-phenylene-bis- [2-hydroxy-4,6-bis- (n-octyl-

thio) -1, 3,5-triazine] (m.p. 98 °): 130 hours; 6- (4-Hydroxy-3,5-di-t-butylanilino-N-acetyl) -2,4-bis (n-octylthio) -1,3,5-triazine

(F. 0.05: 130 °): 395 hours.

Likewise, the connections listed can be made by rolling for 10 minutes at 121 to 127 ° in amounts of 0.1 percent by weight of low-density polyethylene be incorporated. The resulting mixtures are stable to oxidative decomposition. In the same way, the compounds listed can also be produced by rolling at 155 ° in quantities of

0.1 percent by weight of a high-impact styrene-butadiene copolymer be incorporated. The resulting products are also stable to oxidative decomposition.

Claims (1)

Claim: Using small amounts of a triazine compound represented by the following general formulas N N IO Z \ - ^ 7 Y R-2 (a) (R ₁ and R ₂ are independently alkyl, cycloalkyl, phenyl, alkylphenyl, alkylhydroxyphenyl, alkylhydroxybenzyl, cyanoalkyl, alkylmercaptoalkyl, carbalkoxyalkyl, carbalkoxyphenyl groups, R ₃ = hydroxyphenyl, alkylhydroxyphenyl, phenylhydroxyphenyl or Alkylhydroxybenzyl radicals and X, Y and Z are, independently of one another, - S -, - O - ·, one - N — benzyl, - Ν - lower alkyl or - NH - group) Cl N N (b) 35 (R ₅ = a hydroxyphenylamino, alkylhydroxyphenylamino, or alkyl mercapto and R ₆ = a 10 Alkyl hydroxyphenylamino group) N N N N 10 SR ₉ (R ₈ , R ₉ , R ₁₀ and R ₁₁ are, independently of one another, alkyl radicals having 1 to 18 carbon atoms) or Rl ₂ N N (d) R ₁₄ -N ^ _N ^ YR ₁₃ C = O (R ₁₂ and R ₁₃ are, independently of one another, alkyl groups with 1 to 18 carbon atoms, R ₁₄ = an alkyl hydroxyphenyl group, R = an alkyl group and X and Y, independently of one another, are —S—, —O—, a - N - benzyl, - Ν -
lower alkyl or - NH - group) to stabilize polyolefins or styrene polymers against oxidation. Considered publications:
Documentation of Belgian patents nos. 563 210, 583 316. 809 519/701 3.6t O Bundesdruckerei Berlin