DE2107457C3 - Peroxides with condensed arylcycloalkane rings and their use for vulcanizing elastomers - Google Patents

Description

wherein R is a tert-butyl radical or a cumyl radical, R 'represents a hydrogen atom or a teri.-butylperoxy radical nO or 1 mean.

2. Use of the peroxides according to claim 1 for vulcanizing elastomers.

The invention relates to new peroxides with condensed aryl-cycloalkane rings of the general formulas

C OOR C

Ul H

where R is a tert-Uulylrcst or a Ciimylrcst, R 'is a hydrogen atom or a tert-Butylperoxyrest and η O or 1 and the use of these peroxides for vulcanizing elastomers,
Organic compounds with a peroxidic nature are particularly important as generators of free radicals and are therefore well suited as initiators for

Radical polymerizations, crosslinking agents for plasto-

mers and vulcanizing agents for elastomers.

Thus, in GB-PS 10 49 969 organic

ίο tetraperoxides, such as B. l, l, 4,4-tetra- (tert-butylperoxy) -cydohexane described, in vulcanizable mixtures with an Olefinpoiymeren or one saturated copolymers of ethylene with an olefin and a filler are useful. Such Mixtures have a high vulcanization rate and are against the negative influence of Fillers, especially those based on carbon black, are comparatively insensitive.

The organic peroxides according to the invention draw

good resistance and low volatility at temperatures higher than room temperature and are consequently used both as vulcanizing agents for elastomers and as Crosslinking agents for plastomers can be used well. As has been found, these peroxides are both that known dicumyl peroxide as well as the peroxides known from GB-PS 1049 969 are superior. Like attempts showed, provide the peroxides according to the invention, compared with the known peroxides, Vulkanisa-

jo tion products with better physical properties.

Examples of compounds according to the invention which correspond to the above formulas are:

2 £ -di (teit-butylperoxy) indane

1,1-di- (tert-butylperoxy) indane

1,133-tetra (tert-butyIperoxy) indane

2,2-di (cumyIperoxy) indane

1,1 -Di- (terL-butylperoxy) -1,2,3,4- tetra-

hydronaphthalene
2 ^ -Di- (tert-butylperoxy) -1,2,3,4-tetra-

hydronaphthalene
2,2-di- (cumylperoxy) -l, 2,3,4-tetra-

hydronaphthalene

1-tert-butylperoxy-1 »cumylperoxyindane
2-tert-butylperoxy-2-cumylperoxyindane

The peroxides or peroxyketals according to the invention have a relatively high decomposition temperature with good resistance and low volatility at temperatures higher than room temperature, on. As a result of these properties, they can be used well in saturated elastomers as well as vulcanizing agents as well as in plastomers as crosslinking agents in a homogeneous manner and without the occurrence of unpleasant Incorporate side effects.

The peroxyketals according to the invention can be prepared in a manner known per se.

In the preferred embodiment, the peroxyketals according to the invention are prepared by reacting a cycloaliphatic ketone having 5 or 6 carbon atoms fw = O or n = 1 in the general formulas), which is condensed with a benzene ring and dissolved in a suitable solvent, with an organic one hydroperoxide in the presence of a dehydrating agent and, if necessary, acting. in the presence of an acid catalyst at temperatures between -40 and +70, preferably -20 and +40 ⁰ C.

Examples of carbonyl compounds for the purpose of producing the peroxides according to the invention are suitable are:

Indanone-1

Indanone-2

lndandion-1.3

Tetralone-l (or l-oxo-1,23,4-tetra-

hydronaphthalene)
TetraIon-2 (or 2-oxo-l3,4-tetra-

hydronaphthalene)

The hydroperoxides that can be used for the conversion to the peroxides according to the invention, consist of monohydroperoxides and dihydroperoxides.

Examples of such connections are:
tert-butyl hydroperoxide and cumyl hydroperoxide.

The solvents that can be used in the reaction can be selected from linear aliphatic, cycloaliphatic and aromatic hydrocarbons exist, which may also be halogen-substituted could be.

The molar ratio of carbonyl compound to hydroperoxide should be between 1: 2 and 1:10, preferably between 1:22 and 1: 3.

Particularly suitable catalysts are those with a strongly acidic nature, such as HCL and H2SO

The peroxyketals according to the invention are chlorinated and non-chlorinated aliphatic and aromatic hydrogens soluble. In the cold they point in Alcohols and other solvents only a small amount Solubility on.

The inventive 'peroxides act as excellent Vulcanizing agents for saturated elastomers, as crosslinking agents for plastomers and as initiators for radical polymerizations.

The vulcanization can take place at temperatures between 140 and 190 ° C, preferably between 150 and 170 ° C Spans of 5 to 200 minutes, preferably 5 and 15 minutes, can be carried out when one Ethylene-propylene copolymer used The concentration of the peroxide should be 0.5 to 10, preferably 2 to 5 wt .-%, based on the weight of the Elastomers. A particularly useful approach to vulcanizing an ethylene-propylene copolymer has the following composition, for example:

Ethylene-propylene copolymer

(Molar ratio 1: 1)

Soot HAF

ZnO (or MgO)

sulfur

peroxide

100 parts
20-80 parts
1-10 parts
0.15-0.5 parts 0.005-0.02 MoI.

Among the most notable advantages of using the peroxides according to the invention when Vulcanization of saturated elastomers and the crosslinking of plastics results in the following:

1) short vulcanization time and low vulcanization temperature

2) the absence of "blooming"

3) the fact that the greater effectiveness of the peroxides according to the invention also in the presence of fillers, reinforcing agents, additives, additionally used agents, plasticizers, Pigments and antioxidants of the generally known kind remain unchanged.

The following examples serve to further illustrate the invention:

example 1
5

20 cm ³ of n-hexane, 60 cm ³ benzene, 2R g indanone 2 and 10 g of ground calcium chloride were placed in a flask equipped with a stirrer, the mixture was abgekünlt with stirring to 0 ⁰ C, and then in the course of 5 minutes 80 g 73% sodium tert-butyl hydroperoxide are added the temperature rose during the addition to 5 to 6 ⁰ C, was then decreased again to 0 ⁰ C, then, over the course of 12 minutes dropwise 8 cm ³

55% HCl added. The temperature rose again to 3 to 5 ° C. during the addition. The mix was Stirred for 5 hours. After this time, 50 g of water and ice were added, whereupon 2 phases were formed farewell.

The organic phase was washed with water, then with aqueous 5% NaOH and then again with water. Then the organic phase over anhydrous magnesium sulfate, was dried and then filtered The solvent was evaporated under vacuum at 40 ⁰ C so that a residue of 4WG remained. Recrystallization from 100 cm * methanol gave 39 g of a white crystalline product which could be identified as 2,2-di- (tert-butylperoxy) -indane. This product had the following characteristics:

Melting point 43-45-C Decomposition temperature 110 ⁰ C Half-life at 118 ° C 30 minutes active oxygen 10.84% Iodine number 99.85% Carbon content found 69.2% calculated 69.4% Hydrogen content found 83% calculated 8.85%

Example 2

20 g of n-hexane, 50 cm ^{3 of} benzene, 10 g of indanone-1 and 5 g of ground calcium chloride were placed in a flask equipped with a stirrer. The mixture was then ^{stirred at 0 °} C., 60 g of 77% strength tert-butyl hydroperoxide being added dropwise over the course of 5 minutes. After 10 minutes, 5 cm ^{3 of} 36% HCl were also added dropwise over the course of 10 minutes, care being taken that the temperature did not exceed +5 ° C. The mixture was then at a temperature between 0 and 5 ° C C. Stirred for 4 hours At the end of this period, the mixture was taken up with 50 ecm of cold water and the organic layer was washed first with water, then with aqueous 5% NaOH and finally again with water. The entire solution obtained in this way was dried _{over anhydrous MgSO 4} .. The solvent was evaporated mbar under vacuum at 30 to 35 ⁰ C at a final pressure of 0.2666 in this way, there was obtained 16.5 g of an oily liquid product containing as l, 1-di (tert-butylperoxyI) - indan could be identified. This product had the following characteristics:

Decomposition temperature
Half-life at 145 ° C
active oxygen
Iodine number
Carbon content

found

calculated
Hydrogen content

found

calculated

Example 3

40 cm ^{3 of} n-hexane, 25 cm ^{3 of} benzene, 10 g of tetralone-2 and 5 g of ground anhydrous calcium chloride were placed in a flask equipped with a stirrer. The mixture was then cooled to 0 ° C. with constant stirring over 10 minutes 30 g of 73% tert-butyl hydroperoxide were added dropwise. Then, while the temperature was maintained at 0 ° C., 5 cm ^{3 of} 36% HCl were introduced very slowly (over 15 minutes). The mixture was then introduced at 0 ° C. for 4 hours stirred, whereupon the organic phase was washed with water, then with 5% aqueous NaOH and finally again with water. After drying over anhydrous MgSQ4, the solution was evaporated in vacuo at 30 ° C. until a residual pressure of 03332 mbar had been established. The solvent was removed in this way. There remained 16.5 g of an oily residue which could be identified as 2,2-di (tert-butyI-peroxy) -l, 23,4-tetrahydronaphthalene. This product had the following characteristics:

21 130 ° C 07 457
6th Example 5 90 "C 30 minutes Decomposition temperature 30 minutes 8.50% Half-life at 105 ° C 7% 78.2% active oxygen 91.5% Iodine titer 68.8% 5 carbon content 76% 69.4% found 77.6% calculated 9.0% Hydrogen content 7.4% 8.85% found 7.2% ίο calculated

n '"' = 1.4880 Example 4 124 ° C d (20 ° C) = 037 30 minutes Decomposition temperature 9.08% Half-life at 130 ° C 873% active oxygen Iodine number 70.1% Carbon content 70.1% found calculated 9.1% Hydrogen content 9.1% found calculated

80 cm ^{3 of} n-hexane, 10 g of tetralone-1 and 5 g of ground calcium chloride were placed in a flask equipped with a stirrer. 50 g of 73% tert-butyl hydroperoxide were then added dropwise over 5 minutes at 0-5 ° C. While the mixture was kept at a temperature between 0 and 5 ° C., 8 cnr * 6% HCl was added over the course of 10 minutes. The mixture was then stirred at this temperature for 4 hours. The organic phase was then separated off , washed with water, with aqueous 5% NaOH and again with water. The organic solution was dried over anhydrous magnesium sulfate, then filtered and finally freed from solvent by up to a final vacuum of 0.266 mbar was distilled at 35-40 ⁰ C. In this way, 8 g of a yellow liquid remained as residue, which could be identified as 1,1-di- {tert-butylperoxy) -1,23,4-tetralin. This connection had the following characteristics:

no -1.4450 Example 6 125 ° C Decomposition temperature 30 minutes Half-life at 115 ° C 635% active oxygen 61.2% Iodine titer C content 69.4% found 70.1% calculated H content 9.2% found 9.1% calculated

30 cm ^{3 of} n-hexane, 20 cm ^{3 of} benzene, 5 g of indanone-2 and 5 g of ground anhydrous calcium chloride were placed in a flask equipped with a stirrer. Thereafter dropwise 60 g of 57% cumene hydroperoxide over 20 minutes at -2O ⁰ C was added in solution in hexane. The solution obtained in this way was then mixed with 5 drops of 36% HCl. The mixture was stirred at the same temperature for 2 hours. At the end of this time, the organic phase was separated from the mixture. The organic phase was washed with water, with aqueous 5% NaOH and again with water. The solution was then dried over anhydrous magnesium sulfate, filtered and freed from the solvent by evaporation at 25-30 ° C. to a final pressure of 036 mbar. In this way, 12 g of an oily liquid were obtained, which as 2,2-dicumyl-peroxy -indan could be identified. This connection wts the following characteristics:

50 cm ^{3 of} benzene, 5 g of indanedione-13 and 5 g of ground anhydrous calcium chloride were placed in a flask equipped with a stirrer. In the course of 10 minutes, 65 g of 78% tert-butyl hydroperoxide were added at 0 ° C. and - still at the same time Temperature - 5 cm ^{3 of} 36% HCl added. The mixture was stirred for 4 hours and 30 minutes at 0 ° C. The organic phase was then separated off and washed with water, aqueous 5% NaOH and again with water. The organic solution was dried over anhydrous magnesium sulfate, filtered and freed from the solvent by distilling in vacuo at 30-35 ° C. In this way, a pale yellow solid residue (i 13 g) was obtained which could be identified as i, 133-tetra- (tert-butylperoxy) indane. This connection had the following characteristics:

Decomposition -.> Ti ". Temperature
Half-life at 125 ° C
active oxygen

125 ° C

30 minutes

10.93%

Iodine titer

C-Gchalt
found
calculated

H-Hall
found
calculated

76.4%

64.7% 63.8%

8.4% 8.9%

Example 7

The curing tests were carried out with mixtures of an ethylene-propylene copolymer. In Table I are the vulcanization rates compiled, which were found on mixtures, which - except for the peroxide - the same Composition, the following peroxides were contained in the mixtures:

2.2 Di (tcrt.-butvlncroxylindan.

2.2- l) i (cii my I peroxy) indan,

1.1.3.3 -Tel ra- (tert-buty1pcro \ y) indan.

2.2-Di (tert-butylperoxy) -l.2.3.4-lelrahydronaphihalin.

r) icumylpcroxide (comparative compound) 1.14,4-Tctra- (terl-butylpcroxy) -cyclohcxane

(Comparison compound) and 2.2.5.5-Tctra- (tert-butylperoxy) -hexane (Comparison connection).

The vulcanization rate was measured at a constant temperature of 177 C in a Monsanto TM-IO rheometer determined.

The mixtures used had the following compositions on:

Ethylene propylene -Copolymer 100 parts (Molar ratio I: I) 50 parts HAP-RuB 3 parts ZnO (or MgO) 0.32 parts .Sulfur 0.01 mole Pcioxid

In Table II are the physical properties of the vulcanized products that are produced when using

2.2-di (tert-butylperoxy) indane,
2.2-l) i (icrt.-bulylpcrox>) - 1.2.3,4-lctra-

hydronaphllialin
ll3.3-Tctra (tert-butylpcroxy) indane

for vulcanization / citing between 5 and 60 minutes 150 C have been obtained with those of vulcanized Compared to products obtained using dicuniylpcroxide at 165'C in 30 minutes (these are the optimal conditions for iJicumyi |> eroxiii) iiiiu iivi Use of I.M ^ -Tetra-iterl.-butylperoxyJ-cyclohexane and 2.2.5.5-Telra (tert-butylperoxy) -hexane at 150 ° and 165 ° C. in 30 minutes each are.

From the results compiled in Table II one recognizes. that a low temperature, a high vulcanization rate and better physical Properties of the vulcanized products correspond when using the peroxides according to the invention used instead of the peroxides used for comparison. This means that when you use the Peroxides according to the invention compared with the known peroxides Vulkanisationsproduktc with better physical properties can be obtained.

Table I.

Vu I kaimation speed wedge

peroxide
Type

Vulcanization in the rheometer Parts per 100 g of ethylene-propylene copolymer Vulcanization- Vulkanisalions-

lemperaiur time

g 100% mole 'C min.

0 (X (CH ₁ I.,

0OC (CH ₃ ),
CH ₃

2.94

177

CH ₃

4.22

177

14th

CH ₃

OOQCHj),

Vy 0OC (CH ₃ ),
((H ₁ I ₁ (OO 0OC (CH ₃ ),
0Oi (CH ₃ ),

■■ Ί \

/ / Q (X (CH ₃ ),

4.70

3.08

177

177

l'orlsel / iiiii!

ίο

peroxide
Type

( ₁ ), 0 (K ¹ ICM ₁ ),

CH ₁ C CM, CM, C (H ₁

0 (K (CM ₁ ), 0 (K ¹ ICM ₁ ),

Vulcanization in the rheometer file per KX) g ethylene-propylene-copolymer Vulcanization- Vulkanisulions-

0OC (CTI ₁ ), g K) O ", '. Mole temperature
C. Time
Min Dicujfiyl peroxide 00C (CH ₁ ). 2.70 0.01 177 14th (CHj) ₁ COO ^
/ \ 3.27 0.0075 177 7.5 (( ¹ Mj) ₁ COO

0.0075

177

7.8

Table Il

peroxide
Type

Vulkani- physical. Features d. vulcanized products

station line

Parts per 100 parts at 150 C tensile / tear module b. Module b. Module b. Shore A

Ethylene propylene strength elongation 100% 200% 300% Marie Copolymer elongation [elongation elongation

Mol g 100% in min. N / mm ² % N / mm ² N / mm ² N / mm ²

0 (K (CM ₁ ),
0 (K (C ¹ H,),
OC) C (CH ₁ ),

(CHj), COO

Dicumyl peroxide
(C ¹ Hj) ₁ COO

0.015

0 015

(J 0.005

0.006

0.01

OC) C (CM ₁ ), 0.0075 3 27

(CHj) jCOO OCK (CM ₁ ) J

OCXT (CH ₁ ) JC) OC (CHj),

I I 0.0075 3.28

CH ₁ -C-CHi-C ¹ H _{2 -C -CM 1}

OCX (CH ₁ (J OCK (CHj) ₁

5 18.92 400 2.35 5.79 11.18 65 66 66 IO 19.23 420 2.45 5.98 12.16 65 66 15th 20.11 460 2.16 5.59 11.38 65 30th 20.01 460 2.26 5.98 12.07 65 60 20.7 470 2.45 6.08 11.58 66 5 20.11 500 2.75 6.18 11.28 68 70 IO 21.29 430 3.24 7.55 13.73 69 15th 20.99 430 3.04 7.46 13.15 70 30th 21.29 410 3.63 8.24 15.11 70 60 21.09 430 3.43 7.65 13.54 70 5 9.61 600 1.37 2.55 4.22 62 to 16.97 550 2.06 4.22 7.75 6- 15th 19.82 500 1.96 5.49 10.3 67 (. ΊΊ ι in KO 60 ί ^ 52 440 OK 6, »Ί ΪΪ65 70 5 16.58 490 2.26 5.2 9.22 65 IO 19.03 330 3.53 9.12 15.99 68 70 15th 18.64 320 3.63 9.81 17.27 69 71 16.78 270 4.22 11.48 - 70 70 ^ 71 60 18.15 300 3.92 10.11 - 65 165 C 17.66 410 2.06 5.69 11.67 30 min. 66 150 C χ 30 19.13 408 2.06 5.1 11.77 65 165 χ 30 ^ 9.42 420 1.96 4.9 11.28

150'C χ 30 18.64 420

165 χ 30 18.93 435

1.86 2.06

4.6! 5.1

10.3 10.59

Claims (1)

Patent claims: 1. Peroxides with condensed aryl-cycloalkane rings of the general formulas ROO OOR \ /
CH / V \ / C-H C (R ') ₂ or