DE1923085A1 - Peroxyketals - Google Patents

Description

DipL-lng. Dip !, oeb. publ. RM ¹ do

DSETViCH LEWINSKY ^{ü> May Ia69}

PAT.JvTAM.VALT 558l-T.II / St

8 Munich 21 - Gctthardstr. 81

Telephone 56 17 62

Pennwalt Corporation, Three Penn Center Plaza, Philadelphia 2, Pennsylvania (V.St.A.)

¹¹ peroxy ketals "

U.S. priority dated May 7, 1968 from U.S. patent application 727,336

This invention relates to peroxyketals which can be used as free-wheel alkali polymerization initiators, Crosslinking agents and chemical intermediates are useful.

Certain peroxyketals are, for example, from the United States patent 2,455,569 known. This invention, on the other hand, relates to a new group of peroxyketals, these compounds having two peroxy groups which are attached to a common! which forms part of an aliphatic group which has at least three carbon atoms and at least one Having hydroxyl group or acyloxy group or both. the Hydroxy or acyloxy group is or are connected to primary or secondary carbon atoms which are other than those to which the two peroxy groups are attached.

The compounds of the invention are useful as sources; free radicals which can be used to initiate the polymerization of monomers; as synergistic agents with organic bromine compounds in flame retardant preparations; as a crosslinking agent or curing agent in unsaturated polyester resin compositions; as a crosslinking agent; and better known as [ chemical intermediates in the general way; Peroxyketals. ·

909848/1442 -2- j

- 2 The peroxyketals according to the invention have the formula:

R ₁₁ -OOCOOW
R ₂ Z

in which

(i) R ₁ and Rp are each divalent, primary or secondary aliphatic radicals or divalent secondary cycloaliphatic radicals, provided that R ₁ and R ₂ are connected to one another to form a ring

_k can; 0
Ψ

(ii) Y = H, OH, or -0-CR _x ;

0 ⁵
(ill) Z = OH or -0-CR ₃ ;

(iv) R, an aliphatic, cycloaliphatic, aryl, alkoxy, Denotes amino or alkylamino radical;

(v) Rj _{1 is} hydrogen or an aliphatic or cycloaliphatic radical which can be bonded to W to form a ring; and

(vi) W is hydrogen or an aliphatic or cycloallphatic radical which can be bonded _{to R 1 J to form a ring;} with the proviso that in the event that Rjj = hydrogen and Y and Z are both groups other than OH, the symbol W is also

- C - OH

or

C - 0 - OH

R ₂ can be Z.

-3-909848 / 1442

Illustrative compounds of the invention are:

3j 3-dihydroperoxy ^ 2-methyibutyl pivalate, H , 4-bis (t-buty! Peroxy) -1-pentanol,

1,3-diacetyloxy-2j2-bis (t-buty! Peroxy) propane, * », I | -Bis (pin« 5tnylperoxy) pentyl benzoate, 5,8-dihydroperoxy-5 * 8-dimethy1-3,6,7,10-tetraoxa-2,11-dodecadione,

2,2-bis (t-butylperoxy) propyl caproate, 3,3-bis (t-butylperoxy) -1-butanol.

In the above definitions, "aliphatic" includes substitution by aryl radicals (araliphatic radicals) and by cycloaliphatic radicals; "Cycloaliphatic" includes substitution by aliphatic radicals and by aryl radicals. "Aryl" includes substitution by aliphatic radicals and by cycloaliphatic radicals. Cycloaliphatic radicals and Aryl radicals can be single ring radicals such as phenyl and cyclohexyl, multiple ring radicals such as biphenyl, binaphthyl, Bicyclopropyl, Bicfclopentyl, or fused ring radicals w such as naphthyl and decahydronaphthyl. All of the above radicals can contain substituents which do not cause the desired reaction affect. In general, such non-interfering substituents include halogen, oxygen, sulfur and Nitrogen and groups containing these elements.

In general, R ₁ and R ₂ each have 1-10 carbon atoms in the aliphatic, divalent radical, 3-12 carbon atoms in the cycloaliphatic, divalent radical or 7-12 carbon atoms in the aralkylene. In general, R ₁ and R _{2 are} alkylene, phenalkylene or cycloalkylene or the corresponding halogen-substituted radicals.

In general, R1 has 1-18 carbon atoms in the aliphatic Radical, 3-12 carbon atoms in the cycloaliphatic radical, 6-12 carbon atoms in the aryl radical * 1-12 carbon atoms

909848 / UU -IJ- ^;

in the alkoxy radical or 1-10 carbon atoms in the alkylamino radical. Preferred is R, alkyl with 1-12 carbon atoms, phenalkyl. with 7-12 carbon atoms, cycloalkyl with 4-8 carbon atoms ,,, Phenyl with 6-12 carbon atoms and · the corresponding halogen-substituted radicals, alkoxy with 1-6 carbon atoms or Alkylamino with 1-6 carbon atoms.

In general, R ₁ J and R ₁ - are identical or different radicals, hydrogen, aliphatic radicals with 4-12 carbon atoms or cycloaliphatic radicals with 4-12 carbon atoms _: men. Preferably R ₁ J and R 1 - are identical or different radicals, hydrogen, aliphatic hydrocarbon with 4-10 carbon atoms "or cycloaliphatic hydrocarbon with 4-10 carbon atoms and each radical has a tertiary carbon atom, the latter being bonded to a peroxy oxygen atom is, for example:

CH ^ -CH ₉ -C-OO-

^ ² I.

CH,

CH-

00-

90 9 848 / 1U2

The hydroxy products according to the invention can be prepared by reducing peroxyketalcarboxylic acids and esters and by saponifying acyloxyperoxyketals. The acyloxyperoxyketals are also a new class of peroxy compounds which can be prepared by reacting acyloxy ketones with hydrogen peroxide or hydroperoxides in the presence of strongly acidic catalysts.

Representatives of ketones which can be used to prepare the acyloxyperoxyketals according to the invention include: acetonyl acetate, acetonyl isobutyrate, acetonyl pivalate, acetonyl chloropivälate, acetonyl 3-chlorobutyrate, acetonyl M-chlorobutyrate, acetonyl-2 ethylhexoate, acetonyl caproate, acetonyl laurate, acetonyl benzoate, acetonyl 3-chlorobenzoate, acetonyl M-nitrobenzoate, acetonyl il-methylbenzoate, acetonyl naphthoate, acetonyl methyl carbonate, acetonyl carbamate, acetonyl carbonate , Acetonyl dimethyl carbamate, M-acetoxy-2-butanone, 4-pivaloxy-2-butanone, it-benzoyloxy-a-butanone, ¹ »-acetoxy-3-methyl-2-butanone, 4-isobutyryloxy-3-methyl- 2-butanone, 4-acetoxy-3-n-butyl-2-butanone, Jl-acetoxy-1-phenyl-2-butanone, 1,3-bis (acetoxy) acetone, 1,3-bis (isobutyryloxy) acetone , l, 3-bls (benzoyloxy) acetone, 1-acetoxy-2-methyl-3-pentanone and 2- (3-acetoxypropyl) -l-cyclohexa * er. non.

To illustrate the type of products that can be obtained from the ketones in the list above, let us explain: that the reaction of acetonyl acetate with hydrogen peroxide in the presence of acidic catalysts is a mixture of compounds which are commonly known as ketone peroxides. Among the components of this mixture are structures like

-6-

909848/1442

H
O
O
ι P. H H
0
Q 0
(I. 0 CH ₃ C-CH, , -OC-CH ₃ 0
O CH, C-CH
3ι 2-0-C-CH ₃ 2-0-C-CH ₃ O CH ₃ -C-CH 0 0 O 0 2-0-C-CH ₃ H CH ₃ -C-CH
0 CH, C-CH
3 1 -0-C-CH,
^ Il J 0 I.
0 0 H H

expected. On the other hand, if the reaction with t-butyl-hydro perixid is executed, the simple structure can be:

! (CH ₃ J ₃

0
CH ₃ -C-CH ₂ OC-CH ₃

be obtained

To representatives of the perketal esters (and perketal acids), which can be reduced to the hydroxyperketals according to the invention, count: methyl 3,3-bis (t-butylperoxy) butyrate, ethyl-3 »3-bis

909848/1442 " ⁷ "

(t-butylperoxy) butyrate, η-butyl- ¹ !, M-bis- (t-butylperoxy) valerate, n-butyl-5,5-bis (t-butylperoxy) -hexoate, n-butyl-6,6- bis (t-butylperoxy) heptanoate, diethyl- ¹ !, j-bis (t-butylperoxy) heptanedioate, n-butyl-4,4-bis (t-amyl-peroxy) valerate, n-butyl-4,4-bis (pinanylperoxy) valerate, ethyl 3- \ 2-Cl, 1- bis (t-butylperoxy) cyclohexyl} propionate, n-butyl- ^ iJ-bisicumylperoxy ^ alerate, 2,2-bis (t-butylperoxy) propyl- acetate, 2,2-bis (t-butylperoxy) propyl-caproate, 1,3-bis-acetoxy-2,2-bis (t-butylperoxy) propane, 2,2-bis (chloro-t-butylperoxy) propyl acetate, 2,2-bis (t-butyl peroxy-propyl- ¹ !, 4-bis (t-butylperoxy) valerate, 9-acetoxymethyl-3 _s 3 »6,6,9-pentamethyl-1,2,7,8 -tetraoxacyclononane.

The reduction of diethyl - ^^ - bis (t-butylperoxy) -heptanedioate gives 4,4-bis (t-butylperoxy) -l, 7-heptanediol. The reduction of butyl ¹ !, IJ-bis (t-amylperoxy) valerate gives ¹ J, 4-bis (t-amy! Peroxy) -l-pentanol. The reduction of butyl- ¹ !, M-bis (pinanylperoxy) valerate gives ^, JJ-rbispinanylperoxy-1-pentanol. The reduction of 2,2-bis- (t-butyl-peroxy) propyl acetate gives 2,2-bis (t-butyl-peroxy) -1-propanol. The saponification of 2,2-bis (chloro-t-butylperoxy) propyl acetate gives 2,2-bis (chloro-t-butylperoxy) -1-propanol. The reduction of ethyl 3-lJi-il, l-bis (t-butylperoxy) cyclohexyl) propionate gives 3-i-Cl, l-bis (t-butylperoxy) cyclohexyl}] -1-propanol. By the reduction of 2,2-bis (t-butylperoxy) propyl-ijj ^ -bis (t-butylperoxy) valerate gives a mixture of 2,2-bis (t-butylperoxy) -1-propanol and ¹ J, H -bis (t-butylperoxy) -1-pentanol. The saponification of 4-pivaloxy-3-methyl-2,2-bis (t-butylperoxy) -butane gives 3-methyl-2,2-bis (t-butyl-peroxyJ - ^ - butanol. The reduction butyl 4, 4-bis "(cumylperoxy) valerate gives 4, ^ - bisicumylperoxy) -1-pentanol. ■

Typical acidic catalysts which can be used to prepare the peroxyketal esters include: sulfuric acid, phos-; phosphoric acid, p-toluenesulphonic acid, methpmsulphonic acid, perchloric acid | acidic and strongly acidic ion exchange resins such as Amberlite 200 and

909848 / 1U2 -8-

Amberlyst 15.

If the peroxyketals are prepared using hydroperoxides, they can be reacted further to form the alcoholic products according to the invention, in which Y = H or OH and Z ·· OH. When the peroxyketal group

\ 00R ₁

is formed in the peroxyketal ester part which is directly attached to the Is attached to the carbon atom, which carries the carbonyl oxygen, the hydroxyperoxyketal can be obtained by the peroxyketal ester with a reducing agent from the class of complex metal hydrides such as lithium aluminum hydride and its chemical equivalents (Reduction With Complex Metal Hydrides, Norman G. Gaylord, Interscience Publishers Inc., New York, 1956), which are known to reduce esters to alcohols under mild conditions. But when the peroxyketal group is located in that part of the ester which is bonded to the carbonyl carbon atom via an oxygen atom is, the hydroxy perketal can be obtained by " either simply hydrolyzed or saponified, or by, if desired, the ester with the reducing agents indicated above reductively splits.

Typical hydroperoxides which are used to prepare the inventive Products that can be used include: t-butyl hydroperoxide, t-amyl hydroperoxide, chloro-t-butyl hydroperoxide, 1,1,3,3, -Tetramethyl-butyl-hydroperoxide, cumyl-hydroperoxide, p-menthanyl hydroperoxide, pinanyl hydroperoxide, diisopropyltoenzene-h hydroperoxide, 2-methyl-2-hydroperoxy-i | -hydroxypentane.

To illustrate some of the general methods of preparing and using the products of the invention,

909848 / U42 -9-

selenium given the following examples.

example 1

A. MANUFACTURE OF ACETONYL CAPROATE

A mixture of 30.2 g (0.22 mol) sodium caproate, 25 cm ' Caproic acid and 18.5 g (0.20 mol) of chloroacetone is stirred and Heated for 5 hours at 110-120 ° C. After cooling to 30 ° C., 25 cor pentane is added and the pentane layer is decanted off and washed with water and 5% sodium hydroxide solution. After this Drying over anhydrous magnesium sulfate, the pentane is removed under reduced pressure. The product, weighing 16.7 g, is in 48.5 / Kiger yield obtained.

B. PREPARATION OF 2,2-Bis (t-butylperoxy) propyl caproate

: (CH ₃ ) ₃

A mixture of 12.9 g (0.075 mol) of acetonyl caproate and 19.7 g (0.20 mol) of 90% t-butyl hydroperoxide is stirred at 0 ° C, while 9 * 8 g of 77% sulfuric acid are slowly added. That The reaction mixture is then stirred for 4 hours at 0 ° C. and the organic layer is separated off. The product is washed with water, 5 hours of sodium hydroxide solution and finally with water and then dry over anhydrous magnesium sulfate. The severed

90 9848/1442 -io-

Product weighs 22.2 g (89 lb. extraction). The iodometric evaluation indicates that the product contains 98 % of the desired compound.

Example 2

A. Preparation of ⁱ t-Plvalyloxy-3-methyl-2-butanone

0 CH,

(CH,), CC-O-CH ₀ -CH-C-CH,

J J ' * it J-

A mixture of 60 g (0.6 mol) of 4-hydroxy-3-methyl-2-butanone and 70 g (0.7 mol) of triethylamine, dissolved in 225 enr Xther, is stirred at 25-30 ° C while 72 g (0.6 mol) of 95% pivalyl chloride, dissolved in 75 cm of ether, slowly added. After the addition is complete, the reaction mixture is stirred for 16 hours at 30 ° C., the precipitated triethylamine hydrochloride is separated by filtration and the ether solution is washed with 200 cm ^{3 of} tartaric acid solution, sodium bicarbonate solution and water and then dried over anhydrous magnesium sulfate. The ether is removed under reduced pressure and 109 g of product are obtained (98 iige yield).

B. Preparation of 3,3-DJhydroperoxy-2-methylbutyl pivalate

H
0

I i 3 ti
CH ₃ -C-CH-

0 0
H

CH, 0
_t i 3 ti

-0-CH-CH ₂ -OC- (CH ₃ ),

-11-

9098A8 / UA2

A mixture of 7.35 g (0.04 mol) 3 ^ .- exo-2-methylbutyl plvalate, (i »-pivalyloxy-3-methyl-2-butanone), 5.64 g (0.08 mol) 50 Ziger j hydrogen peroxide solution and 30 cnr ether is stirred at 0 ° C, j while adding 0.98 g (0.01 mol) of 95% sulfuric acid. j After stirring for 4 hours at 0 ° C, the organic layer is removed! separately and with saturated ammonium sulfate solution and water j washed neutral. The ethereal solution is over anhydrous magnesium sulfate dried and the ether removed under reduced pressure.

The 6 ₉ 46 g predominant product containing 21.6% of the calculated amount of active oxygen as determined by iodometric analysis, and is obtained in a yield of 15.1%.

By further reaction of the 3,3-dihydroperoxy-2-methyl-butyl pivalate with 3-oxo-2-methylbutyl pivalate and hydrogen peroxide in the presence of the acidic catalyst, are more complex ketone peroxide structures such as 2,2,6,7,10,11,15,15-0 ^ 3-11 ^ 1 ^ 1-7,10-dihydroperoxy-4,8,9,13-tetraoxa-3,14-hexadecanedione

CH, CH.

[3 j 3 j 3! 3 0

, CC-O-CH ₂ CH-C-OOC CH-CH ₂ -OC-C (CH ₃ )

0 0
0 0

H H

possible components of the product mixture.

Example 3
Production of 3 »3-bis (t-buty! Peroxy) -l-butanol

9098A8 / UA2

OC (CH,) 0 " ⁵

A solution of 3.08 g (0.082 mol) of lithium aluminum hydride, dissolved in 250 cnr of ether, is stirred at 5 - 10 ° C, while 28.3 g (0.1 mol) of methyl-3,3-bls ( t-butylperoxy) butyrate, dissolved in 50 cnr ether, added slowly. After stirring for 2 hours at 10.degree. C., 75 cubic centimeters of wet ether are slowly added, followed by 40 cubic centimeters of water and then 20 g of sodium tartrate. The mixture is stirred overnight. The ether layer is separated after 300 cubic meters of water has been added in order to completely dissolve the inorganic salts. The ether layer is washed, dried over anhydrous magnesium sulfate and the ether removed under reduced pressure. The product weighs 24.2 g (97 pounds recovery) and is found to contain 12.5% active pounds [active oxygen calculated: 12.8 % ]. This corresponds to an evaluation of 97.5 ί.

example Production of ^ .it-Blsit-butylperoxyy-l-pentanol CH ₃ -C-CH ₂ CH ₂ CH ₂ -OH

OC (CH ₃ ) ₃

A solution of 3 * 08 g (0.082 mol) lithium aluminum hydride, dissolved in 250 a ³ ether, is stirred at 0 - 5 ° C while

909848 / UA2 -13-

a solution of 3 **, 5 g (0.1 mol) of n-butyl-4,4-bis (t-butylperoxy) valerate, dissolved in 50 cm of ether, added slowly, followed by 30 cm of water and 25 g of sodium tartrate. Man let the mixture stir overnight.

The ether layer is separated off, washed with water, dried over anhydrous magnesium sulfate and the ether is removed under reduced pressure (25 ° C., 15 torr). The residue (30.2 g) is taken up in 200 cm × ³ pentane and dried again. The pentane is removed under reduced pressure, 29.7 g of product remaining in a yield of more than 100% (n-butyl alcohol is present, which can be recognized by its odor). Active oxygen calculated: 11.25 % · Active oxygen found: 9.69 % · This corresponds to an evaluation of 86 %.

Example 5
Production of 6,6-bis (t-buty! Peroxy) -l-heptanol

QC (CH,) 0 ^y

CHjC

OC (CH ₅ ).

A solution of 1.0 g (0.026 mol) of Lithima-Alualniumhydrld, ■ placed in 235 ca 'Xther, is stirred and kept at 20-25 ° C, while one k _s Z g n-bufcyl-6 _J 6-bls (t-buty! peroxy) - heptaneate Cgewoaaen- mm of an incompletely fetodig "" reaction of the ester ¹ with a solid amount of ®.a LiAlH ^), dissolved in 25 cnr

Ether, slow feiiisusetsfe »Haeh 2 & $ fhaü & g <sm Mteesi become 50 cm · ⁵

wet Xtfa ^ rs feae, nsBug $ e9tst _a raa Silema ^ aglertss IiIMEs, gin hydroworaufhin one long © «® 50 enr" Ifeists ⁵ hiins "gibt- so §00848 / 144

BATH ORIGINAL

complete hydrolysis is guaranteed. About 15 grams of sodium tartrate are then added and the mixture is stirred to dissolve the inorganic salts. The ethereal solution of the product is separated off, washed, dried over anhydrous magnesium sulfate and the ether removed under reduced pressure, 2.7 g of product (93% recovery) remaining. Active oxygen calculated i 10.95 Jt. Active oxygen found: 9.35 % · This corresponds to an evaluation of 86 %. Some of the n-butyl alcohol which was formed during the reduction of the ester remains in the product and can be easily detected by its odor.

Example 6
Production of 2,2-Bls (t-butylperoxy) propyl acetate

C (CH,),
O ^y *

° 2

CH ₃ C-CH ₂ -OC-CH ₃

O
O

A mixture of 69.6 g (0.6 mol) of acetonyl acetate, and 118.2 g (1.2 »οι) 90 SfIge» t-butyl-hydroperoxjrd, is stirred at 0 ⁰ C, while "to 59.1 g 77% sulfuric acid is slowly added within 50 minutes * The mixture is then stirred for k hours at ⁰ ° C., the organic layer is separated off and washed with cold 50% sodium hydroxide solution and finally with water and then weighed over anhydrous magnesium sulphate . 126> S g (77. JH.gejodometrisshe Auawertung to seigt that the Prodn-t ^ W contains the desired compound.

909848/144 2 '"'. ■

BATH

Example 7 ....

Manufacture of l ^ -Dlacetoxy ^^ -bls ^ -butylperoxy) propane

ο ° ο

CH ₅ -CO-CH ₂ -C-CH ₂ -OC-CH,

A reaction mixture which contains 17% S- (0.1 mol) 1,3-diacetoxyacetone, 21.7 g (0.22 mol) 90% t-butyl hydroperoxide and 70 cm.benzene is heated to 0.degree stirred while 10.8 g of 77% sulfuric acid are slowly added. The reaction mixture is then stirred for M hours at 0 ° C. and the organic layer is separated off. The organic layer is washed with water, 2% sodium hydroxide solution and finally with water and then dried over anhydrous magnesium sulphate. The product weighs 7.8 g. ■ The iodometric evaluation shows that the product contains 96.5 Ϊ of the desired compound. I.

909848/1442

Example 8

Production of 4, ¹ l-Bls (l, l, 3,3-tetramethylbutylperoxy)

pentyl benzoate

CH,

CH.

CH ^ C-CH ₀ -COOCOOC-CH ₀ -C-CH

³ ι

CH

CH,

I

CH ₂

CH

CH

C = O

^C 6 ^H 5

A mixture of 8.2 * 1 g (0.0 * 1 mol) 4-oxopentyl-benzoate, 18.80 g (0.10 * 1 mol) 1,1,3,3-tetramethylbutyl-hydroperoxide (85 2ig) and 25 cnr ether, the mixture is stirred at 10 ° C. while 9.0 g of 77 % sulfuric acid solution are slowly added. The reaction mixture is then stirred for ¹ hour J at 0 ° C, diluted with cold water and the organic layer separated, washed with 5 £ Lger sodium hydroxide solution then washed until neutral and washed with water. The ether solution is dried over anhydrous magnesium sulfate and the ether is removed under reduced pressure.

The product weighs 20.0 g, that is 101.3 % of the calculated value of active oxygen, determined by iodometry.

9098A8 / UA2

Example 9 Preparation of 4, M-BIs (pinany! Peroxy) pentyl benzoate

CH.

A mixture of 18.0 g (0.08 mol) pinanyl hydroperoxide, 8.24 g; (0.04 mol) 4-oxopentyl benzoate and 50 cm. Ether, becomes at 0 ° C stirred while slowly adding 9.0 g of 77% sulfuric acid solution added. After stirring for 4 hours at 0 ° C, the organic Layer separated, washed with 5% sodium hydroxide solution and finally washed neutral with water. The solution is dried over anhydrous magnesium sulfate and the ether is under removed under reduced pressure »

The evaluation of the 18.34 g of product gives 98.4 % of the calculated amount of active oxygen, determined by iodometric evaluation, corresponding to a yield of 85.8 % of theory.

-18-

909848/14 42

Example 10
Manufacture of SiS

tetraoxa-2,11-dodecadione

CH, CH,

I ³ ! ³

CH - ^ - CO-CH ₀ -COOC-CH ₀ -OC-CH-.
Jn cr ι ^d η J

⁰ OO ⁰
0 0

HH

A mixture of 10.9 g (0.16 mol) of 50 Äigem hydrogen peroxide, 0.98 g (0.01 mol) 95 fciger sulfuric acid and 30 cm ^ ether is 2 at - 5 ° C stirred while 18.58 g CO, 16 mol) acetoxyacetone added within 15 minutes. The reaction mixture is stirred for a further hour at 0 ° C, the ether layer is separated off, washed with cold 40% ammonium sulfate solution and then treated with solid sodium bicarbonate in order to adjust the pH of the aqueous layer to a pH of 5 * The ether layer is separated off, dried over anhydrous magnesium sulfate and the ether removed under reduced pressure. This leaves 15.57 g of product with a rating of 7.01 % active oxygen, determined by iodometric titration (43.5 % of the calculated active oxygen for the desired product).

-19-

909843/144

Example 11

ΐ SPI-EXOTHERMAL TESTS

! Hardening of a polyester resin base

Samples of l-acetoxy-2,2-bis (t-butylperoxy) propane (from Bei-

! game 6) with a rating of 99.2 % (compound A) and 1-caproxy-2,2-bis (t-butylperoxy) propane (from Example 1) with a rating of 98 % (compound B) are in the SPI -Exotherm test on a polyester resin basis and compared with t-butyl peroxybenzoate (tBPD) with the same active oxygen content. The bath ο

temperature is 115 C and the percentages by weight used are 1 % tBPD, 0.71 % of compound A and 0.85 % of compound B.

tBPD connection A connection B

Gelation (min.) 5.5 5.9 7.0

Hardening (min.) 6.7 7.2 8.3

Peak ° C <223.9 225.6 224 _S 4

Barcol ⁺ 40-45 45-50 40-45

Tests are carried out under comparable conditions on samples of the hydroxy perketals, which in these examples were obtained by reducing the perketal esters. The compound D [4,4-bis (t-butylperoxy) -l-pentanol (from example 4) with a rating of 80 jO and compound E [3,3-bls (t-butylperoxy) -l-butanol (from example 3) with a rating of 97.5 % J are used in amounts of 0.84 % of compound D and 0.65 % of compound E compared to 1 % tBPD at a bath temperature of 115 ° C.

-20- • 9 09848 / U4Z

(min.) tBPD Connection D Connection E Gelation (min.) 5.5 4.2 3.0 Hardening 6.7 5.3 4.2 Peak ⁰ C 223.9 226.7 225.6 Barcol ⁺ 40-45 40-45 40-45

■. Reading on
Barcol-Impressor (model QYZj- 934-1)

Polymerization tests are carried out using the "SPI operation for the course of exothermic curves polyester resins", Published in preprint of 16th Annual Conference - Reinforced Plastics Division, Society of the Plastics Industry Inc., February 1961.

The tests are performed on a general purpose polyester resin, the "base" of which is unsaturated, which is Resin corresponds to the following recipe:

Maleic anhydride 1.0 mol Ph t ha 1 s acid anhydride id 1.0 mol Propylene glycol 2.2 moles Acid number of the alkyl resin 35-45 Inhibitor (hydroquinone) (% of the final solution) 0.013 Styrene monomer (Jt of the final solution) 32 - 34

909848 / U42

- 21 Example 12
Curing a cobalt-containing polyester resin

A sample of 5> 8-dihydroperoxy-5,8-dimethyl-3,6,7,10-tetraoxy-2,11-dodecadlone (from Example 10) (Compound C) with a rating of 43.5 % is recorded in the SPI -Exothermic test used to cure a cobalt accelerated polyester resin formulation. This cobalt-accelerated polyester resin composition is a polyester resin base to which 0.2 % of a 6% cobalt-cem solution has been added. Cobalt-ten-Cem is a registered trademark of Mooney Chemicals Inc., Cleveland, Ohio and the substance referred to is the cobalt salt of a long-chain, organic acid. Compound C is compared in activity with LUPERSOL DDM, a commercially available ketone peroxide catalyst. The samples are compared with one another with equal contents of active oxygen ti percent by weight LUPER30L DDM, 1.55 % of compound C). The data at: room temperature (about 23 ° C.) and the gelation times (in minutes) at 30 ° C. are recorded. r

Compound C LUPERSOL DDM + Gelation at 30 ° C
Oiling at
Rough temperature 9.8
15.5 Peak ⁰ C
Barcoi ;: }. $ '' ^ - ♦ her fsmxxa &'ta. L®m sag- voss Dtattthf l-piifelftl% t- 25.5 y
36.1 123.9 i
% more active! -22- _{

0098487

Example 13

A sample of 1-acetoxy-2,2-bis (t-butylperoxy) propane (from Example 6) with a rating of 99.256 is used as a synergistic agent in a flame retardant formulation for styrene at a concentration of 0.198 % (0.4 % dicumyl peroxide equivalent) and 0.4 % tetrabromithane tested.

The prepared styrene is self-extinguishing in 2, H seconds, which shows that the synergistic agent is a good Peroxydprodukt respect Piaminverzögerung.

Flame retardation test

In this test, ASTM D-635-56T and discussed more fully in USA-patent 3,388,861, "is a sample which contained only the 0.4% Tetrabromathan (no peroxide) '* are not self-extinguishing.

90984S / 144 2

j - 23 -

Example l4
Cross-linking of polyethylene

Crosslinking by means of peroxide of polyethylene (Union Carbide DYNH-I, density 0.919, melt index 2.0, Bakelite polyethylene injection molding material) is carried out by mixing 0.01 equivalent of peroxide with 100 g of polyethylene on a roller mill and cure the samples in a heated press for 30 minutes to crosslink the polyethylene. The extent of networking is determined by extracting the crosslinked samples with hot xylene, the undissolved fraction being the crosslinked material is.

phr hardening r- ** C wetting %

l-acetoxy-2,2-bis (t-butylperoxy) propane 1.4 l60.0 67.4 (from Example 6) J «.J« J.5

l-caproxy-2,2-bis (t-butylperoxy) propane 1.7 160.0 73.5 (from Example 1) J71, l 73.1

++ parts peroxide per 100 parts resin.

909848 / 1U2

- 24 Example 15 Crosslinking of polyvinyl chloride

Crosslinking of polyvinyl chloride is accomplished by incorporating 0.015 moles of the peroxide compound into 100 parts of Exon 905 polyvinyl chloride resin (Firestone, general purpose resin) and 5 parts of Dyphos PG ⁺ lead stabilizer, dibasic lead phosphite from National Lead Co., and then the formulations in one heated press cures at different temperatures. The extent of crosslinking is determined by immersing the cured samples in tetrahydrofuran for 16-18 hours at 25 ° C. and determining the amount of undissolved material. In the table, the weight of the peroxide compound is given in "phr" (files per 100 parts of resin).

Ejector
tion % phr Hardening (min)
Temp ° C / time 15th
15th Networking J.AAcetoxy-2,2-bis
(t-butylperoxy) propane
(from example 6) 95.8 2.1 176.7
190.6 15th 7k j
92 l-caproxy-2,2-bis
(t-butylperoxy) propane
(from example 1) 57.6 2.5 176.7 85.8 -j LUPERSOL 230 (commercial
usual perketal) 15th
15th n-butyl-4,4-bis
(t-buty! peroxy) valerate ~ - 2.5 176.7
190.6 46.8
80.4

909848 / U42

Claims (5)

Oip1.-ln ₃ . D pi. eac. puöl. _R y, _QRQ DIETSICHLEWiNSKY 5th Shark WRI ■ PATWTANvVALT
8München2l-Gotthardstr. 81 % $ 55öl-III / pc Telephone 56 17 62 Pennwalt Corporation, Three Penn Center Plaza, Philadelphia 2, Pennsylvania (V.St.A.) Patent claims:
Peroxyketals of the formula: R ₁ Y
R ₁₁ -OO-C-0-O-W in which i) R ₁ and R _{2 are} each divalent, primary or secondary aliphatic radicals or divalent secondary cycloallphatic radicals, with the proviso that R ₁ and R ₂ can be linked to one another to form a ring; Ii) J hydrogen, OH or -0-CR ,; ¹ ^ * 0 ill) Z s OH or -0-CR _{5 is 5} In aliphatic «» radical »cjrcloallphatisches ■ s is aryl, alkoxy-j amino or alkylamino radical; v) Rj ₁ hydrogen © äer an aXlphmtisehes or cycloallphatlsch © 8 Mdikal is good to be utlefeet with W Kater Ringbll-Sung ^ © rbunänen 0OS848- / 1442 BAD ORtGtNAL vi) W is hydrogen or an aliphatic or cycloaliphatic radical which can be linked to form a ring / Rh, with the proviso that in the event that R ^ = H and Y and Z both mean groups other than OH, W also _nv R ₁ Y -C-OH YR ₂ Z or -CO-OH.
R ₂ Z 2. Peroxyketals according to claim 1, characterized in that R ₁ and R _{2 are} each primary or secondary aliphatic ^ hydrocarbon radicals with 1-10 carbon atoms. 3. Peroxyketals according to claim 1, characterized in that R ₁ and R ₂ each represent secondary cycloaliphatic hydrocarbon radicals with 3-12 carbon atoms. 4. Peroxyketals according to claim 1, characterized in that R ₁ and R ₂ each represent an alkylene, phenalkylene or cycloalkylene radical which optionally contains halogen substances. 5. Peroxyketals according to claim 1 to 4, characterized in that that at least one of the symbols 7 and Z is a " -0-CR ₃ Is a radical, where R _{3 is} an aliphatic radical with 1 to 18 carbon atoms, a cycloaliphatic radical old 3'-12 carbon atoms or an aryl radical with β-12 carbon atoms. 6. peroxyketals Naeh claim 1 through ₅ characterized ^ g that at least one of the oils & SySS t and Z <2 sia Radical ", where E ₃ © in alky! Radical old % - % t \. Atoms, a phenalkyl radical with? - 12 substances 909848 / 1442- ". ■ -3 BAD ORlQJNAi denotes a cycloalkyl radical having U- 8 carbon atoms, a phenyl radical or an alkylpkenyl radical having 7-12 carbon atoms, which optionally contains halogen substituents. 7. Peroxyketals according to claim 1 to 4, characterized in that that at least one of the symbols Y and Z equals _t , -0-C-R, where R is a lower alkoxy radical or a lower alkyl substituted amino radical. 8. Peroxyketals according to claim 1 to 7, characterized in that R ₁ ^ is an aliphatic or cycloaliphatic radical with ¹ J - 12 carbon atoms. 9. Peroxyketals according to claim 8, characterized in that R ₁ J is a tertiary radical. 10. Peroxyketals according to claim 8 or 9 »characterized in that that Rjj is alkyl or cycloalkyl. 11. Peroxyketals according to claim 1 to 10, characterized in that W is an aliphatic or cycloaliphatic radical with ¹ J - 12 carbon atoms. 12. Peroxyketals according to claim 11, characterized in that j W is a tertiary radical. 13 · Peroxyketals according to claim 11 or 12, characterized in that that W is alkyl or cycloalkyl. I ¹ J · 3 »3-dihydroperoxy-2-methylbutyl pivalate. <L5. 4,4-bis (t-butylperoxy) -l-pentanol. I. 9 0 9 8 4 8 / U 4 2 -4- J. « 16. 1,3-Diacetoxy-2 ₃ 2-bis (t-butylperoxy) propane. 17. ^ j ¹ I-BiS (pinanyl peroxy) pentyl benzoate. 18. 5j8-dihydroperoxy-5,8-dimethyl-3,6,7 » 10-tetraoxa-2,11 · dodecadione. 9098A8 / UA2