DE1593704A1 - Safe to handle diacyl peroxide compositions - Google Patents

Description

88 561

Wallace & Tiernan Inc., Belleville, New Jersey "V.St.A. Safe to handle diaoyl peroxide compositions

The invention relates to compositions containing dissolved diacyl peroxides which can be safely handled _, transported, used and stored, and to safe processes for the preparation of such compositions.

The diacyl peroxides with a short carbon chain contained in the compositions according to the invention, namely peroxides, which are derived from carboxylic acids with 2-6 carbon atoms are valuable polymerization initiators or catalysts,

• ORIGINAL BATHROOM

009848/1873

In the pure state these peroxides are extraordinary dangerous connections. They are very sensitive to impact and shock «Rapid heating leads to violent explosions. For these reasons, their technical manufacture and Usage so far set limits »

Diacetyl peroxide is only commercially available as a 25% solution in dimethyl pithhalate. Care must be taken to prevent this solution ^{from precipitating out of this solution by cooling to 0 0 0} j (32 ° P), an ambient temperature that is common in winter, from precipitating shock-sensitive crystals of diacetyl peroxide. Due to the presence of dimethyl phthalate, a nonvolatile plasticizer, in considerable amounts, the use of this solution is limited to those applications in polymerizations in which the presence of this plasticizer is not harmful.

Dipropionyl peroxide has only recently been brought onto the market as a 25% solution in heptane. The evaporation of the heptane increases the peroxide concentration and leads to a very shock-sensitive product. Storage at -10 ⁰ O (13 ⁰ F) or below causes this solution to segregate, forming a shock-sensitive lower surface

Diisobutyryl peroxide has not yet been commercially available because of its dangerous properties. In the literature

009848/1873

It was reported that an attempt to make a solution of about 10 g of this peroxide in diethyl ether resulted in a violent one The explosion ended

The aim of the invention is therefore the safe production of lower aliphatic diacyl peroxides.

The invention further aims to handle "certain such Diacetylperoxyde in solution compositions containing the factors * vein suitable for example sur use as Polymerisationeinitia ¹ as crosslinking agents.

Surprisingly, these were now safely manageable Compositions found that are essentially aliphatic

Diacyl peroxides of the formula

0 0

H »t

R-O-OO-C-R,

wherein R is an aliphatic group having 1-5 carbon atoms means, and in such an amount that the composition is rendered safe, one or more of the compounds of the class hereinafter referred to as "safety solvents" dtr aliphatic hydrocarbons, the aliphatic ketones, the aliphatic ethers, the aliphatic ethers and the aliphatic alcohols which are essentially the same Evaporation rate as the peroxide has, whereby

00984B / U73 _BAD original

dangerous concentrations in the liquid or vapor phase Become termies.

Advantageously, the security solvent evaporates at practically the same speed as the peroxide in it, i.e. at the same speed as that the peroxide concentration remains essentially constant. Its concentration of the peroxide down to a dangerous level is avoided both in the liquid phase and in the vapor phase.

This general invention can also be applied to other classes of organic peroxides which are dangerous in their pure state, including aliphatic peroxyesters, alkyl peroxides, ketone peroxides, peroxyketals and gyA & gperoxides .

Definition of safely manageable compositions

To determine the safety of diacyl peroxide compositions known test methods were used as a measure of thermal stability

4 ■ ■ V

Act and manageability of peroxides applied * Each test result was evaluated and from the overall evaluation of all These tests revealed the safety of the composite set

009848/1873

The following test methods were used - 1 * pressure vessel test (Pressure Vesael Test (PVT))

The test apparatus consisted of a cylindrical brass vessel (235 cc volume) with a replaceable, apertured disc in the side wall, closed on the top with a rupture disc · There was used an aluminum i miniumzerreißscheibe containing up to 90 # prestretched their breaking strength and tested at 6.86 to 7 * 0 atmospheres (98-100 psig) 74 apertured disks, where the bore diameter increased exponentially from t mm to 24 mm, were available.

When a sample is rapidly heated in the test device with the aid of a Meker burner, the tear disk tears or remains entirely, depending on the pressure developed by the decomposition and the degree of gas discharge, which in turn depends on the size of the hole in the perforated disc used «The size of the hole in the perforated disc» which is required to prevent the rupture disc from bursting, There is a hatred for the violence of the decomposition and for them developed Gaem «n £ e»

It has been experimentally determined that _s a sample of 5.0 g of For comparison purposes, suitable “dUh” reproducible results

009848/1873 bad original

For the comparative test, organic peroxides supplied in this test was benzyl peroxide ($ 98) ale Reference substance chosen as it is a well-known multiple is a tested substance used in technology. It causes the rupture disk in the case of an exhaust gas ~ opening width of 14 * 9 mm.

2n sole sensitivity

In this test, a sample of peroxide is exposed to the bottom of a known weight that is a ground distance on an impact tester under reproducible Conditions for sample size and dimensions fail «The Sensitivity to floor slap or impact is determined after a bang, smoke formation or obvious decomposition of the sample.

3 ° Checking the evaporation rate

Samples of diacyl peroxide-solvent compositions were made at room temperature (20-25 0) in relatively thinner Sohioht left to stand too. determine whether they become dangerous (sensitive to shock) when they evaporate. In a Petri dish with an inner diameter of 90 mm and a height of 20 mm, 10.0 g of the biaoyl peroxide composition. The weight loss and the change in the sample due to evaporation of the

BATH ORIGINAL

009848/1873

Solvents and / or peroxides were measured ο During the duration of the experiment, regular shock sensitivity tests were carried out ₀

Heat sensitivity (rapid heat test)

In this test, a 1 g sample in a test tube at a controlled rate of 4 ⁰ C per minute he = d hitzt is. The decomposition temperature and the type of decomposition are noted

The test methods mentioned are described in more detail by Noller and Bolton, Analytical Chemistry, 35t 887 (1963) and Noller et al, Ind. Eng. Chern. 56, ^ 12, 18-27 (1964) described »

Show safe peroxide ~ solvent ~ compositions the following characteristics with regard to the test methods mentioned

on:. ""

1 »You require in the assessment after the pressure vessel test

an exhaust port of 10 mm or less;

2ο they show no shock sensitivity in the impact test * ability

009848/1373 _ßAD original

■ "■ - 8 -

3. In the assessment after the son's success test they exhibit a mild to rapid decomposition form, however no explosive decomposition. on and

4 «they show no changes in the peroxide content or in the concentration of active oxygen »which lead to impact-sensitive compositions.

The diacyl peroxides

The diacyl peroxide component of the safety compositions according to the invention can be used in an Ublioher manner by base-catalyzed conversion of the desired lower aliphatic Carboxylic acid anhydride or halide "with hydrogen" - peroxide are produced.

In US Pat. No. 2,458,207 the manufacture of diacetyl peroxide in dimethyl phthalate.

The lower aliphatic diaoyl peroxides which are contained in the safety combinations according to the invention » • ind connections of the? Ornel

0 0 η «t

R-O - 0 - 0 - 0 - C-R »

009848/1873

in which R is an aliphatic group with 1-5 carbon atoms and preferably an alkyl group having 1 ~ 4 carbon atoms means. Examples of such diacyl peroxides include diacetyl peroxide, dipropionyl peroxide, dibutyryl peroxides, Di pentanoyl peroxides and dihexanoyl peroxides, acetylpropionyl peroxide, acetylpentanoyl peroxides and di2-methylpentanoyl peroxides

In the context of the invention, safety compositions with aliphatic diaoyl peroxides are particularly preferred, which derived from diacetyl peroxide, dipropionyl peroxide, diisobutyryl peroxide and di ~ 2 ~ methylpentanoyl peroxide.

Safety Solvent Safety solvent for the diacyl-

peroxides have to be able to dissolve in addition to their normal solubility for

the peroxide have certain properties *. "

A. Since the lower aliphatic diacyl peroxides in concentrated form are very sensitive to shock, the solvent must have practically the same rate of evaporation as contain the peroxide, thereby avoiding dangerous peroxide concentrations in both the liquid and the vapor phase. In general, this condition is

009848/1873 bad

use of a solvent, since practically in the same bath <rich as peroxide boils, sufficiently precisely fulfilled.

The safety agent must not have a boiling point that is too high, otherwise the rate of evaporation is changed in the opposite way. Acetyl peroxide, for example, verifiable volatilized even at room temperature easily from dimethyl phthalate as a solvent (20-25 ⁰ C) and under certain conditions the vapor explodes when heated.

B. Dae solvent must not have any harmful effect on the catalytic activity or the usual stability (Lifetime daa diacylperoxyda) have *

0. The solvent must also have a deadening effect against heat echo and impact sensitivity.

Suitable safety solvents are aliphatic hydrocarbons, aliphatic ketones, aliphatic eaters, aliphatic ethers, aliphatic alcohols and mixtures thereof which have the abovementioned evaporation ability. Printed in temperature values, these solvents boiling in the range of about 140 - 21O ⁰ O at 760 mm Hg, d, h "daa solvent may einsigen a true boiling point within this range, or within this range Siedebereioh

009848/1873 _BAD

have »or its boiling range can eloh over the entire specified range or a Löeungeraittelmisohimg can have a number of boiling points in this range.

Typical examples of preferred security solvents are the following (d.r. means boiling range):

low boiling Haphtha (dr 150 - 17O ⁰ C); odorless Teetbenzin (dr 175-205 ⁰ C); Methyl isoamyl ketone (dr 141-148 ° 0) j Butyläthylketon (dr 143-150 ⁰ C); Diisobutyl ketone (dr 163-173 ⁰ C); Methyl amyl (dr 146-150 ⁰ C); Hexylaeetat (dr 165-170 ⁰ C);

Xthylenglyoolmonobutylätheraoetat (dr 168-192 ⁰ C); Xthylenglyoolmonomethylätheraoetat (dr 154-152 ⁰ C); Xthylenglyoolmonoäthylätheraoetat (dr 145-164 ⁰ O); Xthylenglycolmonobutyläther (dr 171-173 ⁰ C); . i Diethylene glycol ethyl ether (dr 188 - 19O ⁰ O)? Diethylene glycol dimethyl ether (dr 194-198 ⁰ O); Diaoetone alcohol (aoetone free) (d.rV 169 - 172 ⁰ C); 2-ethylhexyl acetate '

009848/1873

BATH ORIGINAL

- 12 -. Compositions according to the invention

The security solutions of the invention contain the security solvent described above at least in such a slope that the compositions be done safely _o The required to ensure the safety eioh amount varies with the present in the composition in each case Diacylperoxydο

According to the invention, safety compositions contain the following exemplary amounts in weight8- # of the composition:

a. Aliphatic diacyl peroxide generally about 10-70%, usually about 20-55 $> _9, preferably about 25-50 $> and

b. Security solvents generally around $ 30 ~ $ 90 usually around $ 45-80 and preferably # 50-75

Exemplary diacyl peroxide safety compositions are:

Diacetyl peroxide (DAP) and ethyl butyl ketone (EBK) in an amount which is sufficient for at least the risk of danger

For example, about 20-50 $> DAP and about 50-80 # EBK, or about 25-30 # DAP and about 70-75 $> EBK.

BATH ORIGINAL

009848/1873

Dipropionylperoxyd (DPP) and low boiling naphtha with a boiling range of about 150 to 170 ⁰ C in a few tens sufficient to Gefahrlosmachen the composition amount 'example as well as about 20 "= × 50 7» DPP and about 50 to 80 $> low eiedendes naphtha , or about 25 - 30 # DPP and 70 - 75 & low-boiling naphtha «

Diieobutyryl peroxide (DIBP) and odorless white spirit with f

a distillation range of about 175-205 ⁰ C "sufficient in a Meng _e least in Gefahrlosmachen of the composition, for example, 40 - 70 # DIBP and about 30 - 60 $> odorless mineral spirits (OMS) _9, or about 50 $ DIBP and about 50 J * OMS.

Manufacture of the safety equipment

For di · Manufacture of security cooperation inventive * g statutes / was found without danger process. Hydrogen peroxide and a lower aliphatic carboxylic acid anhydride are mixed with cooling in order to avoid an increase in temperature. The mixing is carried out in the presence of one or more of the safety solvents defined above . Eb Jet SioherheltelÖBungninLttB]. present that the finally obtained DlaoylperojcyfUöiiuru; aLs ni.oherholtszuaammsnüotaung ^r it> r i'irfirduri / f vor Liegt, fi.nrihclHm ilao Ί / aniiHr'Mfcoffperoxyfl and Am

0 0 9 8 4 0 / I 8 7 3 _BAD original

Anhydride are mixed, so much alkali is partially suggested that nan receives a neutral product. Anteilweiee The term "! ¹ * i" t is not only the addition of beetimmten Binzelmengen alkali eondem a continuous addition at such a rate · that practically no temperature increase occurs, to understand.

In any case, it turned out to be favorable leutralieation to make under cooling. Suitable alkalis include, for example, the alkali metal hydroxides, the Er4 ~ alkali hydroxides and the alkali carbonates.

Bin "acylperoxydsioherheitasusamnensetzungen more safe Me ¹ UiOdS aur Preparation of Di is that one vermisoht the above defined Sioherheitelöaungpoittel and an aqueous AlkaliitSsung, in this mixture under hollows water" stoffperoxyd in at least stöOhiometrischer amount intervenes and then dis ResJctionsaitohung under cooling with a stoichiometric amount added to lower aliphatic carbonic acid halide.

One gives; sufficient aqueous alkali solution from the outset to In the reacfcionemieohung during and at the end of the implementation • Insu alkaline pH, i.e. about etm? to obtain. Man flihrk farner iu la0 sqm Pinili §ina

ODDB / .B / U73

- 15 composition is available ,

The reaction mixture is allowed to settle and the dfe is separated organic phase containing the diacyl peroxide and the safety solvent, and washed with water. After removal of the wash water, the organic liquid is dried to obtain a diacyl peroxide solvent safety composition o f

The following process examples show exemplary procedures for carrying out the Siohor unit method according to the invention

Manufacture and testing of diacyl peroxide compositions

example 1

A reactor, which was provided with a stirrer and cooling device, was filled with 104 _f 0 g (0.8 mol) of propionic anhydride and 120 g of low-boiling naphtha carbonate

i.
Solvent *. (dr 150-170 C) charged. After the mixture had reached a temperature of about -2 ⁰ O, 27.5 g (0.4 mol) of hydrogen peroxide (50% aqueous solution) were added and the mixture was stirred for 5 minutes "Then a total of 144 g of a 25% aqueous sodium carbonate solution were added over a period of about 15 minutes in order to

0098A8 / 1 873 _BAD original

To bring the reaction mixture practically to the neutral point. During the reaction, the temperature was kept at about O ⁰ O + 10 ⁰ C. After settling, the organic phase was separated at about 10 * 15 ⁰ C and 7.0 g of anhydrous magnesium sulfate getrocknetο After filtration 198 g of solution were obtained with a _s of 26 4 Dipispionylperoxydgehalt f ° *

Example 2

The procedure of Example 1 was repeated using odorless mineral spirit - repeated as security solvent (d r _{o o} 175 205 ⁰ C). A solution was obtained with a dipropionyl peroxide content of 25? 8 $> *

Example 3

The procedure of Example 1 was repeated, except that hexyl acetate (dr «165-170 ⁰ C) was used as collateral solvent wurdeο A solution having a Dipropionylperoxydgehalt of 27 $ _f 7 was obtained as a product.

Example 4

The operation of <Example 1 was repeated with low siedenclem Naphtha (d "r 150-170 ⁰ C.) As the Sioherheitslösungsmittel. This was used in such an amount that one

BATH

009848/1873

solution with a dipropionyl peroxide content of 51 i ° was obtained as a product »

Example 5

Following the same procedure as in Example 1 was Diisobuty ketone! (D _o r _o 163-173 ° C) as Sicherheitalösungsmittel Yerwendet * A solution is obtained with a Dipropionylper- d oxide content of 25.5 i>.

Example 6

When using Äthylenglycolmonobutyläther (dr = 170 - 173 ⁰ C), ale safety solvent, a solution was obtained with a 26.0 Dipropionylperoxydgehalt ^ as a product

Example 7

The procedure of Example 1 was repeated using 152,5g heptane - as solvent (dr 45 96 ⁰ C). Because of its low boiling point, additional heptane was required to obtain a product of the desired level. 195 g of product with a dipropionyl peroxide content of 26.0 #o were obtained

Comparative values that make up the security of the foregoing

009848/1873 _{irMMÄ |}

BATH ORIGINAL

Dipropionyl peroxide compositions can be seen after given in Table I.

009848/1873

Table I.

! Testing of propionyl peroxide compositions

Security checks Impact wedge; Rapid heat test Pressure vessel test

ο size of the exhaust opening at »

cd bursting of the tear disk ο »ia mm

** "* Evaporation rate JJ ν25 ⁶ C) *

- * time, (hours)

^ ₄ Change in salary in ψ

Weight loss in $>

Change in impact sensitivity

2. 3. 4 _O 5. 6o NSS (5)
HSS NSS NSS NSS NSS NSS (2)
120 ⁰ C (D
90 ⁰ C (D-
90 ⁰ C (D
85 ⁰ C (D
80 ^{c c} (D ■
94 ⁰ C (D
86 ⁰ C

V / o

(1) «rather mild decomposition from ° C,

(2 'Form explosion at ° (

ί 3) not sensitive to shock

(4) sensitive to shock

4.0

5 5 2 5

+ 3.0 none none +6.0

55 ₉ 0 15.0 20.0 25.5

no no no no

4th
no

26.2
no

4th
-1.7

no

> 24

80

(4)

■ at '12.7 mm (1/2 ")

593704

- 20 BeianßielJJ

! Am Realster jacketed, equipped with a stirrer and a thermometer, 30 g Äthylbuty ketone was mixed with 21 "2 g (0 206 _f mol) of acetic anhydride, (dor 143 -. 151 ⁰ C), 7.2 (0.206 mol) of Hydrogen peroxyä (50 5S aqueous solution) 5 ml of water charged *

To -6 ⁰ C a solution aue 12.5 g (0 "118 mol) sodium carbonate in 37 ₉ 5 ml of water slowly trains pass, to bring the Reaktionemischung substantially to the neutral point with stirring at -2 ,, After complete addition, the reaction mixture was 5 minutes at 5 "x 10 ⁰ C continued and then allowed to settle ge las8en, the aqueous Shase was removed and the organic phase over anhydrous magnesium sulfate 'After filtration were 37» 1 g security product with a Diacetylperoxyd content of 23.8 $ > received.

Example 9

The Working procedure of Example 8 was repeated wherein the amount of Xthylbutylketon eo was reduced, that has a security product with a Diacetylperoxydgehalt $ 50> obtained

009848/1873 bad original

ν 21 Example 10

By the procedure of Example 8, other solvents were tested * Using methylene isoarayXketon (dor, 141 -. 148 ⁰ C) as a Sicherheitslö'sungsmittel Diaeetylperoxydsioherheitslösung was "get 8 $>" with a Peroxydgehalt 25

Example 11

The procedure of Example 8 was repeated using methylamyl acetate (d * r _e 140-15O ⁰ C) as a safety solvent. A safety product with a diacetyl peroxide content of 25% was obtained

Example 12

The procedure of Example 8 was repeated "where Äthylenglycolmonoätheracetat (dr" 145 to 164 ⁰ C) ale Safe * was used heitslösungemittel. A safety product was obtained with a diacetyl peroxide content of $ 2515>■>

ßAD ORIG'NAL

009848 / 18.7 3

Yersuoh 13

For comparison purposes in the test, a 25? 5 ige solution of diacetyl peroxide in dimethyl phthalate (DMP) commercially available product, Terwendeto This solution is not sure"

The results of the safety tests with the diacetyl peroxide compositions Examples 8-13 are set out in Table II below

BATH 0 0 9 B 4 a / 1 8 7 3

Security checks Sensitivity to impact

Rapid heat test Bruckgefäßprüfung

(xrcjsse the exhaust openings at Bursting of the tensile lines in mm

Evaporation rate

Table II ■ & - -Zns azamsns e t solutions 11a 12, 13, Exam VOi i-Ptaoetylperosi 1Oo NSS NSS (6)
NSS 8th, -SL--. · NSS (1)
92 ⁰ C (D
78 ⁰ G (3)
90 ⁰ C (4)
NSS NSS (D
94 ⁰ C {'0
95 ⁰ C (2)
90 ⁰ C

Time (hours)

none 35.0 change in impact sensitivity none

- * Change of salary in

*** Loss of profit in? S

5 6th 5 no +1.7 +1.0 36.0 37.0 ? 5.0 no no no

<1

<1

no

= 10.0 10.4
no

(1) very mild decomposition

(2) mild decomposition at about

(3) explodes at about ⁰ C (4) not sensitive to etoB

(5) sensitive to shock

(6) frosted sensitive to shock

(7) Peroxide evaporates from EMP

¹ O

o, cn .cd

example

A reactor equipped with a stirrer and a thermometer, jacketed reactor was charged with 285 ml of water, "100 g (1 * 25 MOX) sodium hydroxide (50 5S ~ strength aqueous solution) and 60 g odorless mineral spirits (d 'r ~ 175-205 ⁰ C) loaded.

Under stirring at <-5 ° C was slowly added 37 _t 4 g (0.55 mole) of water stoffperoxyd (50 f * aqueous solution) zugesetzt-. With further stirring at -5 ⁰ C were 113 g OcO mol) of 93 "6 # sodium isobutyryl chloride was added in a period of 30 minutes," After phase separation, the organic phase was washed with water until a pH of about 8 washed "Bae product dried over anhydrous magnesium sulfate. After filtration to give 128 _p 0 g of Sicherheiteprodukts with a Diisobutyrylperoxydgehalt of 51 "E $"

Example 15

The procedure of Example 14 was repeated using a smaller amount of odorless white spirit as a safety oil, thereby providing a safety product. β :? with a diisobutyryl peroxide content of $ 70> raised »

UQ ^for ? O /. ß / 1

^BATH

- 25 ~ Bajgpiel 16

The procedure of Example 14 was repeated with enough odorless solid fuel to give a safety composition with a diisobutyryl peroxide content of 25 # cool vfurdeo

Example 17

Following the procedure of Example 14, but using iron ethylene glycol monobutyl ether acetate (dr, 188 192 ⁰ C) as the safety solvent , a safety product with a content of _{50 0} 5 ^ was obtained

Example 18

The procedure of Example 14 was repeated using diisobutyl ketone (dor, 163-173 ⁰ ) as all solvent solvents .

Example 19

BUeobufcyrylperoxyd was (! ^ B Dutylcelloso, ^{dr? V} n ° C) using vca aoviel KfchylönglycolmonobufcyUlfcher uln Slnherhe'fcnLüöungBmibtBi hergeHfcti '! I b that iVodulri, m ·,. '. \ Tv: un fj *; hf. Lt 'do \ Μ., \>'& »Rim! '<; / · Mtrtid ■

ΰ o ^{ J ü ^ π / ι R 7: i

BATH ORIGINAL

Example 20

Diisobutyrylperoxyd was repeated using such an amount of diacetone alcohol (d r _{o 0169-172} C ⁰⁾ as the solvent Sieherheits that a security product was obtained with a content of 53 »$ 3>.

In the following Table III the values are given which in the safety testing of the M-isobutyryl peroxide compositions described above was received «

Diisobutyrylperoxyd is at room temperature (20-25 ⁰ C) a thermally relatively unstable peroxide and must be stored at low temperatures, so that the content remains active oxygen · The pure Feroxyd can decompose violently if it is not frozen suffer istο The compositions of this invention very mild decomposition at room temperature, as found on control samples in connection with the evaporation rate: according to tests. Sammensetzungen These security door occurs no segregation in shock sensitive "layers under TiefkUhllagerung (0 bia -30 ⁰ C).,

000848/1873

It was found "that the inventive diisocyanate perosyd safety compositions are excellent low-temperature initiators for the polymerization and copolymerization of yinyl and styrofoam compounds"

η η <> μ / ,, η / η 1 ^7;

BAD ORIG'NAL Security checks

3 -hla ^ sapf indlichl-eit

5 ehnelLerhx certification test

rc ", l-iftSf äSprüf ung

e the exhaust opening bsin bursting the rupture in mm

^ 'Evaporation rate »(25 ⁰ C)

t *> time (hours) change in salary in $>

Table III 16. -Compositions 18 _e 19 2Oo Examination of Di isobutyryl peroxide NSS
(3)
55 ⁰ C 17th NSS
(4)
43 ⁰ C NSS
(4)
38 ⁰ C NSS
(4)
37 ⁰ C 14th .15- NSS
(4)
41 ⁰ C (5)
NSS
(4)
47 ⁰ C NSS
(4)
42 ⁰ C

* r? i'.vichtaverlu3t in £

■ e ■ ·

5! Charge of the strike sensitivity =

(D

22.0

no

5 4th (2) -16 29.2 15.0 no no

^ 5 4.0

5 3

(2) (2) -21.0 = -10

16.4 17.0

none none

<5 15

(2) -28

24.5 none

ο ■ * ■ *

2 ^; * "'In a versohlo ?? Senen control sample also an Gehaltsverluat of 15 entered.

r- 2) The closed control samples also lost about the same amount of content.

^: Z '· rtil-äe decomposition at ⁰ ° C

i wash decomposition at ⁰ C

: r.i-.hi: stoSoa-flnalich

(2) -32

28.2

none ^

Oi CD CO

~ 29 ~

Example 21

Following the procedure of Example 14, a di-2-methylpentanoyl peroxide safety composition was prepared using 2-methylpentanoylochloride in odorless white spirit (d * r> 17? - 205 ⁰ O) as the safety solvent. A safety product with a peroxide content of 58.8% was obtained.

Example 22

The procedure of Example 21 was repeated using a smaller amount of geruohloeen teatbenzine as a collateral solvent, resulting in a safety product having a di-2-methylpentanoyl peroxide content of $ 70 o

Example 23

The procedure of Example 21 was repeated with low-boiling naphtha (dr 150 ^ 170 ⁰ O) as all safety solvents. In this way a safety product with a di-2-methylpentanoyl peroxide content of 58.7% was obtained,

009848 / 1S73

- 30 Example 24

The procedure of Example 21 was repeated using diisobutyl ketone (dr * 163-173 ⁰ O) as a safety solvent. A safety product with a di ~ 2 ~ methylpentanoyl peroxide content of 50% was obtained.

Example 25

Following the procedure of Example 21 using 2 ~ Äthylhexylaoetat (dr 192 - 25O ⁰ O) middle Sicherheitslösunga as a security product was nethylpentanoylperoxyd obtained with a content of di ~ 2 ~ 50 96th

When the Sioherheitsprüfung Di described in Examples 21 ~ 2-methylpentanoylperoxydausammeneet2ungen values obtained are shown in Table I. ¥! given below.

ORiGi _NAL

D0S648 / 1873

Table IT HSS unenaeteungen 25th Examination from Tue-J > -methylpentanoyli (3) 21st 22nd 43 ° C HSS (D HSS (3) HSS HSS (3) 42 ⁰ C (3) (3) 41 ⁰ C 43 ⁰ C 40 ⁰ C

Security checks Sensitivity to impact

Son success test

to pressure vessel testing

* Size of the discharge opening at <C 5 4.10 ^ 5 O ^ i

_m advise the tear disk in • ^ well

cd evaporation speed 2 (25 ° C)

Time (hours) Change dea Gehaita in # Weight aver loss in i>

> Change in impact sensitivity

ο 2 Q (1) not sensitive to shock

> (2) sensitive to shock

(3) low decomposition at ⁰ ° C

(4) A sealed control sample lost approximately the same amount of content

5 4th ■ 5 4th 3 (4) (4) (4) (4) (4) -24.2 -22.2 «Ϊ9.2 -22.3 -19.8
* 18.2 20.3 26.5 20.1 11.5 no no no no ketjö 13704

Claims (2)

b »a Sloherheitlusmittel for this peroxide in an amount sufficient to render the composition safe at least "one or more of the The following compounds contain an aliphatic hydrocarbon, an aliphatic ketone, an aliphatic setter, an aliphatic ether, a aliphatic alcohol or et aliphatic compound with at least two identical or rereohieden ketone, Ester, Xther or alcohol groups in the molecule and practically the same rate of evaporation as contains peroxide, which avoids dangerous concentration of the peroxide in the liquid or vapor phase. 009848/1873 2. Composition according to claim 1, characterized in that that it contains a diaoyl peroxide of the formula given in claim 1, in which R is an alkyl group with 1.4 carbon atoms » 3 * Composition according to claim 1, characterized in that » that it contains diacetyl peroxide, di-propionyl peroxide, diisobutyryl peroxide, dipentanoyl peroxide or di-2-methylpentanoyl peroxide as diacyl peroxide. Ao composition according to claim 1, characterized * that it contains a solvent boiling in the range τοη about 140 - 210 ⁰ C at 760 mm Hg " 5- Composition according to claim 1, characterized in that it contains the acyl peroxide in an amount of about 10 - 70 i> and there. » Contains solvent in an amount of about 30 90 ^ » 009848/1873 BATH ORIGINAL