DE1905915A1 - Compound having a peroxy group and an aliphatic azo group - Google Patents

Description

16849

WALLAGE & TIBRFAIT East Orange, H. «Χ. / UNITED STATES

"Compound with a peroxy group and an aliphatic

Paw group "

Ms invention relates to new compounds that contain both peroxy and aliphatic ^ azo groups in the same molecule, and also contain? their use alo Hittel in the production of polymers, whereby they generate free radicals in several stages.

~ »2

BAD OFUGtNAi.

909837/1546

Description of the prior art

The common presence of an azo group and a peroxy group in the same molecule is not new in and of itself. The following such connections have been described: - ■ -

O O

It It

COOC-IJs = N-COC ₂ H ₅ (1)

"fi

1 _

It tt

COOC-O- ^/ -4-N = NU -HX ^ (2)

where X ', X ^s ^, X ^ ₂ ^and % ■' 3 can mean ^{the following:}

O 11

H-, NO ₂ , HH ₂ , J, C ₂ H ₅ O-, CH ₃ C-NH, CH ₅ O-, SO3H,

COCH ₃ , CH ₃ , Br, XC ₃ H ₇ , C ₂ H ₅ , CN and ITOo ^ "

GH »

3 O

OT ₃ -CMC-OH ₃

CN 0 0

909837/1548

CH,

O O O O

(CH ₅ ) ₃ C

ψ 2

E ¹ j (5)

0
H

where R ⁵ -ρ R ^f 2 and R '^ are organic radicals which are inert to azo and hydroperoxide radicals.

None of these known azo peroxides can be used as agents for multistage One such use for these compounds has also been used to generate free radicals not considered. The compound (2) has been reported to be a polymerization initiator which is used in is used at low temperatures. The compounds (3) and (4) have also been used as initiators for vinyl polymerization * The compounds of structure (5) were stated to be photopolymerization initiators and are thermal polymerization initiators, that is, they release free radicals either by irradiation or by heating form what is typical for conventional azo and peroxide initiators. In each of the connections (1), (3) * (4) and (5) the peroxy and azo groups are attached to the same carbon atoH. Thus, these connections suffer eirse equilateral aao and peroxide decomposition and can

909837/1546

accordingly cannot be used as a means for generating free radicals in multiple stages as in the new ones Compounds according to the invention is the case * In the compounds according to the invention Compounds are the azo and peroxide groups not bonded to the same carbon atom, and as a result decomposition can occur in several stages, as is illustrated in the examples.

In the compound (2), the azo part of the molecule is not "Generators of free radicals, at least in the broad temperature range in which vinyl polymerizations are usually carried out. The peroxide part is a generator of free radicals, which is useful for vinyl polymerizations. The azo part in this structure is attached to two phenyl or substituted phenyl radicals, and structures of this type are typical azo dyes · Of these structures is known to be stable and to absorb certain wavelengths of visible light. Thus, the azo part of the Compound (2) for activating the peroxide part through the visible Light can be used and he can also act as a dye can be used to create a color, but it does not settle under conventional vinyl polymerization conditions, eo that free radicals arise. The compounds of structure (2) cannot be used as agents for the stepwise generation of free radicals in the manner as the new compounds according to the invention are used »

(1) Japanese Patent 28,459, Issued December 16, 1965 to H. Minato

(assigned to Teijin Ltd.) j CA. £ 6, 1109Oh (1966).

(2) U.S. Patent 3,271,384, issued September 6, 1966 at Polaroid Corporation.

909837/1548

(3) British Patent 988 255, issued April 7, 1965 at Monsanto Company »

(3,4) Canadian Patent 750,380, issued January 10, 1967 to Monsanto Company »

(5) a) U.S. Patent 3,278,304, issued 11 “10.1966 to Gevaert Photo-Production U.V.

b) British patent 1,054,125, issued January 4, 1967 to the same company.

Summary of the invention

1. Connections

The compounds according to the invention contain both sine Peroxy group as well as an aliphatic azo group and have the general formula

wherein (1) m is an integer from 1 to 2;

(2) η is an integer from 1 to 20;

(3) R ^f -

, 1, 1

(^ N) -CR ₅ - (X) or C = K) -CR ₅ -YR ₆ - (X)

R ₂ R ₂

means;

ORIGINAL INSPECTED 909837/1548

(4) X one of the following containing a peroxygrappe Radical means

0 0 R ₁

M If 1 'j

-C-OOR ₅ , -OC-OOR ₅ I -C-OOR ₅ , R ₅ OO-C-OOR ₅ ,

R ₁ R ₁

0 0 0 0

η if it ir

-C-OO-G-, -00H, -OC-OO-CO- and 0 R ₁ R ₁ 0

W. 11 I'J'Ti

-C-OO-C-Rc-C-OOC-;

1 J I

R ₁ R ₁

(5) Y is a divalent radical, viz

0 0

ti Il

Is -CO- or -OC-;

(β) R ₁ denotes an aliphatic radical having 1 to 10 carbon atoms

. (7) Rp means one of the following radicals:

0 0 0

Il It Π Il

R ₁ OC, H ₂ ITC, R ₁ -, R ₁ O-, R ₁ OCO, R ₁ CO, ArO- ₉ 0

ti

ArCO-, KC-, N ₅ -, Cl- and Br-, where Ar is an aromatic radical having 6 to 12 carbon atoms;

(8) R _{5 is} a tertiary aliphatic.es radical having 4 to 10 carbon atoms;

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(9) Ης a divalent aliphatic radical with Means 1 to 10 carbon atoms;

(10) Bg a divalent aliphatic radical with

1 to 10 carbon atoms or a divalent aromatic radical bit 6 to 12 carbon atoms means;

(11} B | and Bc together ax the tertiary carbon atom in B * a trivalent cycloaliphatic Hadikal can mean and

(12) B a) a tertiary aliphatic radical with 4 to 10 carbon atoms,

b) (Β · -Χ) or

c) B *, if m is equal to 1, means, where Σ is a bivalent radical "

2. Polymerization process

A. A process of the invention produces a block polymer by the following ifeflnahiaen:

(1) Preparation of a polymer having azo groups by reacting a vinyl monomer and an azo-peroxy compound of claim 1 under vinyl polymerization conditions, the conditions being controlled so that the peroxy-oxygen bonds are before the azo-carbon bonds break break and wherein the break of the peroxy oxygen bit ₂ fertilize has the effect of initiating the polymerization; and

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(2) Reaction of vinyl monomer with your polymer from the stage (1) under such conditions that the Ago-carbon bonds of the polymer of stage (1) break * whereby a block polymer product is formed.

B. Another inventive method results in a Block polymer by the following measures s

(1) Production of a polymer which contains peroxy groups on » has, by reacting a vinyl monomer and a Azo-peroxy compound of claim 1 under Yinylpolymerisationsbedingungen, the conditions being controlled so that the azo-carbon bonds prior to breakage of the peroxy-oxygen bonds breaking, the breaking of the azo-carbon bonds has the effect of initiating polymerization; and

(2) Reaction of vinyl monomer with the polymer of step (1) under such conditions that the peroxyoxygen bonds of the polymer of step (1) to give a block polymer product.

Description of the invention and the examples

1. Connections

The compounds according to the invention have the general formula

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They can be simple compounds when η is 1 and m is 1 or 2, or they can be polymeric compounds when η is 2 to 20.

In the definition of R ¹ as a divalent radical

-C-Rc-R ₂ -J

(X) or (»Bf)

-C-Rc-Y-Rr-

the azo nitrogen (= N) and the peroxy radical (X) are shown, to show the relation of the groups to the group R '.

.R | can be any aliphatic radical having 1 to 10 carbon atoms. In general, R _{1 is} an alkyl radical »

Rg can be any aliphatic radical having 1 to 10 carbon atoms, especially an alkyl radical, or a cyano radical (-CH) or an alkoxy, aryloxy, acyloxy, alkoxyearbonyloxy, alkoxycarbonyl, carbamoyl, aroyloxy, Be azido, chloro or bromo radical.

Rf- can have any aliphatic divalent radical with 1 to 10 carbon atoms and is especially an alkylene radical.

Y is a radical of the formula

ti

-CO- or -OC-.

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Eg can be an aliphatic divalent radical with 1 to Carbon atoms, in particular an alkylene radical, or an aromatic divalent radical with 6 to 12 carbon atoms, such as a phenolic or capaphthylene radical.

X corresponds to the definition in the summary given above of the invention (1st compounds),

In the divalent radical

0 R ₁ B * 0 -C-00-C-Hij-C-OOC-

R ^ can be a tertiary carbon atom and an R ^ together form a cycloaliphatic divalent radical.

R can (a) a tertiary aliphatic radical with 4 to 10 carbon atoms, in particular a t-alkyl radical, or

(b) the combination radical R "-X or

(c) if m is the same, t and X is a bivalent radical according to the definition above, then be equal to R «.

The compounds may be open-ended or closed, d _o h. cyclic, be. Example 1 shows a cyclic compound wherein R ^ R ^ -CCJFjCiCH ^ CHgCHg-; m = nl and X - (O) -COQ-C (O) - means.

90SS37 / t546

Various exemplary compounds of the invention are prepared in the examples given below.

Usability

The compounds of the invention can be used in any reaction in which a corresponding azo compound in Absence of the peroxy group or a corresponding peroxy compound could be used in the absence of the azo group, taking the presence of the azo group into account pull is. These compounds can be used as curing initiators for mixtures of yinyl monomers and unsaturated monomers Polyester resins can be used. They are important initiators for polymerization reactions, especially for polymerizations of vinyl monomers. The initiator can be chosen so that the aso and peroxy groups are simultaneous or break successively. The use of connections with different breaking speeds given conditions allows the preparation of polymers with either azo groups or peroxy groups as Part of the polymer. These polymers are ideal for making block or graft polymers, and this is a preferred use of the compounds according to the invention. Examples 6, 7 and 20 illustrate this preferred one Feature of the invention.

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description

2. Polymerization process

These methods are directed to the use of the invention Compounds for the preparation of block polymers by a sequential process in which a compound I wei used to initiate vinyl polymerisation, to make a polymer that is either azo or peroxy « groups as! Peil of the polymer contains, ^ e after, under what conditions the polymerization is carried out. The polymer containing azo or peroxy groups is then further polymerized with vinyl monomer under such conditions that the azo or peroxy group breaks, whereby the Block polymer is formed.

These sequential and / or preferential decompositions of the aiso and peroxide parts of the molecule can be achieved by a wide variety of techniques. One method is to use two different temperatures, taking advantage of the thermal decomposition rates of the azo and peroxide parts of the molecule. Another method, which is also based on different thermal decomposition rates, is to use the same temperature but different reaction times «. For example, the Peroxydteil of azo-peroxide of Example 3 vrtirde be decomposed after 13 minutes at 7O ⁰ C to 50 i> while the Azoteil is decomposed at the same time only less than $ 4. the latter would not have decomposed to 50% for 179 minutes at the same temperature.

Another method is to use an activator

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- 13 -

for the peroacyd part, for example an amine, a transition metal salt etc., which keeps the azo part intact, since the azo structures in the compound X against such activators are insensitive. The azo part can then follow decomposed either hermically or by irradiation (e.g. ultraviolet). Another one Technique consists in thermally decomposing a part (either the azo or peroxide part) and then to decompose the other part by irradiation or vice versa. Another method is two different To use irradiation sources successively, with an irradiation preferably a part and the second irradiation preferably the other part of the azoperoxide molecule attacks.

Thus, a wide variety of techniques can be used for the gradual Free radical generation can be used when taking advantage of the difference in physical and chemical properties of the new azo peroxides Formula (1) is used. Multi-step free radical generation is very common in the vinyl polymerization field useful. Block copolymers can be made from a variety of combinations of polymerizable vinyl monomers will.

The stepwise generation of free radicals is also used in the conventional polymerization of ethylene and styrene. Currently this is done using two or more polymerization initiators with different thermal stability achieved.

Any vinyl monomer that can be polymerized by free radicals can also be used to make the azo or per-

909837/1546

Oxide-containing polymers can be used and any combination of the individual vinyl monomers can be used to produce the block polymers, typical vinyl monomers are ζ.Β.ϊ styrene, vinyl chloride, vinyl acetate, A "thylacrylate, methyl methacrylate, butadiene acrylonitrile, acrylamide, acrylic acid, methacrylic acid, vinyl carbazole _t vinyl toluene, vinyl pyridine, vinylidene chloride, and the like.

Conventional polymerization techniques can be used be, i.e. block, solution, suspension or Emulsion Polymerizations. The choice depends on the usual considerations for the choice of technique, for example on the water and oil solubility of the monomer and / or of the initiator, of the desired molecular weight range of the polymer, temperature control (or control of the exothermic reaction), etc.

The temperatures at which the polymerizations are carried out depend on the polymerization technique, the monomer, the solvent or the suspending medium and the ± m polymer desired physical properties, but mostly azo-peroxide initiator and the decomposition of the azo or Peroxide part of the initiator selected process. Activation of the peroxide part by amines, reducing agents, transition metal arbosylates, etc. "can be carried out from below -2O ⁰ O to au its normal setting temperature" The same applies to the activation of the peroxide or azo parts by irradiation. The sources of irradiation can be ultraviolet rays, In In the presence of photosensitizers (ie certain azo compounds), visible dust can also be used. The temperatures used for the thermal decomposition of the azo or peroside parts depend on the thermal

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Stability (half-life) of the azo or peroxide group in the molecule. These half-lives can be quantified for each azo peroxide compound by conventional methods can be determined, for example by gas evolution and by analytical iodometric, ultraviolet or gas chromatographic Techniques where the rate of disappearance of each part (azo or peroxide part) is determined at a given temperature. Such half-lives were observed for the compounds of the examples 1 to 5 determined.

However, it is not necessary to accurately determine the half-life of each part, since most half-lives can be predicted with little error from the most closely related analogous monomeric azo or peroxide structures, many of which are well known. Such ten hour half-life temperature ranges of some typical peroxide and azo structures are given in Tables I and II. (More detailed data on the individual compounds are available when E, R ¹ , R ", and R" ^{1 are} known; this data was used to determine the half-life side ranges of the compounds prepared in Examples 8-19).

There are many references from which the conditions for performing the procedures can be found »All Vinyl monomers can be polymerized, for example, by peroxide or azo initiators. Azo and peroxide initiators are used in all four free radical polymerization techniques. Furthermore it is in the Technology known for a long time, peroxides with amines, thihergangsmetallsalsen and activating reducing agents, and both azo and peroxydiators with ultraviolet radiation or visible light in the presence of photosensitizers to activate.

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General structures of different TABLE I. Ten hours" One hour half-life temperature range
Peroxides 0
ti
R ¹ CH ₂ COOR ildlüWSiuli ¹ '
side area
⁰ C Peroxide class 0
ti
R "CHCOOR 102 R « 66-79 t-alkyl peroxy ester R "'0
• Il
R «-0 - COOR
I. R ¹ 54-55 0
^ C = G-COOR 0
Il 98-105

Diacyl peroxides

(R ¹ CH ₂ CO-)

61-69

0 (R »-CH-CO-).

I '

R ^f

27 - 34

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fermentation peroxide class

General structures

Ten hour

half-life

Zeitbereiek

54-75

Malkylp eroxides

Β »'Β» «

9 t

! »« - α-ο-ο-σ-Β »

8 *

B

B *

117 - T128

Mp eroxyketal e

1"

)IF

101-110

0
It 99 O ~ alkyl ~ O, Ot-alkyl-
monoperoxy carbonate B ⁵ OCOOR 0 0
η η . 45 Peroxydicarbonates E ¹ OCOOCOB ¹ 155 - 172 * Hydroperoxide e BOOH

where B is a t-alkyl radical and

E ', B ⁿ and B "" mean aliphatic ^ or aromatic »

* Alkyl and aralkyl hydroperoxy oils are generally used in low temperatures in common with bedox catalysts emulsion vinyl ionization polymerizations are used.

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* Ji

- 18 -

TABLE II

Ten-hour half-life temperatures of various azo compounds ^

General structure ten-hour half-value

time range o «

Il

OH,

P CH ₅ -CF = SN-C-OH ₅

CH CH

CIf

79

^r ntf \ ΛΤΤΓΙΤΤ 7 O f \

R = R '"(

0 R ³ ^ ROCCH ₂ CH ₂ 7β -

r R'-RCOCH ₂ 77 -

R + ■ R «» -

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- 19 Continuation of IABEELE II

General structure "ten-hour half-value"

time range

+ E <* - (CH _{2) 7-55}

CH _x CH, CH, -C-H = K C-CH,

CHjCaO O = CCH ^

Examples

Exemplary compounds according to the invention and exemplary Uses of some of these compounds in the Bind processes of the invention in the following working examples which are not to be interpreted in a restrictive sense.

909837/1546

B_e_i s pie 1 1

Preparation of 6,9-dimethyl-6,9-dicyano-A, 1,2-dioxa-7 »6-diazacyclododecane-3,12-dione.

CH, .. .. OH ^

OH ₉ GH "

CHp CHp

V /

c-oo— c

ο ■ ο

Compound I wherein HsR ⁹ «-0-0H ₂ -CH ₂ -J in« 1; η a 1 and

Og CK

X = -COOC-.

30 ml of methylene chloride were added to a solution which contained 2.0 g (0.028 mol) of 50% strength hydrogen peroxide and 4.8 g (0.0616 mol) of 50% sodium hydroxide in 100 ml of water. The resulting mixture was abgeMihlt to 1O ⁰ C and stirred while a solution containing 8.4 g (0.0264 mol) of cis-4 * 4 Bisäurechlorids ^s contained azobis- (4-eyanovaleriansäure) in 50 ml of methylene chloride while a period of 40 minutes sugegeben x ^ urde, wherein the Realetionstemperatur was maintained during the addition of 8 to 10 ⁰ C. Bas Eeaktionsgemiscli was further stirred for 3 hours at 0 to 10 ⁰ C. Then, 30 ml of a saturated solution were added by Hatriumbicarbonat and the reaction mixture was stirred for 15 minutes at 1O ⁰ C "The Methylencliloridschicht was separated, cooled to 0 to 3 ⁰ C and KweiEjal al 40 with a 5 ^ strength ITatriumbicarbonatlösungr

90983 7/1546

then washed three times with 20 ml of a 3% potassium hydroxide solution and then twice with water, dried over anhydrous sodium sulfate and filtered. The resulting methylene chloride solution was concentrated to about 40 ml and at -2O ⁰ C for several Cage to crystallize allowed to stand. The methylene chloride solution was decanted off and the remaining white solid was dried ^{under vacuum at 0 ° C.} The methylene chloride solution was further concentrated and stored at -20 ⁰ C again, and a further batch of crystalline product was obtained. The combined products weighed 2.6 g (35.4 # yield) and additional product was still present in the methylene chloride mother liquors.

The product did not melt up to 103 ⁰ C, at which temperature it exploded with a loud bang. Its infrared spectrum agreed with the structure of 6,9-dimethyl-6,9-dicyano-Δ, 1,2-dIoxa-7,8-diaaacyclododecane-3 , 12-dione. It showed absorption bands for the cyano and diacyl peroxide groups. The product is sensitive to Sehlag and Zersetzungsgeschwindigkeitsstuäien showed that the Diacylperoxydteil in o-dichlorobenzene considerably faster (τ * / "& * 99 minutes at 70 ⁰ C) than the Azoteil Ct ₁ Z ₂ ^ * 236 minutes at 70 ⁰ C. ) of the molecule decomposed. The product can be long at -20 ⁰ C to be stored than 1 month.

example

Production of the polymeric peroxide of trans-4 »4 ⁹ -azobis- (4-eyanovaleric acid), which is terminated with carboxylic acid groups.

909837/1546

/ TO OH, OH, O--OC (GH ₂ ) ₂ 0-Η «Π-0- (CH ₂ J ₂ OO X CI CH y η

CH * «■ ->

Compound I, wherein RR · »-C-CH ₂ CH ₂ -, m * 1, η 4.3 and

S 8 on

X «-COOO-,

To a stirred solution containing 2.29 g (0.057 mol) of sodium hydroxide and 0.965 g (0.028 mol) of hydrogen peroxide in 30 ml of water was added a mixture containing 3 ×> 0 g of sodium dihydrogen phosphate, 3.0 g of disodium hydrogen phosphate and 60 ml of water contained, bsi 0 to 5 ⁰ C sugegebsm. Ser to the stirred solution dropwise x-zährencl 25 minutes, a solution of 8 ₅ 5 g (0.027 mol) of the diacid chloride of trans-4,4'-Äzobis ~ (4 - cyanovaleric acid) in 60 ml of methylene chloride, keeping the temperature "Dae Eeaktionsgeiaisch was kept during the addition below 3 ⁰ C cold more i was stirred for 1/2 hour and then filtered. The solid product was washed with methylene chloride and Viasaer and then dried. Sa weighed 4 * 9 g (66.2 $> prey) and had an active oxygen content (determined by iodometric titration) of 4 »4 $? which corresponds to an average η value of the above structure of 4.3. The product was sensitive to impact and decomposed at 106 ⁰ C with a loud bang »

A further 1.8 g (24.3 i <> yield) of a product with low pur molecular weight (average η value ~ 1> 585) siit an active oxygen content of 1, β8 fo was prepared from the aqueous methyl en chioridfiltrat by Abdaiapfen of the methylene chloride obtained with a stream of nitrogen gas o That

BATH 909837/1546

The product was less sensitive to blows than the first isolated Product.

The infrared spectra of both products agreed with the above Structure. Decomposition rate studies of the first product indicated that the peroxide bonds break in water considerably faster (t.j / p * »= * 369 minutes

at 6O ⁰ O and 102 minutes at 7O ⁰ C) decomposed than the azo-1/2

bonds Ct ₁ / _o * & 860 minutes at 6O ⁰ C and 231 minutes at

This product un cured an unsaturated polyester resin material
softenable resin.

Polyester resin and styrene at 100 ⁰ C in a hard non-er

B_e i s ρ i e 1 3

Preparation of the polymeric peroxide of trans-4,4 ^c -azobis- (4-cyanovaleric acid), which is terminated with sodium carboxylate groups *

/ ^ Q CH, OH *

/ ti! 2 1 y

Na - {- OC (CH ₂ ) ₂ 0-ίί = * ϊϊ-σ- (CH ₂ ) ₂ C0-j Na

\ CN CN ^ y η

»^
Compound I, wherein R = R ^; = -C-CH ₂ CH ₂ -, m - 1, η - 2.62 and 9 8

Zv. a stirred solution, which contains 0, ^ 2 g (0 _? 013 mol) of ifetrium

909837/1 5 4 6

»11 1 1

* 1 ill

- 24 -

hydroxide and 0.225 g (0.0066 mol) of hydrogen peroxide in 13 ml of water, a solution containing 1.9 g (0.006 mol) of the diacid chloride of trans-4,4 ^f -asobis- (4-cyanovaleric acid) in 12 ml methylene chloride contained ₉ at 0 to 5 ⁰ O was added. It formed a white precipitate. The reaction mixture was stirred for 2 hours and then filtered. The solid product was washed with water and with methylene chloride and then dried in vacuo. 33s ' weighed 0.8 g (41.2 # yield) and decomposed at 97 ^° C. with a loud bang.

The product was shock sensitive and its infrared Spectrum agreed with the above structure · 25 © r Active oxygen content, determined by iodometrisohe litration, was su 3.2? $ found what an average η value in the above structure corresponds to 2.62.

The product is partially soluble in water and Zereetzimgegeschwindigkeitsstudien showed in water so that the Peroxydbindungen considerably faster _(t1 / ₂ <= 3 minutes at M3

"Translated as the azo bonds (i at 70 ⁰ C).

70 ⁰ C) decomposed than the azo bonds (tj />, «= * ¹ ^ 5 minutes

Example 4

Preparation of the di-t-butylperoxy ester of eis-4,4 * -azobis- (4-cyanovaleric acid).

0 / K «IL 0« / \ it

J-CH ₃ CH ₅ -C- (CH ₂ ) ₂ C00C ₄ H _g -t

909837/1546

? ^Η 3 2

Compound I, wherein R "R" X and R ¹ = -C- (CH ₂ J ₂ -, X "

CH m «1 and n * 1,

2.18 g (0.024 mol) of 99.3 were added to a solution which contained 3.8 g (0.012 mol) of the diacid chloride of cis-4,4'-A) 3obi8- (4-cyanovaleric acid) in 40 ml of methylene chloride # Pure t-butyl hydroperoxide at 0 to 5 ⁰ C issued. The resulting solution was stirred at 0 to 5 ⁰ C, during which time 1.9 g (0.024 mol) of pyridine in an equal volume of methylene chloride was added "The reaction mixture was stirred to 3 ⁰ O 4 3/4 hours at 0 and then at 21 ⁰ Allowed to warm to C, whereupon it was ^{cooled to below 10 0} O and washed with 20 ml of water. The cold methylene chloride reaction solution was then washed in the following manner:

1) once with 20 ml of dilute hydrochloric acid,

2) once with 20 ml of water,

3) once ml of a solution containing 5 $ of sodium sulfite and 5 i "contained Satriumacetat 20,

4) twice with 20 ml of a 5 # solution of sodium bicarbonate, and

5) twice with 20 ml of water.

The resulting methylene chloride solution was poured over magnesium sulfate dried and filtered, and the methylene chloride was evaporated to give 4.0 g (78.6 $ yield) of the di-t-butyl peroxyester of cis-4 »4'-azobis- (4-cvanovalerlaa9äure) obtained bp 104-106 ° 0 with decomposition.

The product has an active oxygen content {be

909837/1546

correct by joint titration) of 7 »37 $, what indicates a purity of 97.7 #. The infrared spectrum of the Product agreed with the above structure and showed perester carbonyl and t-butyl peroxy absorption bands and no carboxylic acid, acid chloride or hydroxyl absorption bands »

The infrared spectrum of the product did not change when it was ^{left to stand at 21 °} C. for 2 days, which indicated stability at room temperature. The product was only moderately sensitive to sagging. Zersetzungsgeschwindig · = keitsstudien in trichlorobenzene showed that the Azoteil considerably faster Ct ₁ y ₂ ^ a 92 minutes at 80 ⁰ C) decomposed than the Peresterteil the molecule Ct ₁ / g '=' 319 minutes at 8O ⁰ C).

example

Preparation of the mono-t-butyl peroxide ester of diacid chloride of trans-4,4'-azobis (4-cyanovaleric acid).

0 CH

tC ₄ H _g 00C (CH ₂ ) ₂ C-CH

s. ο

CH-C-CCH ₂ ) ₂ CC1

CU

Compound I, wherein m «t, n» 1, E «ClC- (CH ₂ ) ₂ C-, OH, 0

f -> II

R «S = -c- (CHg) ₂ - and X» -CO0C ₄ H ₉ t. OTT

909S3771546

Solution to a stirred cold (O to 2 ⁰ C) 2.18 g (0.024 mol) of 99 »3/3 of pure t-butyl hydroperoxide and 1.35 g (0.024 mol) in Kaliumhydroacyd 41.5 ml water was over a period of 10 minutes to a solution containing 3.8 g (0.012 mol) of the diacid chloride of trans -4 »4'-azobis (4-cyanovaleric acid) in 30 ml of methylene chloride, the reaction temperature during the entire The addition was kept at 0 to 2 ^° C. The reaction mixture was stirred cold for an additional 18 minutes and then the layers were separated. The methylene chloride layer was washed twice with 10 ml portions of 5% sodium bicarbonate solution and once with water, dried over magnesium sulfate and filtered. The methylene chloride solvent was evaporated to give 4.6 g (theory> 4.5 g) of a low melting product,

Recrystallization from benzene-pentane at -7 ⁰ C gave 2.55 g of product that contained an active oxygen content of 4.30 # (theory "4.32 So). Its infrared spectrum agreed with the above structure and showed both perester ale and acid chloride carbonyl absorption bands. Decomposition studies in Dioetyiphthalat at 9O ⁰ C showed that both the azo and the Peresterbindungen at this temperature simultaneously decomposed "The product had a half-life of about 28 to 32 minutes. Obviously, at this relatively high temperature, the perester suffers induced decomposition.

ORIGINAL INSPECTED 9098 3 7/1546

Example 6

A. Preparation of an azo-containing polystyrene using of the azo peroacyd initiator * from Example 1

OH,, polystyrene - (OH ₂₎ GO-JfoN-O- (OH _{2) 2} -R polystyrene

OS CN

0.7285 g of 6,9-3) im ethyl-6,9-dioyano »Δ ⁷ , 1,2-UiOXa - ?, 8-dia2Äcyclodoüecan ~: 3.12-dicm (from Example 1 ), dissolved in 3 g of methylene chloride, was added. The heat ion mixture was stored in a sealed tube for 24 hours at 50 ⁰ O under nitrogen and then dissolved in benzene. The polystyrene was obtained by precipitation from the benzene solution by adding methanol. It was autogenized again in benzene and reprecipitated with methanol. After a further reprecipitation, 5.245 g of azo-containing polystyrene were obtained.

An empty attempt, but under the same conditions run without initiator gave only a 0.5% Conversion of styrene into polystyrene by thermal polymerization «,

B. Production of a polystyrene / polymethylethyl acrylate block polymer from the azo-containing polystyrene yob J

A mixture of 9 g of methyl methacrylate and 1 g of the azotole Polystyrene from A was made under nitrogen in one

909837/1546 ORIGINAL fNSPECTI ©

closed tube ^{heated to 75 0} G for 7 hours. The resulting reaction mixture was taken up in benzene and the block copolymer was precipitated with petroleum ether. After drying, it weighed 4 »5 g. Its infrared spectrum showed the characteristic absorption bands of polystyrene and polymethyl methacrylate.

In a üeerversuch Methylmethaerylat gave after 7 hours at 75 ⁰ C, no polymer.

Another indication of the formation of a polystyrene / polymethyl methacrylate block copolymer was the following Get demise tests:

Polystyrene homopolymer

Polymethyl methacrylate homopolymer

Polystyrene / Polymethylmethacrylat-Blockmis ehpolymer

chloroform
Demise time

comparison
14 P pests

0.614 g

8.772 g
0.5 hours

Test 1
$ 21 solids

0.614 g 0.614 g

0.614 g

0.614 g

Test 2 14 i> Solids ^

0.614 g 0.614 g

0.614 g

8.772 g 13.158 g> 145 hours, 41 hours

The ability to stabilize is determined in the laboratory by empirical tests in which the stabilized solution with a comparison solution is compared. The time for the appearance of two separate layers is measured. It

909837/1546

• * ■ »· J i JJ $

* Λ »i YY YYY #

JJ J>. IJ J J. J

- 30 -

It should be noted that the results are not for comparison the effectiveness of the various polymer systems that can be used, 4a even "the polymer molecular weight considerable changes in the separation since the two systems made from the same monomers. However, the laboratory tests are at the Identification of potential stabilizers of importance.

It is known that when two different polymers are brought into solution in a common solvent (this is actually a dispersion) the solution (dispersion) separates into two layers ₃ (ie it mixes) over time have different polymer compositions. Homogeneous melts of two different polymers often show undesirable segregation or formation of a heterogeneous dispersion of one polymer in the continuous phase of the other polymer when solidifying is maintained, the stability of the dispersion is important. A third component of the mixture which improves the dispersion stability of the mixture is known as a stabilizer in certain specific fields. This stabilizer is referred to as a "compatibilizing agent".

909837/1546

A. Preparation of a peroxide-containing polystyrene using the azo-peroxide initiator from Example 4.

OH _x

t-CL HqOOC (CH ₂ ) 2-C polyetyrene

A solution of 5 g of styrene and 1 g of di-t-butylperoxyeeters of cis-4F4 ^l ^ azobis (4-eyanovaleriansäure) (from Example 4) 110 Hinuten was heated to 70 ⁰ C under nitrogen in a sealed tube. The cooled reaction mixture was dissolved in benzene and poured into methanol in order to precipitate the peroxide-containing polystyrene, which after drying weighed 3> 2 g.

Its infrared spectrum showed the characteristic absorption bands from polystyrene and from the t-butyl peroxyester groups.

B. Preparation of a B polystyrene-polyethyl methacrylate block copolymer from the peroxide-containing polystyrene from A.

A mixture of 2 g of methyl methacrylate and 1 g of the peroxide-containing Polystyrene from A was heated to 85 ° C. under nitrogen in a sealed tube for 3 hours. After cooling down the resulting reaction mixture was dissolved in a benzene / acetone solvent mixture, and the polymethyl methacrylate homopolymer was made by adding hexane

909837/1546

precipitated and filtered off. After removing the solvent before the filtrate under vacuum remained 0.8 g of block poly » mer back.

Its infrared spectrum showed the characteristic absorption bands of polystyrene and Polym®thylinethaerylat _e

Another sign of the formation of a polystyrene / polymethyl methacrylate blockmisohpolyii @ rs was obtained from the following delineations.

comparison
5 * $ 3 fixed
fabrics (Dest
5.3 mill
fabrics Polystyrene homopolynos 1 g 1 g Polymethylinethacrylathoino-
polymer 1g 1 g Polystyrene / polymethyl methacrylate
lat block copolymers 0.7 g chloroform 37.5 g 51 g Disappearance time 30 min 150 min Example 8

Preparation of di- [4-t-butylazo-4-cyanovaleryl3-peroxide.

CH- O O CH,

ι J - η st s-

-σ-υ ^ ΐϊ-ο (oh «)

90S837 / 1 54

CEL O

» ·> η w

Compound I, in which R - t-CJSg-, Ε ¹ = -C-CH ₂ OH ₂ - * X * -COOC-, m β 2 and η «1.

To a solution of 0.48 g (0.012 mol) Natriumhydroperoxyd and 0.40 g (0.006 mol) of a 50 jSigen hydrogen peroxide in 10 ml of water at 1O ⁰ C a solution of 2.7 g (0.0118 mol), 4- t-Butylazo-4-cyanovaleryl chloride in 10 ml of benzene was added over the course of 5 minutes. After the addition was complete, the reaction mixture ^{was stirred for a further half an hour at 10 °} C. and then for a further 15 minutes, during which the temperature was allowed to rise ^{to 23 ° C.} A further 10 ml of benzene were added, the benzene layer was separated off, _{washed with 30 ml of 10% NaHCO 3} solution and 15 ml of water, dried over anhydrous sodium sulfate and filtered off, whereupon the benzene was driven off. A white crystalline solid was formed which weighed 2.3 g (93 $> yield). The product had a melting point of 87 to 88 ^° C. with decomposition and a melting point of 91 to 92 ^° C. after recrystallization from benzene / pentane. The material was 100 # pure by HJ analysis. The product was not impact sensitive and its infrared spectrum agreed with that of the desired product.

Has the Azoteil the molecule a 10 hour half-life temperature of approximately 76 ⁰ C, while the Peroxydteil has a 10 hour half-life temperature of approximately 63 ° C.

ORIGINAL INSPECTED

909837/1546

'* * * YY Λ ii J it

Be i a ρ ie 1 9

Manufacture of t-Biatyl-4-t-butylazo-4 - eyaEQpero3Eyvaler @ .t <

t J

OS

O η

Compound I, in which H = t-Ο, Ηη-, S ⁸ = -0-CH ₀ GH ₀ -, X »

-GOOC ₄ H ₀ t-, ma 1 and η »1.

3.74 g (0.03 mol) of 45% KOH were added to a solution of 2.7 g (0.03 mol) of a 99% strength thydroperoxide in 15 ml of water at 5 °. The solution was cooled to 3 ⁰ C and a solution of 6.3 g (0.0275 mol) of 4-t-Butylaso-4-cyanovalerylehlorid in 10 ml of benzene was added during half an hour, during which the temperature is between 3 ° rand 5 C was held. After the addition was complete, the reaction mixture was stirred for an additional hour at tree temperature. The benzene layer was separated, washed twice with 10 Seiger 3SaHCO 3 solution and once with water, dried over anhydrous sodium sulfate and filtered off, after which the benzene was driven off. A liquid weighing 6.8 g (88 <fo yield) was obtained.

Iodometric analysis gave the product a purity of .88 1/2 5 & O The infrared spectrum agreed with that of the desired Product and there were no signs of it

909837/1546

f C I

- 35 -

free t-butyl hydroperoxides are present. Sas product was

not hit

Nitrogen.

not sensitive to impact. It developed slowly at 90 ⁰ C

The Asoteil of molecules besitet a 10-hour Halbwertsseittemperatur of approximately? 6 0 °, while the Peroxydteil has a 10-hour half-value period temperature of more than 102 ⁰ C.

Example 10

Production of 1,3-dimethyl-3- (t-butylperoxy) -butyl-4-t ~ butylazo-4-oyanovalerate.

(CH ₅ ) 5C-

CH, 0 CH,

ι ■> η t ->

car CH ₅ CH ₅

CH, 0

Compound I, where R = tC ^ Hg-, R '= -C-CH ₂ CH ₂ CO-CH-CH ₂ -,

CiT · CH ₃

X «-COOC ^ Hg-t, m = 1 and η = 1 H

A solution of 5.0 was added to a solution of 4 _{t of} 15 g (0.0219 mol) of a 97.5 2-methyl-2-t-butylperoxy-4-hydroxypentane and 3 ml of pyridine in 15 ml of ether at 5 ^° C. g (0.0219 mol) of 4-t-butylazo-4-cyanovalerylehloriä in 10 ml of ether were added. A white precipitate of pyridine hydrochloride formed immediately. The addition of the acid chloride

»09837/154

solution was carried out at 5 ° O for 15 minutes. The reaction mixture was stirred for a further hour at room temperature. The reaction mixture was filtered off and the ether filtrate was washed with 5 # HOl, 10 # NaHCO ^ solution and water, dried over anhydrous sodium sulfate and filtered off, whereupon the ether was driven off, leaving a light brown liquid weighing 7.4 g (yield 88 1/2 $) remained.

The product was chromatographed over aluminum oxide and eluted with fentan. Formed after evaporation of the fentan 6.3 g of a yellow liquid. The infrared spectrum of the purified product agreed with that of the desired one Product. The product was not shock-sensitive «

The Azoteil of the molecule has a 10-hour Halbwerte- 'life temperature of approximately 76 ⁰ C, while the Peroxydteil has a 10 hour half-life temperature of approximately 126 ⁰ C. ·

Example 11

Preparation of 1,1-Tetramethyltetramethrlen _r 4I4-bis- (4-t-butylazo-4 cyanoperoxyvalerat).

CH, 0 CH, CH, S CH,

CN CH ₃ CH ₃ CN

OH «t *

Compound I, wherein R «tC ^ Hg-, R ¹ = -C-CH ₂ CH ₂ -, m = 2,

CN

909837/1546

η = 1 and X «

CH,

CH,

! I

-COOC-CH ₉ CHp-C-OOC-

CH,

CH,

To a solution of 2.72 g (0.0152 mole) of 2,5-dimethyl-2,5-dihydroperoxyhexane and * 5 ml of pyridine in 30 ml of ether of 10 ⁰ C was added a solution of 7.5 g (0.0328 Mol) 4-t-butylazo-4-cyanovaleryl chloride in 10 ml of ether are added for 10 minutes. The reaction mixture was stirred for a further hour at room temperature and filtered off in order to separate off the precipitated pyridine hydrochloride. The ether filtrate was washed successively with cold 5 # KOH, 5 # HCl, 10% HaHCO, solution and with saturated HaCl solution, dried over anhydrous sodium sulfate and filtered, after which the ether was driven off. A viscous liquid weighing 6.8 g (79 # yield) was obtained. The liquid solidified when standing in the refrigerator. The pesticide was recrystallized from pentane / benzene, a white crystalline solid with a melting point of 90 to 92 ^° C. being obtained.

The infrared spectrum of the product - ^M »matched that of the desired product. An iodometric analysis of the compound showed that 5-77 $ active oxygen was present (theoretical active oxygen = 5.65 #). The product was not impact sensitive.

The Azoteil of the molecule had a 10-hour half-life temperature of approximately 76 ° C, while the Peroxydteil having a 10 hour half-life temperature of approximately 102 ⁰ C.

90 9837/1546

Example Ij?

Production of 4,4 * -Azobis- Γ [1,3-dimethyl-3- (t-butylperoxy) -butyl] -4-cyanovalerate j

CH, O CH 1, CH, O CH _x

) 5COO-G-CH ₂ -CHOC-CH ₂ -CH ₂ -C-IrSIi-C-CH ₂ -CH ₂ -COCH-CHg-C-OO-C (CH ₅ )

__ ₃ CH ₃ CIT ClT CH ₃ CH ₃

CH, O

β ·? ft

Compound I, where R = R'X and R '= -C-CH ₀ CH ₀ -COCH-CH ₀ -,

₃ car

X a = COOC _A H _Q -t, m = 1 and η ~ 1.

To a solution of 4.75 g (0.025 mol) of 2-methyl-2-t-butylperoxy-4-hydroxypentane and 5 ml of pyridine in 25 ml of benzene was a solution of 3 »2 g (0.01 mol) of trans-4 , 4 ^5-azobis (4-cyanovalerylchlorid) was added in 25 ml of benzene at 20 ⁰ C for 15 minutes while the temperature was maintained at 20 ⁰ C 'the reaction was stirred for 1 hour, after which the acid chloride was added to end. The pyridine hydrochloride was filtered off and the benzene filtrate was washed with 5% HCl, 10% UaHCO, solution and saturated SraCl ° solution, dried over anhydrous sodium sulfate and filtered, whereupon the benzene was driven off. A viscous liquid weighing 5.2 g ( $ 85>. Yield) was obtained «

909837/1546

The infrared spectrum of the crude material indicated that some unreacted alcohol was present. A sample of 3.4 g of the crude material was dissolved in 5 ml of benzene and chromatographed on alumina. The first batch was eluted with 75 ml of pentane. After evaporation of the pentane, 1.9 g of viscous liquid were left in the refrigerator solidified, preserved. The infrared spectrum of the product agreed with that of the desired product. The second batch contained some of the unreacted Alcohol and vrorde discarded.

The Azoteil of the molecule has a 10 hour half-life temperature of approximately 65 ⁰ C, while the Peroxydteil has a 10 hour half-life temperature of approximately 126 ° C.

Example 13

Production of 2,2'-azobis [2-methyl-1- (t-butyl-peroxycarbonyloxy) propane]

O CH, CH, O

Il 1> I S Il

j) 5C-OOCOCH ₂ -C-II = Ii-C-CH ₂ OCOOC (CH ₃ ) ₃

CH,

CH,

I ·>

Compound I, wherein R = R ¹ X and R '- -C-CH ₂ -, X

-t. m = 1 and η = 1.

909837/1546

To a solution of 1.8 g (0.02 mole) 100? 5iges t-Butylhydro · peroxide and 1.6 g (0.02 mol) of pyridine in 25 ml of ether of 5 ⁰ O was added a solution of 3.0 g (0.01 mol) 2,2'-azobis (2-methylpropylchloroformate) in 25 ml of ether was added. The ether solution of the chloroformate was added dropwise with stirring over 15 minutes, during which the Eemperatur to 5 ⁰ C was maintained. The formation of the pyridine hydrochloride began immediately. The reaction was stirred for an additional half hour at 5 ° C and the pyridine hydrochloride was filtered off. The ether solution was washed successively with 2 # HOl, 10 # UaHCO ^ solution and saturated salt solution, dried over anhydrous sodium sulfate and filtered off, whereupon the ether was driven off. A liquid weighing 1.8 g (44 1/2 # yield) was obtained.

The infrared spectrum of the product indicated that considerable OH groups were present, so the product was chromatographed over alumina. The first batch was eluted with 75 ml of pentane. After evaporation of the pentane, 1.25 g of a colorless liquid were obtained. An infrared spectrum of the material was consistent with that of the desired structure, except that a small amount of OH groups remained. The sample was examined for the content of t-butyl hydroperoxide by a sulfite method and for the total content of active oxygen by an FeCl ^ method. The material contained 73 $ percarbonate and 1.9 5 ^ t-butyl hydroperoxide.

The Azoteil of the molecule has a 10 hour half-life temperature of approximately 162 ⁰ C, while the Peroxydteil having a 10 hour half-life temperature of approximately 99 ⁰ C.

90983 7/1546

Example 14

Production of 2,2 '~ A2obis- (2-> cyano ~ 5-t-butylperoxycarbonyloxypentane)

0 CH * CH * 0

^{ti J- 7} I &quot; ti

) ₅ COOGO {GH ₂ ) ₃ CN ~ HC (GH ₂ ) ^ OCOOC (GH ₅ ) ₅ CN CH

CH

Compound I, wherein R ^ R ⁹ X and R ^{ - -C- (CHoU-. O CiI

It

χ _s -O-COOC ^ Hg-t, m - 1 and η ^ 1.

To a solution of 1.9 g (0.0212 mole) of sodium t-butyl $ 100 "hydroperoxide and 1.6 g _(0? 0212 mole) of pyridine in 25 ml ether at 4 ⁰ C was added a solution of 4 g (0 , 0106 mol) 4.4 ⁵ ~ Asobis- (4-cyanopentylohloroformiat "added) in 25 ώΐ Itiier, the ether solution of the chloroformate was added dropwise with stirring over 15 minutes maintaining the temperature at 5 ⁰ v.odurcch C. ITachdera the addition was over, the reaction mixture was stirred an additional hour at 1O ⁰ C, the pyridine hydrochloride was filtered off, the Ätherfiltrat was washed with 5 $ HCl, 10 #iger IaHCO ₅ solution -JJ-xl saturated HACL solution dried over anhydrous sodium sulfate and filtered, whereupon the ether was driven off. A liquid was obtained weighing 3.4 g (67 % yield).

The infrared spectrum agreed with that of the desired product. The product was 96 i / 2 9 »pure _s what through

909837/1546

iodometric titration was determined. It wasn't sensitive to impact.

The Azoteil of the molecule has a 10 hour Halbwertszeitteniperatur of approximately 65 ⁰ C, while the Peroxydteil has a 10 hour half-life temperature of approximately 99 ⁰ C.

Β_ ^ iapiel 15

Production of M- (4 ~ t ~ butylazo-4 ~ cyanopentyl) paroxydicarbonate

CH * 0 0 CH,

a ·? »Η 5 2

) 3C-UHC- (CH ₂ ) ₃ οσοοσο (ch ₂ ) ₃ c-Mr-

CIi CH

CH, compound I, in which R - t ^ C ^ Hg-, R ⁸ »_ο-

0 0
t? egg

χ _s -O-COOCO-, si = 2 and η - 1.

0 0 CN

t? egg

To a solution of 10.2 g (0.0395 mol) of 4-t-Butylazo- = 4-cyanopentylchloroformiat in 30 ml of 5 Ither ⁰ C was trop = "fenteise with stirring, a solution of 1.9? g sugegeben (0.022 mol) of 38 fSiges hydrogen peroxide and 3.3 g (O ₅₀₄₂ mole) of pyridine in 10 ml ether. The temperature was kept ^{below 10 ° C. during the addition.} The reaction mixture was stirred for a further half hour at 1O ⁰ C, the Pyridinhydro »chloride was filtered off and was washed with Ätherfiltrat

909837/1546

2 ^ Siger KCl, 10% UaHCO, solution and saturated STaCl = solution, dried over anhydrous sodium sulfate and filtered, whereupon the ether was driven off. A liquid was obtained which weighed 7 * 55 g (80 5 »yield).

The infrared! oektrum of the product agreed with the one of the gevfünsch- πι product, with the difference that something OH on «; -end was »The sample was $ 60 pure thing through jodoEietriscli- * titration was determined. she was not impact sensitivity

The azo part : i as the molecule had a 10 hour half-life temperature of approximately 78 ⁰ G, while the perosyd part has a 10 hour half-life temperature of approximately 45 ° C

Example 16

Production of O ^ -t-butylazo-A-cyanopentyl-O ^ -t-butylmonoperoxycarbonate

GH, 0

(CH,), C-N = H-C (GHo), 0GOOO (CH,) -

YY j ^ - J YY

GN

GH,

Connection 'S. where R - t ~ C ^ H _g ~, E ⁿ «-C- (CH ₂ ) -,

0 CH

X - OGOOG.K ₀ --t, m «'' and η ^ 1 _β

BAO ORIGINAL 909837/1546

To a solution of 1.8 g (0.02 mol) of t-butyl hydroperoxide 100 #igera and 1.6 g (0.02 mol) of pyridine in 25 ml of ether of 5 ⁰ C was added dropwise with stirring a solution of 5 »2 g (0.02 mol) of 4-t-butylazo-4-cyanopentyl chloroformate in 25 ml of ether were added. After the addition was complete, the reaction mixture was ^{stirred for a further hour at 10 0} , the pyridine hydrochloride was filtered off and the ether layer was washed successively with 5% HCl, 10% NaHCO 3 solution and with saturated NaCl solution, over anhydrous sodium sulfate dried and filtered, whereupon the ether was driven off. 5.8 g of a liquid was obtained (92 # yield).

The infrared spectrum of the product was agreed with that of the desired product and the material was not sensitive to impact. It had a purity of 80.0? S, what was determined by iodometric titration.

The Azoteil of the molecules possesses a 10 hour half-life temperature of approximately 78 ⁰ C, while the Peroxydteil having a 10 hour half-life temperature of approximately 99 ⁰ C.

Example 17

A. Production of a peroxide-containing polystyrene from 1,3-dimethyl-3- (t-butylperoxy) -butyl-4-t-butylazo-4-eyanovalerate.

909837/1546

CH _x O

»Ρ it

tC.HQOOC-CH ₉ CH-OC-CHo-CH ₉ -C "~ w polystyrene CH ^

A mixture of 15 g styrene and 3 g 1ι3-dimethyl ~ 3- (t-butylperoxy) -butyl-4-t-butyla2o-4-cyanovalerate, from Example 10, in 36 g of xylene was heated under nitrogen for 6 hours at 9O ⁰ C " The cold reaction gel. was precipitated in an odorless mineral spirit. The resulting polymer was dissolved three times in Benaol and reprecipitated from the mineral fuel. The purified peroxide-containing polymer weighed 13-1 g.

B. Production of a polystyrene / polymethyl methacrylate block · = Mixed polymer made from the ρeroxide-containing polystyrene from A.

A mixture of 15 g Methyliaethacrylat and 3 g of the above polystyrene containing peroxide in 36 g of xylene was heated for 1 hour at 12O ⁰ C and 7 hours at 129 ⁰ C under nitrogen in a sealed Hohr. The cooled reaction mixture was precipitated in odorless mineral fuel. The resulting polymer was dissolved twice in benzene and reprecipitated from mineral fuel. The dried product weighed 12 g.

Its 14 # solution of the end product in chloroform did not separate in 13 stages. A 1: 1 mixture of 14 $ sodium polystyrene in chloroform and 14 $ sodium polymethylmethacrylate in chloroform is segregated in 15 minutes "These tests show that the block copolymer was formed _e

909837/1546

Other products falling within the scope of the invention were also made and are listed in Table III. As in the previous examples, evidence of the structure was made using infrared spectroscopy and analysis of active oxygen content, if applicable Methods were available.

909837/1546

I. ο k I. CO φ 0) .Ω PM ft H φ ID ρ C3 Θ r * 4 * ι. Φ P! 4 => Φ 4 = • σ Ή ö Φ O 4 = CQ CQ 4 » O Φ P 4 » ι ff I CQ Φ M feO cö • Η P CiJ 5ε H

O O O

O O VO

Γ

O O O O

O O

O O CM

VO

O O O

to

flftO
ο Θ · Η
CQ OH

• Η
4 »

• Η

ta • Η

CQ CO

O)

H
$

4 » CQ

to

W ο

ο-ο-ο- ο »ο-ο-ο

OS O CM

(Γ p

O- Ci-

Il

Sz; ο

«4»

4 =

4 »CM

EQ τ » &

CM CM

PJ Φ .α

M α! ο

! Φ

Φ Pi PQ CQ

CO

909837/1546

Posting TABEIiIE III

example

Structure and Name Shape Impact Gas 10 Hour Semi Sensitivity development timeliness temperature

tempera- ■

door azo peroxide

(O CD CO OO CO

cn * ^ cn

20th

COOC (CH ₃

CH,

O CN ^

2,2'-Azobis- [2-cyano-5- [2- (t ~ butylperoxycarbonyl) -benzoyloxy] -pentanej

liquid negative

7O ⁰ C

21

CH,

t s

CH _x

(CH ₃ ) ₃ CN = NC-CH ₂ -C-OOC (CH ₃ CN CH ₃

2- (t ~ Bu tylazo) ^ -y (t-butylperoxy) pentane liquid negative

7O ⁰ C

«5 5-60 ⁰ C

«* 126 ° C

Continuation! TABLE III

CD O CD OO CO

example

22nd

Structure and name

CH.

OH,

(CH ₃ ) ₃ σοοσ ~ θΗ ₂ οσ ~ ϊϊ =

ι j

GH,

GiT

2,2'-Azobis [2-cyano-4-ethyl-4- (t-buty! Peroxy) pentane]

."Shape

Beat sensitivity

Gas 10 hours half

Development value side tempering door

tempera-. ■. . ■■ ■

door azo peroxide

two

fixed

Isomers negative

51-53 ⁰ C
Decomp.

2. Pp

87 ~ 88 ° G

Decomp

negative

55 ⁰ C

40 ⁰ C

9O ⁰ C

VD

(CH _x ) _x C-li = NC-CH _o -C-00C (CH _x ) _X

J J ι <- j PP

Cl CH ₃

2- ( t-Butylazo) -2-chloro-4 ~ iae tnyl = 4- (t-butyIperoxy) -p entane

liquid negative

35 ⁰ C - <

24

CH, ι

CH-ι

CH

2- (t = Butylasso) -2-ine tlaoxy-4-Bietliyl-4- (t-butylperoxy) pentane

liquid negative

7O ⁰ C

«75 ° C

«126 ° C

Continuation of IABELLB III

at
game Structure and lame CH-, CH, 25th (CH ^) ₅ CH = HC-CH ₂ -C-00C (CH ₅ ) ₅ co
O H * CH ₃ ' co
00
co
-4 2- ( t ~ Bu tylasso) -2 ~ a2ildo »4-" ioetbyl-
4 »(t-butylperoxy) pentane cn CH, CH, co 26th (GEr, Uc-U = FC-CH ^ -C-OOC C CH ~ ) ~

0 C = O 3? Orm blow gas unlocked 10 hour half-sensitivity-value-side-barrier- door

tempera- = ~

So

Peroxide

liquid negative 45 ⁰ C <«60 ^o C ^

liquid negative 90 0

2- if t-Butylazo) -2-ace toxy-4-iae thyl 4- (t-butylperoxy) ^ pentane

TABLE III continued

example

Structure and uame form

Impact gas development 10 hour half-sensitivity value s since temperalichkeit ventilation door

tempera- ~

-t _ur azo peroxide

CO O (O OO U)

28

CH, % J

CH, \ J

27 (CH-UC-N = NC-CH ₉ -C-OOC (CH,), JJ \ ^c \ Jj

Br

2- (t-Butylazo) -2-bronio-4-ynethyl 4- (t-butylperoxy) pentane

OH, CH, \ j% J

HOO- C-Οι

CH, CN

CH ₃ CH,
ι J Ο —Ο ι ι

-OOH

CU CH, liquid negative

1O ⁰ C <10 ° C "126 ° C

liquid negative 7O ⁰ C <* 65 ° C »160-170 ° C

2.2 · -Azobis- (2-cyano-3-metlayl ~ 3 " hydroperoxybutane)

TABLE III continued

example

Structure and groves

Blowout

sens-

commendation

Gas vent

as K-

lung

tempera-

door

10 hour half

value time temperature

door

Azo

Peroxide

CO O CO CD CO

29

GH,

C = O t

0 f

CH

1 - liquid negative 65 ⁰ C «» 70-75

2 "t-Butylazo-2-t-butylperoxycarbonyloxy-4-methylpentane

Claims (1)

PAIENIAISPEÖCIE iy compound which is both a peroxy group and contains an aliphatic azo group, the general formula where (1) m is an integer from 1 to 2? (2) η is an integer from 1 to 20; (3) R ⁵ E ₁ 1 ' Ep means; or («IT) -OR, rYE _ß - (X) (4) X represents one of the following radicals containing a peroxy group
0 0 R ₁ -C-OOR ,, -OG-OOE ,, -C-OOR ,, Ε., ΟΟ-0-OOIU, J J J J J JJ 0 0 0 0 0 R ₁ R ₁ 0 -C-OO-C-, -00H, -OC-OO-CO- and -0-00-9-E ₅ -C-OOO-; 909837/1546 (5) Y is a divalent radical, viz O O it Il Is -CO- or -OC-; (6) H _{1 represents} an aliphatic radical having 1 to 10 carbon atoms; (7) R2 means one of the following radicals! 0 0 0 0 "II! I M il R ₁ OO-, H ₂ NO-, R ₁ -, R ₁ O-, R ₁ OCO-, R ₁ CO =, ArO-, Il ArCO-, ITC-, My-, Cl- and Br-, where Ar is an aromatic Radical with 6 to 12 carbon atoms be = indicates? (8) R ^ a tertiary aliphatic radical with 4 to 10 Means carbon atoms; (9) Rc is a divalent aliphatic radical with 1 to Represents 10 carbon atoms; (10) Rg is a divalent aliphatic radical with 1 to 10 carbon atoms or a divalent aromatic radical with 6 to 12 carbon atoms; (11) R-. and R ₁ - together with the tertiary carbon atom in R ^{5 can} denote a three-fold cycloaliphatic radical and (12) R a) a tertiary aliphatic radical with up to 10 carbon atoms, 909837/1546 b) (R ¹ -X) or c) R ¹ , if m is 1, denotes where X is a divalent radical. (CH ₃ ) ₃ COOCOCH ₂ - CN = N - C CH, ti -CH ₂ OCOOC CH CH ₃ (CH ₅ J ₃ COOC - CH, 0 t; -GHo-CHOC- (CH ₉ ) - CH, ■ σι cn CH, ι J ti ο ο -! ϊβΗ-σ- (CH ₂ ) ₂ σο (CH ₂ ) ₅ ~ c ~ CIT ο ο G (CH,), 909837/1546 ⁶ · —Σ OH" CH ₉ ο — συ CH ₀ t * CHo 7th CH ι Il -N = NC (CH _{2) 5} 0C-0 ₂ ) ₅ CN 8th. It CH, C- (CH ₂ ) ₂ -C00C-CH ₂ -CN CH, 9. t 3 OH _x
I ■> CH, OH,
t J ι J •OH HOO-C— -C - -N = N-C — C - t r t ι CH ₅ CN CN CH ₅ 10. Process for the production of a block polymer, marked by (1) Preparation of a polymer in which azo groups are present by. Implementation of a vinyl monomer and an azoperoxy compound of claim 1 under Vinylpolymeri- ■ sationbedingungen, wherein the conditions are controlled in such a way v / ground that the peroxy oxygen bin fertilize before 37/1546 the rupture, breaking the azo ~ carbon bonds and being the rupture of the peroxy oxygen formation has the effect of initiating polymerization; and (2) Reaction of vinyl monomer with the polymer of the step (1) under such conditions that the azo-charcoal ~ break fabric bonds of the polymer öer stage (1), resulting in a block polymer product. . 11. Process for the preparation of a polystyrene / polymethyl methacrylate block copolymer characterized in that one (1) Styrene with an initiating amount of the cyclic azo peroxide of claim 6 in a nitrogen atmosphere for 24 hours at 50 ⁰ C, and that one (2) in a nitrogen atmosphere, reacted for 7 hours at 75 ⁰ C, the methyl methacrylate with the azo-containing polystyrene of step (I), 12. Process for the production of a Bloclonic polymer, characterized in that one (1) A polymer which has peroxy groups is produced by reacting a yinylnionomer and an azo-peroxy compound of An3r >ruch 1 under ethylpolymerization conditions, the conditions being controlled in such a way that the azo-carbon bonds are broken before the Breaking proxy oxygen bonds, the breaking of the azo-carbon bonds having the effect of initiating polymerization; and 909837/1 546 • »i (2) the Vinylinonoiaer with your polymer of stage (I) below implements such conditions that the 2? ero: xysaiae2? ~ break fabric bonds of a polymer of stage · (1), wherein get a Bloclqpol.ymer product "3 ° Process for the production of a Polyethylene / Polyethylene Methacrylate BlockiaiscIapolymers ₅ daflureli galreiiii net j that one (1) a xylene solution of styrene with an initiating amount of azo peroxide of claim 4 in a nitrogen atmosphere for 6 hours at 90 ⁰ G masetsi; ₅ and that man A Xylollösiing of Methylmetüaeryla-i and the polystyrene-containing Peroizyd of step (i) In nitrogen atmosphere eiuer reacting (2) for 8 hours at 120 to 29 ° ^ ö. ORIGINAL BATH 909837/1546