SU390118A1 - The method of producing oligomeric peroxides - Google Patents

Description

The present invention relates to a method of oligopenoxide polynucleus, which can be used as initiators of radical polymerization and block copolymerization, agents for epoxidation and modification of polymers, etc.

A known method for producing oligomeric peroxides by interfacial polycondensation of dichlorohydrides (in ether and benzene solvents) with a bifunctional transition material, for example, sodium peroxide (in a solution of sodium acetate).

However, the oligoperoxides forming according to a known method have a low molecular weight and are considerably heterogeneous in molecular weight (the average degree of polymerization varies between 164-35). Their output is low. In addition, this method allows to obtain oligo-peroxide compounds only with peroxide groups of the same thermal stability; such compounds are unsuitable for providing almost constant initiation rates in a polymerization system with temperature, simultaneously increasing the polymerization rate and molecular weight of the resulting polymers with increasing oligoperoxide concentration, synthesizing block copolymers without admixture of homopolymers.

By the proposed method upon receipt

oligomeric peroxides as the starting peroxide compound, it is recommended to use an organic dinacid. Mono-a-substituted dichlorohydrides are used as the starting dichlorohydrides, but unsubstituted dichlorohydrin can be used if necessary. The resulting oligoperoxides have the following structure:

С- (СНа) ™ -С-О О-С-СН- (GHs) „

ten

C) x

OO

С-ОО-О-

about

where w 2+} 6

rt l-fl5

X is a halide. OCH, OCzlis, etc .; Clh, CH. CjHs, etc.

Such compounds can be, for example: Polyazeloyl diperoxy - "- ra - azelaoyl peroxide

с- (СНа) -С-ООО-С-СН-CHj) e

oo

about sh

-C-0-OJ20

| ,

O The degree of polymerization (CO), or the number of ireoxide groups, is 41. Polymeloylpyroxy-a-C1-azelaoyl-peruke, SP-3Z, IC - fCHa) 8-: -O-O-C-CH (CHg) 6-11; itII I Ltd. CJ Polysebacatoyl peroxymethylsuccinylperoxide, SP-39 Molecular weights is the yield of oligoperoxides in, 10 {„c-tcH2) 8-с-о-с-сн-снг-: II,. LLC SNz-C-O-O-18.: I, The method is carried out as in the well-known case at the border of the fvz, and the dichlorohydride is introduced with a solvent. Diethyl ether is the preferred solvent, since other solvents impair the properties and yield of oligoperoxide, as can be seen from the table. 1. Table 1 Solubility for Dichlorohydrin Solvent

Mono a Br-sebacin 8 & (condensation with sedentary acid) Mono-a-C1-azelan (co-condensation with azelaine dinadic acid) A 10% aqueous solution of diadic acid in KOH is used as the aqueous phase, and for dynadic acids with the number of carbon atoms take equimolar amounts of alkali and dinadic acid. For diadiac acids, it is advisable to take a 100% excess (by volume) of 1 ()% KOH. Note that KOH and NaOH 1 deviate from the given solubility conditions of diacidic acids also reduce the yield and molecular weight of oligo peroxides. The proposed method allows to obtain, with good yields, oligomeric peroxides with increased molecular weight, characterized by uniformity in molecular weight distribution and an increase in the latter. In addition, the proposed method makes it possible to obtain oligomeric peroxides with both different and with identical but not increased stability groups, while maintaining the effect of increased molecular weight to yield. The invention is illustrated by examples. An example. Preparation of polyazeloyl diperoxymethylenesuccinyl peroxide. I - (СНаЬ-С-ООО-С-С-СНг-, II () О О С С. О-О-О. 3000- 45--56 4000- 50-60 4300 4000 6000 4SSY 58 5000- 65 -70 5500 3600- 60-65 5000 5000 6000 3.96 g of finely ground dinadaselic acid is dissolved at 40 ° C in 40.5 ml of 10% KOH with vigorous stirring. After dissolving the dynadic acid, a cooled solution of the acid chloride is added dropwise. itakova acid (t. Kip .. 71 ° at 2 mm Hg. Art., 1.4919) in ether (3 g of dichlorohydrin in 200 ml of ether). Intensive stirring is continued for 1 hour at 0-H5 ° C. Formed with oligoperoxy in the course of the reaction precipitates in the form of small crystals After the end of the reaction, the mixture is diluted with an equal volume of ice water and the precipitate is filtered off on a Buchier funnel. The precipitate is washed successively with water, alcohol, ether and dried under vacuum at room temperature for 12 hours. 6.26 g of peroxide are obtained {90% yield ). Polymerization coefficient 37. Examples 2-10. The preparation of other oligomeric peroxides is carried out under conditions analogous to example 1, but with a change in the ratio of alkali to dinadic acid and temperature. These experiments are given in table. 2

Test conditions and properties of cofAiii obtained: eiiiifi

I-C- (SNg) t-C-O

Iiii

OO

soooooo

II o

2 "

(SI2) b-C-O

II

about

- (CH2) in - C-OO

about

four"

B I-c- (SNg) -c-O-11II

Ooh

- (CH2) b-C-OO

II o

"-C- (SI2) eC-O-IIII

Ooh

- (CH2) 7-C-0-0)

II o

7 "

(CH2) 7-C-0IIIIOo

(CH2) b-C-O-0 R

. II o

(CHjje-C-O-

Iiii

OO

SI, -CO-O-

II

about

10 "Kinematic parameters of some synthesized oligopreoxides, confirming the Kiketic characteristics of the thermal decomposition of oligoperekisy in benzene (C- (CHj), - COO - C-CH- (CHs-e LLC Vg C-O-O II -C (CH2) 7-с -o-OC-CHIIIIII i OOOC - (CH2) b C-OO-II Ki: EI; Cg: Ej

T a b. L II c D 2

2: 1 0 + 5 I 90 37 52.94 5.10 - 9.57 53.50 5.73 - 10.19

2: 1 0 + 5 0.548 24 - - - 9.32 - 1: 1 „3 + 5 1 96 33.0 - - 9.29 7.92

9.38 8.45

2: 1 -3 + 5 1 65 27.0 - - 9.64 7.80 „„ - - 2: 1 -3 + 5 I 91 43.0 54.0 6.54 8.68 7.50 53.1 6.64 8.73 7.87

2: 1 -3-0 1 90 43.0 50.4 6.60 16.52 6.38 50.1 6.67 16.70 6.68 in

1: 1 -3-0 I 63 17.1 49.25 6.07 17.03 5.85 - - - 2: 1 -3-0 1 87 41.0 48.1 6.09 (7.67 6.74 47.9 ii i.7.74 7.10

2: 1 0 + 5 1 90 39 -

9Л8

- 9.70

2: 1 10 + 15 1 70 22.5 53.82 5.93

8.80 54.54 () .67 - 9.70

t a b l n c a 3 the difference in the thermal stability of peroxide groups is given in Table. 3, 6.3.97 2.79 105.9 5.43 171.8 10.00 23.31 29.93 -4., - +9.1 12.59 2.21 22.394.15 37.15 8.32 25.14 32.00 -20 - | -M, (, ASi are the closest to the Pomtest : AS :; OTlioC5iTi-; i to v.Tii.noiifioM from the H.OurOid —Spati,: Subject of the Invention WITH SPECIFICALLY GETTING SINGLE-MEASURAL ROOMY PEROXIDES ME MEHG: Polycondensation of Dichlorine Anhydride with Bifunctional Co-Writing 5 Unity; that, with the purpose of obtaining oligomeric peroxides with improved properties, an organic dinacid is used as the starting functional functional peroxide compound.