SU621692A1 - Stabilized composition - Google Patents

Description

The invention relates to a stabilization bath composition based on an unsaturated compound and an inhibiting system. It is known to inhibit unsaturated compounds by introducing into them a stable nitroxyl radical of the general formula, NO, where apkip, aryl or 1. and Rl form the cyclic structure tlj. Osh {AKO with such inhibition the efficiency of the inhibitory action of nitroxyl radicals is small. In addition, the action of the nitroxyl radical is one-time, i.e., it is not regenerated in the inhibition process, and for this reason, only one reaction circuit of the OKA and ampli- minates per nitroxyl molecule. In order to increase the inhibitory effect and the time of inhibition, a composition based on an unsaturated compound and an inhibitor is proposed, additionally containing a synergist - alif-. tic amine of the general formula, where, 1. and R. are hydrogen, alkyl, arip, alkylaryl, cycloalkyl, vynylaryl, and pi alcohol of the general formula R jCHOH, where R / and R are alkyl, aryl, cycloacyl, and the inhibitor is taken in the amount of 4 10 - IlO mol, and the synergist 0.001-2, LLC mol per 1 liter of unsaturated compound. The oxidation rate is measured volumetrically with the absorption of oxygen. To intensify the oxidation process, an initiator, azobisisobutyronitrile (AIBN), is added and the process is carried out at a suitable temperature. The effectiveness of the inhibitory effect of the composition of the inhibitor-synergist in the oxidation of a HUA sample is determined by comparing the amount of absorbed oxygen per unit of time in the presence of the inhibitory composition of the same value as in the presence of the inhibitor alone.

Nitroxy. the radicals are weak inhibitors outside the composition with the synergist, and the rate of oxidation for this reason, when introduced, decreases spabo. In a mixture with a synergist, the effectiveness of inhibiting the oxidation reaction sharply increases.

The time of the inhibitory effect of the composition is conditionally determined by the time of the experiment, since, due to the regeneration of the inhibitor, it is not possible to achieve speed. Inhibitors - nitroxyl radicals

2,2,6,6-Tetramethyl-4-oxopiperidin-1-oxyl 2,2,6,6-Tetramethylpiperidin-1-hydroxy l 2,2,6, in-Tetramethyl-4-hydroxypiperidine-1-hydroxy 2 , 2,6,6-Tetramethyl-4-benzoyloxypiperidin-1-oxyl 4,4-Dimethoxydiphenyl nitroxyl 4,4-Dinitrodiphenyl nitroxyl Di-tert-butyl nitroxyl

4,4,5,5-Tetramethyl-2-phenyl-2-imidazolin-3-oxide-1-oxyl

2,2,5,5-Tetramethyl-4-phenyl-3-imidazolin-3-oxide-1-oxyl

2,2,5,5-Tetrameti l-4-feni l-3-imidazolin-1-hydroxy l 2,2,5,5-tetrameti l-3-carbamidopyrrolin-1-oxyl 2,2,5,5- Tetramethyl-3-carbamidopyrrolidin-1-oxyl di- (2,2,6,6-tetramethyl-1-oxyl-4-pyperidine) isophthalate

Tetra- (2,2,6,6-tetramethyl-1-oxyl-4-piperidyl) -orthosilicate

Likloheksan-1-spiro-2- (4-oxoimidazolidin-1-ox-5-spiro-1-cyclohexane (4,4-dimethyl loxazolidin-1-Oxy l) - 2-spiro-1-cyclohexane

2, Synergists

N, N -dimethylcyclohexylamine Di-n-butylamine Tri-n-butylamine

N, N -dimethylaminoethypmethacrylate Cyclohexylamine Triethylamine Triethanolamine Benzylamine Polyethylenepolyamine L-Methylpipecolin Hexamethyleneimine Benzyl alcohol Vinyl alcohol Cyclohexyl alcohol Diphenylcarbinol Isopropyl alcohol

.3. Oligomers

Bis-G (meth) acrylate -triethylene glycol Bis-G (meth) acrylate-tetraethylene-glycol Bis -. (Meth) acryl-L-bis-diethylene glyc-t Bis-G (meth) acryl bis-triethylene glycolft Tetramethacrylate-bis-(trimethyleneol-propane)

growth of uninhibited oxidation. Comparing this time with the theoretical inhibition time determines the minimum stoichiometric inhibition ratio for the composition.

Examples 1-49 illustrate the stabilization of methacrylic and acrylic esters; . Examples 56-66 - stabilization of oligomers} examples 5О-55 - stabilization of compounds of other classes.

Abbreviations to the tables of examples.

НР1 НР2 НРЗ НР4 НР5 НР6 НР7

HP8

НР9 НРЮ НР11 НР12

HP 13 HP14 HP15 HP 16

MLCA DBA TBA

d'am TsGA

TA TEA

BA

PA

SY-MN GMI BS

her cs

DFK

ips

GM-3; TGA-3 GM-4, TGA-4

MHD-9 MTPA

Metimetakripat

Bis-G (meth) acripoxyethenylcarbonate 9-ethanpiop Bis-L (meth) acryl oxyethylenecarbonate t-diethyl No. Gpikop Bio-1 (meth) acripoxyethyl carbonate | -tratetipenepengpicop

4. Other designations.

Efficacy of inhibitory action. Polymerization injection period. Initial given polymerization rate. Polymerization depth.

Sample oxidized in the presence of the composition

In tab. Figure 1 shows the effectiveness of the inhibitory effect and the lower values of the stoichiometric inhibition factors for the composition of the synergist inhibitor.

To clarify the effect of the inhibitory composition on the quantitative characteristics of the polymerization of stabilized compounds, comparative experiments were carried out. Samples are oxidized for 4-6 hours in the presence of 210 mol / l AIBN at bOS, which corresponds to their storage at room temperature: without initiator - up to 3 pt; from 2-1СГ mol / l AIBN up to 1 year. In this case, the inhibitor is consumed by less than 20% (the concentration is determined by the EPR method).

In tab. 2 shows examples of comparative polymerization of samples at

MM A OKM-1, OKA-1

OKM-.2, OKA-2 OKM-4

15

NSP G

Oxydate f

. Polymerization kinetics is followed by calorimetry. The oxidation polymerization is carried out at the expense of the remaining after oxide neHHHj AIBN, 210 mol A l AIBN is introduced into the remaining samples.

From tab. 2 it follows that the synergist has practically no effect on the induction period, the initial rate and the depth of polymerization, i.e. it does not impair the properties of the substance being stabilized against oxidation. In the process of oxidation and polymerization, the substance remains colorless.

Thus, the technical effect of the proposed composition is as follows: the effectiveness of the inhibitory effect increases by 30-60 times and, moreover, the effective inhibition time increases by more than 10 times.

Table 1.

HP1

MMA HP2 Same HP5 HP7 HP9 HP15

n-butylmeta-

NR1. Acrylate NRZ Same

HP6

DMC5, O

DMC5.0

DASHA5,0

DMC5.0

ten

6

6

Continued table. one

Continued gab. one

Continued table. one

Claims (1)

13 Claims of the Invention A stabilized composition comprising a unsaturated compound and an inhibitor — NITROXYLIC or PIPINITrO—; xyp radical of general formup, where RjH P, apkyl, aryl or 1 form a cyclic structure, characterized in that, c. the chain of increase in inhibitory-dyeb and the time of inhibition of the composition, it additionally contains a synergist - an aliphatic amine of the general formula 621692 14 Continued table. 2, where Rg, 1 and alkyl, aryl, alkyl aryl, cycloalkyl, vinyl aryl, or alcohol are of the general formula: tg to snoN where Ipj is alkyl, arip, cycloalkip, the inhibitor taken in the amount of 41 SG 110 t 1 mol and synergist 0.001-2, Ltd. mole per liter of unsaturated compound. Sources of information taken into account in the examination; 1. USSR author's certificate number 166133, cl. C 08 i 45/60, 1962.