JPS5810568A - Metallic salt of dithiocarbamic acid and its preparation - Google Patents

Abstract

NEW MATERIAL:A metallic salt of dithiocarbamic acid expressed by formulaI (R is H, 1-8C straight or branched chain alkyl or aralkyl; M is mono--bivalent metallic atoms; n is a positive integer corresponding to the valence of M). EXAMPLE:Sodium 1,2,2,6,6,-pentamethyl-4-piperidyldithiocarbamate. USE:A stabilizer of synthetic polymers against light, heat and oxidation, and a vulcanization accelerator of rubber. PROCESS:A piperidyl compound expressed by formula II is reacted with carbon disulfide in the presence of an alkali metallic hydroxide, and if necessary the reaction product is then reacted with a halide or sulfate of a bivalent metallic atom to afford the compound expressed by formulaI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a compound of the general formula (I) H2OCf(a (wherein R is hydrogen Atom, 01 to 8 straight or branched alkyl or aralkyl group, M is a monovalent or divalent atom, and n is a positive number corresponding to the valence of M. This article relates to a dithiocarbamine metal salt and its manufacturing method.

The dithiocarbamine compound represented by the general formula (I) was first developed by the present inventors as I! ! This is a new compound that has not been described in any literature.

Traditionally, 2.61
It is known that e-substituted piperidine compounds η are used as stabilizers for synthetic polymers such as polypropylene and polyurethane.

However, since these compounds themselves have high water bathing properties and high transpiration properties, good stabilizing effects can be obtained if they are added to synthetic polymers in a low-I content in such applications. The drawback is that the effect diminishes at high temperatures, and the effect does not last long enough.

Metal groups based on monodivalent gold such as calcium and barium exhibit an excellent stabilizing effect of 4% even when synthetic polymers are treated at high temperatures, and are used as stabilizers for synthetic polymers. Useful.

Dithiocarbamic acid gold powder represented by the general formula (I) is composed of a piperidyl compound represented by the general formula (IT) MaC (IB (in the formula, RU has the same meaning as 营π)) and carbon disulfide. is reacted in the coexistence of an alkali metal hydroxide, or further reacted with a halide of a divalent metal atom or a shoe salt.
&! can be built.

Here, the substituent pores in general formulas (I) and (ii) I include, for example, hydrogen, methyl, ethyl, n-propyl, l-propyl, n-hexyl, n-octyl, benzyl, etc. Further, in the case of M1 in the general formula (I), examples of the metal metal are alkali metals such as sodium, aluminum, and potassium, and examples of the divalent gold metal include zinc, nickel, calcium, barium, and the like.

E-ki! ! ! In the production method, a piperidyl compound represented by the general formula (b) and carbon disulfide are reacted in a polar bath medium such as water, methanol, or ethanol in the coexistence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. As a result, an alkali gold dithiocarbamate monosalt represented by the general formula (I) is obtained. In this case, the general formula ([
The molar W of the piperidyl compound represented by I), carbon disulfide and alkali hydroxide is usually 1:0.8 to 1.5.
: 0.8 to 2, and the reaction temperature is usually -1θ to 60°C.

Thus obtained alkali gold salt of dithiocarbamate and divalent halide or sulfur V! Salts such as zinc chloride, calcium chloride, barium chloride, nickel dust, zinc bromide, barium bromide, nickel salt, and sulfuric acid are mixed in a molar ratio of 1:0.7-5 to 0.25, preferably l: 0
．． 6 to 04, in a polar solvent such as water, methanol, or ethanol at a reaction temperature of 0 to 70°C, preferably 15 to 50°C.
/ A divalent gold:pe salt of dithiocarbamic acid represented by the general formula (bound) can be obtained.

In addition, the alkali gold dithiocarbamate in which R in the general formula (1) is a hydrogen atom, and the width only, are the known fathers of 4-aminopiperidine compounds in which R is a hydrogen atom in the general formula (11) and carbon disulfide. It can also be obtained by neutralizing the 4-aminopiperidyldithiocarbamic acid obtained by the reaction with an alkali foride, but if ■ in the general formula (I) is an alkali gold other than the hydrogen deuteron QL, the general formula ( 4-aminopiperidine compound 11 in which R in [1] is other than hydrogen cannot be obtained only by reacting with divalent carbon,
The 4-aminopiperidine compound and carbon disulfide can be synthesized only by the method of the present invention in which the compound is reacted with carbon disulfide in the presence of an alkali hydroxide.

Specifically, the compound of the present invention represented by the general formula (I) prepared by
4-biperidyldithiocarbamine-'19,l,2,6.6-bentamethyl-4-piperidyldithiocarbamine,■-ethyl-2
．． 2.6.6-Titramethyl-4-piperidyldithiocarbamic acid, 1-n-propyl-2,2,6,6-tetramethyl-4-piperidyldithiocarbamic acid, 1-1
-propyl-2,2,6,6-tetramethyl-4-piperidyldithiocarbamic acid, 1-n-hexyl-2
, 2,6,6-tetramethyl-4-piperidyldithiocarbamin, 1-n-octyl-2,2,6,6-tetramethyl-4-piperidyldithiocarbamic acid, ? and l-benzyl-2,2,6,6-tetramethyl-4-piperidyldithiocarbamic acid, sodium, potassium, zinc, nickel, calcium, and barium.

The present invention will be explained below using examples.

Example 1 1.2,2,6.6-pentamethyl-4-aminopiperidine 17. In a mixed liquid consisting of Of and 89.7 f of water,
Disulfide jfAM7.6f and 101% sodium chloride aqueous solution 40F are simultaneously added dropwise to the chamber side.

After dropping, water is distilled off under pressure at 100°C or less.
Sodium 2,2.6.6-bentamethyl-4-piperidyldithiocarboxylate 2,6f was obtained.

The infrared 1 absorption spectrum of this product shows that the original example, Example 2, l,2゜2.6.6-bentamethyl-4-piperidyldithiocarbamic acid't-
Da 26.8f to Hefei aqueous solution 126.8f, Hanawa! 15% zinc solution in water 45
Lower r by nφ. After finishing dropping, lo.

27.8 f of zinc thiocarbamate is obtained.

This substance is a white solid that decomposes when heated to 200°C.

Elemental analysis value Actual measurement 'tL C47,0%H7,5%N
9.9%zn12.0% Calculated value C47,5%H7,6
%N to, t%Zn 118% Example 8 l-i-propyl-2,2,6,6-tetramethyl-4
-Amino? Example 2: Potassium 1-i-durobi-2.2,6.6-tetramethyl-4-piperidyldithiocarbamate obtained using veridine, carbon difltide and caustic potassium as raw materials in the same manner as in Example 1. 1-1-propyl-2,2,6,
Calcium fi-tetramethyl-4-piperidyldithiocarbamate 58f is obtained.

This substance is a white powder that decomposes when heated above 200°C.

Elemental analysis value
74% calculated value 0588ss%N9)%0a58% actual,
1 strain example 4 l-n-octyl-2,2,6,6-tetramethyl-4
- aminopiperidine, carbon disulfide and caustic soda I
An aqueous solution 8 containing 36.72% sodium 1-n-octyl-2,2,6,6-tetramethyl-4-bi-beridyldithiocarbamate obtained in the same manner as in Example 1 as a starting material.
672 was dropped into a 10% barium chloride aqueous solution 124 over 2 hours. After the dropping was completed, the temperature was raised to 50°C,
Incubate in the same mL solution for 2 hours. Thereafter, it is cooled to room temperature, filtered, washed with water, and dried. In this way, a 40.5F grayish white powder of barium 1-n-octyl-2,2,6,6-tetramethyl-4-piperidyldithiocarbamate was obtained.

Elemental analysis value Real! -11 value 052.1%1 (8B%N
65%Ba 17.0% Calculated value 0524%H8J) No. N6f3%Ba 16.7% Actual example 5 2. Making real sushi using 2,6.6-tetramethyl-4-aminopiperidine, carbon disulfide and caustic soda 10,2 f
70f of water bath liquid containing 2.6t of foamed nickel and 100ml of water
Pour the water into the well-stirred liquid for 30 minutes while stirring.

After the completion of the dropping, the solution was stirred for 1 hour, filtered, and unreacted raw materials and produced food damage were removed by washing with water.
Dry at ~70°C.

Thus 2,6,6-tetramethyl-4-piperidyldithiocarbamine tube nickel9. Get Or.

This substance is a pale yellow powder that can be heated to 200℃.

Elemental analysis value Actual value C458%f (7.1%N10.
5%Nin, 6% calculation injection C46, 1%H7, 3%NI
O,7%Ni1lj3%Example 6 2.2.6.2.2.6.2.2.2.2.2.2.2.6.2.2.2.2.2.2.2.2.2.2. 6.6-tetramethyl-4-piperidyldithiocarbamine potassium 7.
@Tt zinc heptahydrate 2.89 r
Contains water bath liquid 100? The mixture is stirred and added dropwise over a period of 30 minutes. After the addition is complete, the mixture is poured and kept warm at 40-50°C for 2 hours, then cooled for 1 hour and washed 7 times with water.

Zinc 2,2.6.6-tetramethyl-4-piperidyldithiocarbamate 52 is thus obtained.

This product is a white powder and decomposes when heated above 200°C.

Elemental analysis value Actual value C451%1117.1%N10
3%Zll 12W% meter value 045#R7,8%N1
0.6%Zn12A% Reference Example 1 0.26 parts by weight of the dithiocarbamine P divalent resin obtained by the above-mentioned pressing was added to 4 parts by weight of unstabilized polypropylene 100'i, and mixed 4'@Unit. The sheet is heated and formed into a raw material.

Each sheet fades.

Ultraviolet rays were irradiated at 450 m with the instep of the meter, and the time required for the object to reach 4 Z was measured.

? Show fruits and vegetables.

Claims (1)

[Scope of Claims] (11 General formula (wherein, hydrogen is hydrogen, 01 to 8 are linear or branched alkyl groups or aralkyl y, M is a monovalent or divalent metal atom, and n is M) Gold dithiocarbamate, denoted by a positive integer corresponding to the valence of 1 ton ('to), @tan (2
) The piperidyl compound represented by the general formula (n) (wherein represents a hydrogen core, a straight chain or branched alkyl group or an aralkyl group of 01 to 8) and carbon disulfide in the coexistence of an alkali hydroxide. React below or further 21i
The general formula CI) is patented to react with a halide or sulfur q salt of a metal atom of Fi. n is M