SU924040A1 - Alkylene(arylene)-bis-4(1,1-disubstituted) semicarbazides as monomers for water-soluble polymers - Google Patents

Description

The invention relates to new chemical compounds, specifically to the bis-semicarbazide derivatives of the general formula

Κ ^ Ν-ΝΗ-ϋΟ-ΝΗ-Κ-ΝΗ-ω-ΝΗ-ΝΕ ^, I ₅

where K - СНоСН = СН <1, СНдС & Нр СН ^ СНдОН;

K - hexamethylene, diphenylmethane.

Alkylene (arylene) -bis- [4 (1,1-dismution ^ semicarbazides]) are used as monomers for the synthesis of water-soluble polymers that can be used as polyelectrolytes.

Known derivatives of bis-semicarb- and azides - alkylene (arylene) -bis- 4 ^ g (2-substituted) semicarbazides] of the general formula

Η _ί Ν-ΝΕ-ω-ΝΗ-Ρ'-ΝΗ-εθ-ΝΕ-ΝΗ " ₁ ,."

where K is alkyl, СН (} СН = СНг, СНдС ^ Нд, αΟΗιΟΗιχΟΗ, СНоСН (р (;;

K - alkylene, Allen,

2

which are obtained by the reaction of aliphatic or aromatic diisocyanates with a 2-10 fold excess of monoalkyl hydrazine of the general formula Κ-ΝΗ-ΝΗ ^, where K has the above meaning.

These compounds are used as monomers for the synthesis of various polymers, which, due to the presence of the semicarbazide group in the initial monomer, possess a complex of valuable properties [12 and (2). - However, the use of alkylene (arylene) -bis- [4- (2-substituted) semicarb azides] as monomers for the synthesis of polymers leads to the formation of water-insoluble polymers, the processing of which involves the use of toxic flammable organic solvents, which limits their use.

The purpose of the invention is the expansion of the range of substances that could

would be used as monomers in reactions with various

3 924040

four

reagents for obtaining water-soluble polymers with the properties of polyelectrolytes.

This goal is achieved by new alkylene (arylene) -bis- [4 (1,1-disubstituted) semicarbazide compounds of general formula I, which

I

1 ⁴ ΪΑ- = = 0 ->

¹ where K is CH | ^ CH ⁼ CH (^, CH ^ C ^! C, Ο ^ ηΟίηΟΗ ', k is hexamethylene, diphenylmethane. And

To obtain this method of alkylene (arylene) -bis- [4 (1,1-disubstituted) semicarbazides), solvents that are chemically inert to diisocyanates and asymmetric ₂ -di-ethyl dialkylhydrazines are used. chloroform.

For the reaction between the reagents, an excess of asymmetric dialkylhydrazine with respect to the diisocyanate is used, usually 2-2.5 molar excess, with the preferred addition of the solution of diisocyanate to the solution of the asymmetric dialkylhydride- ₃₀ Razin at 5 ”25 ° C.

The product formed during the reaction is isolated from the reaction mixture by known methods — filtration or evaporation of the solvent under reduced pressure, followed by recrystallization of the product. The yield of the target product is 70-95% of theoretical.

The resulting alkylene (arylene) -bis ”[4 (1,1-disubstituted) semicarbazides) are soluble in amide type solvents, alcohols, acetone, water.

Their IR spectra are characterized by the presence of absorption bands in the region of 3420-3200 cm ' ^and (ΝΗ group), 16701640 cm ~ ¹ (C = 0 group).

The presence of two tertiary amine groups in alkylene (arylene) -bis-G4 (1,1-disubstituted) semicarbazides] allows by quaternizing them in reactions with various bifunctional reagents to obtain polymers with a quaternary nitrogen atom in the main polymer chain, characterized by unlimited solubility in water, having the properties of polyelectrolytes.

is obtained by the interaction of aliphatic or aromatic diisocyanates with a more than twofold molar excess of asymmetric dialkylhydrazine of the general formula Ρ.πιΝ11-Ν1Ι (ΐ ⁱⁿ an inert organic solvent at room temperature or cooling:

Example 1. Alkylene (arylene) -bis- [4 (1,1-disubstituted) semicarbazide). To a solution of 6.8 g (0.032 g-mol) of asymmetric dibenzylhydrazines in 50 ml of ethyl acetate, with constant stirring and a temperature of 15 ° C, add 3.75 g (0.015 g-mol) of 4,4-diphenylmethane diisocyanate in 20 ml of ethyl acetate over 20 minutes . Upon completion of the addition of the diisocyanate solution, the reaction mixture is stirred for 1 hour at room temperature, the solvent is removed under reduced pressure, and the residue is crystallized from isopropyl alcohol. The yield of 4,4-diphenylmethane-bis- [4 (1,1-dibenzyl) semicarbazide) is

7.1 g (71%); m.p. (melting point) is 1b2-1b3 ° C.

Found: C 76.35; H 6.26;

N 12.51

Calculated ^: C 76.53; H 6.27;

N 12.45

Example 2. 1,6-Hexamethylene bis- [4 (1,1-dibenzyl) semicarbazide], To a solution of 1.4 g (0.0066 g-mol) of dibenzylhydrazine asymmetric in 20 ml of benzene at 20-25 ° С and while stirring, a solution of 0.5 g (0.003 g-mol) of hexamethylene diisocyanate in 10 ml of benzene is added dropwise. The reaction mixture is stirred for 2 ~ 3 n and the benzene is distilled off under reduced pressure. The remaining oil on standing hardens. It is crystallized from ethyl acetate to obtain 1.65 g (93%) of 1,6-hexamethylene-bis- [4 (1, 1-dibenzyl) semicarbazide) with m.p. 102-104 ^e C.

Found,%: C 72.64; H 7.36;

N 14.38

WITH

Calculated,%: C, 72.94; H 7.48;

N 14.18.

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Example 3. 1, 6-G'examethylene-bis- [4 (1,1-di ~ 2-hydroxyethyl) semicarbazide]. A solution of 1.04 g (0.0062 g-moles) of hexamethylenediisocyanate in 10 ml of chloroform at 5 ^_ 10 ° C and vigorous stirring was added dropwise to a solution of

1.7 g (0.0124 g-mol) of asymmetric di-2-hydroxyethyl hydrazine in 30 ml of chloroform. The reaction mixture is stirred for 1-2 hours at room temperature and the precipitated substance is isolated by filtration, after which it is crystallized from a mixture of chloroform and isopropyl alcohol. The yield of 1,6-hexamethylene bis [4 (1,1-di-2-hydroxyethyl) semicarbazide] is 1, 76 g (70%); m.p. 83-85 ° C.

Found C, 46.86; H 9.01; 20.41

^С 16 ^Н 36 ^М 6 ° 6

Calculated,%: C 47.04; H 8.8;

N 20.57 ₍

Example 4. 4,4-Diphenylmethane-bis- [4 (1,1-di-2-hydroxyethyl) seven- ²⁵ carbazide]. At 5 7 7 ° C and vigorous stirring, a solution of 1.8.3 g (0.0073 g-mol) is added dropwise to a solution of 2 g (0.0167 g-mol) of asymmetric di 2 -2 hydroxyethyl hydrazine in 30 ml of chloroform. ) 4,4-diphenylmethane diisocyanate in 15 ml of chloroform, after which the reaction mixture is stirred at room temperature for 1-2 hours. The solvent is removed from the reaction mixture 35 under reduced pressure and the residue is crystallized from water. The yield of 4,4-diphenylmethane-bis- [4 (1,1-di-2-hydroxyethyl) semicarbazide) is 3.3 g 40

(92%); m.p. 130-132 ° C.

Found,%: C 56.51; And 7.01;

N17.42.

Calculated,%: C 56.31; H 6.99; N17.13.

Example 5 · 1,6-Hexamethylene bis-14 (1,1-diallyl) semicarbazide]. At 15 “20 ° С, a solution of 1.68 g (0.010 g mol) of 1,6-hexamethylene diisocyanate in 15 ml of benzene is added dropwise to a stirred solution of 2.8 g (0.025 g-mol) of asymmetric diallylhydrazine in 30 ml of benzene. The reaction mixture is stirred at room temperature for 2-3 m, the benzene is distilled off under reduced pressure. The residue is crystallized

45

50

55

ten

,five

20

from ethyl acetate and dried in vacuo. 2.67 g (68 ') of 1, 6-hexamethylene-bis- [4 (1, 1-diallyl) semicarbazide 3 are obtained. ^{52-55; and} S.

Found,% ·. C, 59.90; H 9.19; '

N 21.15;

3 <Αθ <λ

C, 61.19; H 9.28;

N 21.41.

Example 6. 4,4’-Diphenylmethane-bis-G4 (1,1-diallyl) semicarbazide}

To a solution of 2.8 g (0.025 g-mol) of asymmetric diallylhydrazine in 30 ml of benzene at 5-10 ° C and a solution of 2.5 g (0.01 g-mol) of 4,4-diphenylmethane diisocyanate in 20 are added dropwise. ml of benzene. The reaction was stirred at room temperature for 1 hour, the solvent was removed under reduced pressure, and the residue was decanted 3 times with cold benzene. 3.85 g (81%) of 4,4'-diphenylmethane-bis- [4 (1,1-diallyl) semicarbazide] are obtained with m.p. 87 ^- 90 ° C.

Found,%: C 68.02; H 7.42;

N 17.43

Calculated,%: C 68.33; And 7.22;

N 17.70.

Example 7. The use of alkylene (arylene) -bis- [4 (1,1-disubstituted) semicarbazides] as monomers in the synthesis of water-soluble polymers.

A mixture of 2 g (0.0051 g-mol) of 1,6-hexamethylene-bis- [4 (1,1-diallyl) semicarbazide] and 1.5θ g (0.0051 g-mol)

1,4-diiodobutane in · 40 ml of n-butanol is kept boiling until it is complete -. reaction. 3.2 g (90%) of a polymer of the general formula are obtained.

i am

© I

i © θ, nd

where K - CH ^ CH = SND,

characterized by unlimited solubility in water. This polymer is a typical polyelectrolyte. The resulting polymers based on the proposed monomers, as well as a polymer based on a known monomer, are examined for complexing ability with divalent metal ions in aqueous solutions and DMF solutions. The results obtained are presented in the table.

7

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Source monomers for the synthesis of polymers

Si '

With

. + +

Not

Famous

y-εν \

Suggested I

Και ^ οΗ-οΗ ^^ - Ν-ΝΗεοΝΗ ^ ζα-ίο) ^ + + +

(αίΟΟΗηρΗ ^^ Ν-ΝΗΕΟΝΗ ^ α-Ι ^ θ + + +

(+) - the formation of "complex;

(-) - lack of complex formation.

As seen from the table, the ²⁰ polymers prepared in contrast to similar polymers prepared by reaction of alkyl dihalide with di-tert-amines [2], have thanks to semicarbazide groups com- ²⁵ pleksoobrazuyuschimi properties with iona-, m- divalent metals.

The use of 1,6 hexamethylene bis- (4 (2-allyl) semicarbazide] [1,4] 1,4-diiodobutane in the reaction leads to the formation of a water-insoluble polymer.

Thus, the resulting alkyl-, flax (arylene) -bis- [4 (1,1-disubstituted semicarbazides), in contrast to the known alkylene (arylene) -bis- [4 (2-substituted) semicarbazides, are capable of with difunctional compounds to form water-soluble polymers with a complex of valuable properties.

The preparation of alkylene (arylene) -bis- [4 (1,1-disubstituted) semicarbazides) is distinguished by its simplicity of execution. It is characterized by a high yield of the desired product, the availability of the raw material. Water-soluble polymers based on them, being typical poly | electrolytes, differ from known analogues in their ability to complex with metal ions. These polymers can also be used to impregnate paper, fabrics, antistatic additives in photographic materials, PVC products, etc. In addition, the presence in alkylene (arylene) -bis- [4 (1,1-disubstituted) semicarbazides] reactive functional groups (allyl, hydroxyl) opens up possibilities for further modification of both the monomers and water-soluble polymers based on them.

Claims (1)

Claim Alkylene (arylene) -bis- [4 (1, 1-disubstituted) semicarbazides] of the general formula I where K - СНо. СН = СН СН ^ П ^. СН ^ СН ^ Ш; K. ¹ - hexamethylene, diphenylmethane, as monomers for water soluble polymers.