RU2792744C2 - Poly-lactate of n,n-diallylacrylamide - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to ionogenic water-soluble polyelectrolytes of diallyl nature. Poly-lactate of N,N-diallylacrylamide of the formula

,

where n=93-112, is described for use as polyelectrolyte of diallyl nature.

EFFECT: obtainment of polyelectrolytes with high molecular weight and expansion of a range of electrolyte means with high molecular weight, high complex-forming properties, adjustable acid-base and hydrophilic-hydrophobic balance.

1 cl, 1 dwg, 2 tbl, 2 ex

Description

The invention relates to ionic water-soluble polyelectrolytes of diallyl nature.

Known polymer systems of derivatives of diallylamine and quaternary ammonium bases of diallyl nature, obtained on the basis of allyl chloride and derivatives of diallylamine [1-3], on the basis of which polyelectrolytes with low molecular weights were obtained.

The closest analogues are polymers based on substituted diallylamines [4], which can polymerize only those substituted diallylamines in which the electron-withdrawing groups (СО, CN, _SO2 ) of the substituents are directly bonded to the nitrogen atom. When these groups are removed from the nitrogen atom by one or two carbon atoms, N– substituted diallylamines do not polymerize. The disadvantage is the duration of the reaction in a nitrogen atmosphere at 80-130 ⁰ C for 16 hours, as well as their low molecular weights.

The objective of the invention is to obtain a diallyl nature polyelectrolyte with a high molecular weight, which has high complexing properties.

The problem is solved by obtaining a new polymer by the reaction of radical polymerization of N,N-diallylacrylamide lactate (PLDAA).

formulas:

where n= 93 - 112 having elemental composition (Table 1)

Elemental composition of N,N-diallylacrylamide polylactate (PLDAA).

Table 1

polymer formula elemental analysis Theoretical composition,% Practical composition,% WITH,% N,% N,% WITH,% N,% N,% PLDAA C ₁₂ H ₁₉ NO ₃ 64.00 8.44 6.22 64.96 9.09 7.26

The structure of the synthesized polymer, N,N-diallylacrylamide polylactate, was confirmed by IR spectroscopy ( ^Fig .). A finely divided polymer sample was mixed with KBr powder and pressed under high pressure into transparent thin disks. The thickness of the pressed disk is 1 mm, the diameter is 12 mm, the transmission is 95%. The wavenumbers of the absorption bands in the IR spectrum of PLDAA in the solid state correspond to the stretching vibrations of aliphatic CH groups in the region of 2923−2853 cm ^-1 ; absorption band C=O amide groups appears as intense absorption maxima at 1662 cm ^-1 ; the absorption band of the -CH=CH ₂ group is shifted and fixed in the region of 1554 cm ^-1 ; there is an intense absorption band in the region of 1444−1403 cm ^-1 characteristic of bending vibrations -NR ₃ , which is consistent with the literature data [5].

The production method consists in carrying out the reaction of radical polymerization of lactate N,N- diallyl acrylamide (LDAA) (Mr=139) in the presence of a radical initiator ammonium persulfate (PSA) at a temperature of 60-80⁰C and the synthesis is carried out at this temperature for 5-8 hours, which leads to the production of polylactate N,N- diallyl acrylamide (PLDAA). After the reaction is completed, the reaction mixture is gradually poured into dry acetone in portions, filtered on a Buchner funnel, washed thoroughly with dry acetone, then dried in a desiccator over phosphorus (V) oxide to constant weight.

2⁰С. Выход полимера 65%, η_прив. =0.32 дл/г (0.5 N растворе NaCl), что соответствует молекулярной массе (ММ) равное 23900. Example 1. 2.25 g (0.1 mol) of LDAA, 10 ml of bidistilled water and 5.0 × 10^-3 mol/l (0.00114 g) ammonium persulfate (PSA). The reaction mixture was heated at 80⁰C within 8 hours. After the reaction is complete, the reaction mixture is gradually poured into dry acetone in portions, filtered on a Buchner funnel, washed thoroughly with dry acetone, then dried in a desiccator over phosphorus (V) oxide to constant weight. Poly-lactate N,N- YAA - beige polymer with decomposition at 406.6

2⁰C. Polymer yield 65%, η_pref.=0.32 dl/g (0.5 N NaCl solution), which corresponds to a molecular weight (MW) of 23900.

2⁰С. Выход полимера 75%, η_прив. =0.38 дл/гExample 2. 4.5 g (0.2 mol) of N,N-DAA lactate, 30 ml of bidistilled water and 1.0 × 10^-2 mol/l (0.00228 g) ammonium persulfate (PSA). The reaction mixture was heated at a temperature of 60⁰C for 5 hours. After completion of the reaction, the reaction mixture is gradually poured into dry acetone in portions. PLDAA is filtered off on a Buchner funnel, washed thoroughly with dry acetone, then dried in a desiccator over phosphorus (V) oxide to constant weight. Poly-lactate N,N- YAA - beige polymer with decomposition at 406.6

2⁰C. Polymer yield 75%, η_pref.=0.38 dl/g

(0.5 N NaCl solution), which corresponds to the molecular weight MM≈24873.

2⁰С. Выход полимера 85%, η_прив. =0.45 дл/гExample 3. 4.5 g (0.2 mol) of LDAA, 30 ml of bidistilled water and 5.0 × 10^-3 mol/l (0.00228 g) ammonium persulfate (PSA). The reaction mixture was heated at 80⁰C for 5 hours. After completion of the reaction, the reaction mixture is gradually poured into dry acetone in portions. PLDAA is filtered off on a Buchner funnel, washed thoroughly with dry acetone, then dried in a desiccator over phosphorus (V) oxide to constant weight. Poly-lactate N,N- YAA - beige polymer with decomposition at 406.6

2⁰C. Polymer yield 85%, η_pref.=0.45 dl/g

(0.5 N NaCl solution), ММ≈25568.

The complexing properties of polylactate N,N-diallylacrylamide (PLDAA) [η _priv .=0.35 dl/g] were studied by photocolorometric method for cations (Fe ⁺³ ), copper (Cu ⁺² ), cobalt (Co ⁺² ). The values of the concentration of metal ions in the resulting complexes with the addition of a 0.1% aqueous solution of the PLDAA homopolymer to solutions of metal salts, at pH= 5.5, t=25 ⁰ C, as well as the operating values of λ are shown in Table 2.

The value of the concentration of metal ions in the complex

table 2

Metal cation, Me ⁿ⁺ λ,nm Concentration of metal ions in the complex, mg-ion/l Fe ⁺³ 625 ^3.68x10-5 Cu ⁺² 625 ^4.15x10-5 Co ⁺² 490 ^2.28x10-5

The technical result of the invention is to obtain polyelectrolytes with high molecular weight and to expand the range of polymers of diallyl nature. The proposed polyelectrolyte has high complexing properties, with adjustable acid-base and hydrophilic-hydrophobic balance, which can be used as flocculants, coagulants, soil structurers, drug prolongators.

Fig. IR spectrum of poly-lactate N,N – diallyl acrylamide

Claims (3)

N,N-diallylacrylamide poly-lactate formula

, where n=93-112, as a diallyl nature polyelectrolyte.

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