Synthesis And Properties Of Polyquaternium

Because macromolecular surfactants have viscosification property and surface activity, it can be widely applied in daily chemicals, coating industry, wastewater treatment, petroleum exploitation etc.This paper aims to synthesize cationic macromolecular surfactants which nitrogen atoms are located in the polymer main chain with long alkyl side chain. The following progresses are made: (1) Use epichlorohydrin、methylamine and long-chain alkyl bromides as the raw material, synthesis of main chain poly(quaternary ammonium) EMR series surfactants by two-step method.①The intermediate product EM is synthesized by using epichlorohydrin and methylamine. Determined reaction conditions of epichlorohydrin which has high conversion rate by single factor:when the reaction temperature is 60℃, reaction time is 6h and the molar ratio of epichlorohydrin to methylamine is 1:1, the conversion of epichlorohydrin is up to 90%②Macromolecular surfactant EMR is synthesized by EM arid alkyl bromide. Determined the reaction conditions of EMR-12 which has highly [η] and CD by single factor:when the volume of methylamine solution is 20mL、the molar ratio of epichlorohydrin to methylamine is 1:1、the molar ratio of bromododecane to methylamine is 0.3:1、reaction time of EM and bromododecane is 6h、reaction temperature is 80℃and volume of alcohol is 60mL, [η] is up to 35.23mL/g, CD is up to 14%. (2) Evaluate the surface activity of EMR surfactants in aqueous solution and salt aqueous solution, and study on the composite property with anionic surfactant and non-ionic surfactant, respectively.①The result shows that the curves of y-C have double turning points by measuring surface tension of EMR surfactants in aqueous solution. The concentration of the first turning point C(pl) is 1g/L; When the number of carbon atoms are less than 12,γp1 decreases with increasing the number of carbon atoms at the first turning point, and ypi increases with increasing the number of carbon atoms subsequently. The cmc decreases with increasing the number of carbon atoms at the second turning point; When the number of carbon atoms are less than 12,γcmc decreases with increasing the number of carbon atoms, andγcmc increases with increasing the number of carbon atoms subsequently. When the number of carbon atoms are more than 12, cmc of EMR is similar or less than DTAB,γcmc is lower than DTAB. The more CD of EMR-12, the lower cmc andγcmc.②In the experimental concentration of NaCl solution, cmc,γp1 andγcmc decrease with increasing concentration of NaCl for EMR-12; C(p1) keeps almost unchanged And in the experimental concentration of CaCl2 solution, cmc andγcmc decrease with increasing of concentration of CaCl2 for EMR-12; when the concentration of CaCl2 is less than 0.5%, C(p1) keeps almost unchanged,γp1 decreases with increasing of concentration of CaCl2;and when the concentration of CaCl2 is more than 0.5%, the first turning point disappear. The addition of salts can enhance the surface activity of EMR.③Compare with EMR-12 solution, C(p1) keeps unchanged for EMR-12/SDS composite system, butγp1 decreases a little. The cmc of EMR-12/SDS composite system is lower than EMR-12 solution and higher than SDS solution;γcmc is lower than EMR-12 and SDS solution. C(p1) andγp1 of EMR-10 decrease after mixture of EMR-10 and OP-10. Within the range of test study,γcmc of composite system is similar to OP-10, but cmc is lower than any of single-component. The value of cmc are 1/20～1/16 and 1/5～1/4 for EMR-12 and OP-10, respectively. (3) EMR have highly anti-swelling、good stability of anti-swelling properties and flocculation properties for clay. Study on the effect of the length of hydrophobic group of EMR for anti-swelling properties.①When the concentration are 0.3% and 0.5% for EMR-14 and EMR-16 respectively, anti-swelling rates are up to 94%～95%. As a comparison, more than 1% concentration are required to achieve the similar effect for the highest anti-swelling rate KCl; The anti-swelling rates of clay treated by EMR are the same as original after 24h soaking, however, the anti-swelling rates of clay treated by inorganic clay stabilizers after 24h soaking are lower than original.②Discusse the relationship of anti-swelling rate and molecular structure of EMR. The anti-swelling rate is quickly increased with the increase of hydrophobicity of EMR. When the anti-swelling rate reach constant value, the concentration of [EMR-8]、[EMR-10]、[EMR-12]、[EMR-14] and [EMR-16] are 1%,0.8%,0.6%, 0.5% and 0.3%, respectively. The highest anti-swelling rate is increased with the increase of hydrophobicity. The highest anti-swelling rate of each EMR is 95% EMR-16>94%EMR-14>91%EMR-12>90%EMR-10>89%EMR-8.③Analyze the reason why EMR has highly anti-swelling rate and good stability of anti-swelling properties:Because many quaternary ammonium salt groups of EMR can strongly adsorb with negative charges on clay surface and its many hydrophobic side groups expose to outside of clay that can associate hydrophobic layer by dispersive force, so it can prevent water molecules spreading towards clay. Within the range of test study, the more hydrophobic groups, the more thick hydrophobic layer, the more stronger shielding effect for water, and the better anti-swelling properties.④Study on the flocculation properties of clay suspension solution for EMR. At the condition of same concentration, the more carbon atoms of hydrophobic groups of EMR molecular chain, the much higher light transmittance of clay suspension solution, the more supernatant liquid.