Preparation And Performance Of Guanidine Salt-cationic Polymer Supramolecular Composite System

The cationic acrylamide polymers(CPMA)are products of modified acrylamide polymers.It can adsorb compounds with negative charge for multiple quaternary ammonium groups on its molecular chain.They have the ablity of turbidity removal,decoloring and adsorpt.So be widely used for dyeing,paper making,metallurgy,mineral processing,coal and oil field.As shale inhibitor,CPMA can form multi-point adsorption on the surface of clay particles due to their structural characteristics,and as a result of that,it has the properties of low dosage,high efficiency and wide range of applicable pH.At present,the application of network crosslinked polymer and hyperbranched polymer has become an important work for oilfield chemists.Compared with the linear polymers at same molecular weight,hyperbranched polymers have lower viscosity and better solubility.In addition,because of the large number of active functional groups at the end of their molecular structure,which can be modified with different methods and used in different fields.In this paper,CPAM and a guanidine of h-PAMAM were compounded in an aqueous solution to obtain a kind of guanidine-polymer supramolecular networks,which provided a theoretical basis for using in inhibiting the hydration and expansion of clay in oil fields.The main research contents are as follows:(1)The functional monomers of 1-allyl-3-phenyl thiourea(APTU),1-allyl-3-methyl thiourea(AMTU),and another monomer named ally]p-toluene sulfonamide(ABSM)were synthesized and characterized by FT-IR and 1H NMR.(2)P(AM-DAC-ABSM),P(AM-DAC-APTU)and P(AM-DAC-AMTU)were synthesized by aqueous solution polymerization respectively using V50 as initiators,and all of them were characterized by IR and investigated the content of monomers.Then the optimum synthesis conditions of copolymers were obtained by means of single factor method.P(AM-DAC-ABSM):m(AM):m(DAC)=6:4,the dosage of ABSM is 0.8 wt%,the dosage of V50 is 0.3 wt%,the reaction temperature is 65? and the reaction time was 8 h.P(AM-DAC-APTU)and P(AM-DAC-AMTU):m(AM):m(DAC)=7:3,the dosage of APTU(AMTU)is 1.0 wt%,the dosage of V50 is 0.3 wt%,the reaction temperature is 55? and the reaction time was 8 h.(3)The intrinsic viscosity of these three copolymers were 706 mL/g,659 mL/g and 734 mL/g.The thermogravimetric analysis indicated that P(AM-DAC-ABSM)and P(AM-DAC-APTU)which contained benzene had better thermostability than P(AM-DAC-AMTU).(4)The h-PAMAM and guanidine of h-PAMAM were synthesized and characterized by FT-IR and 1H NMR.Studies have shown that the addition of guanidine in polymer solution can increase the anti-swelling ratio of polymers with thiourea functional groups by 4 percentage points and reduce the concentration of polymers with the maximum anti-swelling ratio by about 2000 mg/L,while only the anti-swelling ratio be increased in guanidine-P(AM-DAC-ABSM).In order to facilitate the observation in later performance study,the compound system was formed by guanidine concentration of 100 mg/L and the polymer concentration of 5000 mg/L.(5)In this paper,the anti-swelling ratio of three kinds of single polymers,named P(AM-DAC-ABSM),P(AM-DAC-APTU)and P(AM-DAC-AMTU),and their composite solutions with h-PAMAM guanidine in common inorganic salts(NaCl,NH4Cl and KCl)were studied.The results showed that the interaction between polymer and h-PAMAM guanidine would be destroyed when the salt concentration was too high.However,due to the anti-swelling effect of these commonly used inorganic salts,the anti-swelling of the three polymers and their compounds with guanidine in the salt solutions were firstly increased slightly and then decreased or stabilized.In three salt solutions,the maximum anti-swelling ratio of guanidine-P(AM-DAC-ABSM)solution was 92%and the maximum anti-swelling ratio of P(AM-DAC-APTU)and P(AM-DAC-AMTU)compounded systems was about 94%and 96%,respectively.(6)The retention values of anti-swelling ratio of the six solutions were determined at different temperatures and different washing times.Results showed that anti-swelling ratio of the complex system of P(AM-DAC-APTU)(or P(AM-DAC-AMTU))and guanidine were firstly slightly increase and then decrease with the temperature rising and at 100?,the retention value of anti-swelling ratio were 76.1%(73.1%).With the increase of temperature,the anti-swelling ratio of P(AM-DAC-ABSM)-guanidine compound solution and three single polymer solutions decrease.And its anti-swelling ratio was 71.5%at 100?.(7)The recovery rate of shale experiments of six solution systems were carried out and the influence of these solutions on the crystal spacing of montmorillonite was investigated.The results showed that the polymer and its composite system not only had good property of anti-swelling,but also have excellent long-term property.The crystal spacing of the montmorillonite samples treated by the three composite solution systems was not significant different,while the single polymer solutions was just a little bit worse.(8)The shear behavior and viscoelasticity of six solutions were studied.The results showed that the shear dilution and viscoelastic properties of the composite system of P(AM-DAC-APTU)and P(AM-DAC-AMTU)with guanidine were better than that of the single polymer solutions,while the composite system of P(AM-DAC-ABSM)with guanidine was not significant different with the three single polymer solutions.The all six solutions have good shear recovery performance and the viscosity loss rate is less than 3%.