Acrylic acid (AA), butyl acrylate (BA), methyl methacrylate (MMA), hydroxypropyl acrylate (HPA), hydroxyethyl methacrylate (HEMA) and vinyl triisopropoxy-silane (A-173) were used as polymeric monomers, benzoyl peroxide (BPO) and tert-butyl benzoate peroxide (TBPB) as initiators, macromolecular emulsifiers which can be used as emulsifiers for aqueous acrylate emulsion were synthesized. Then, water-based acrylic acid soap-free emulsion was synthesized by emulsion polymerization and mixed with pigment to prepare water-based ink. The structure and properties of polymers were characterized by FTIR, DSC, TEM and SEM. The effects of different amounts of initiator on macromolecular emulsifiers and the effects of different amounts of acrylic acid (AA) on soap-free aqueous acrylic emulsion and ink were investigated. The results showed that when the minimum surface tension of macromolecular emulsifier was 40.43 mN /m, the amount of AA in the water-based acrylic emulsion was 1.0% of the total monomer mass, the resin storage stability was good, the mechanical properties of the film was good, the tensile strength could reach 5 MPa, the elongation at break was 195%, and the glass transition temperature was 18.5 ℃. The prepared water-based ink has moderate viscosity, adhesion level of 1 and friction resistance level of 4.5.