Waterborne Polyurethane Acrylate Research Articles

Synthesis and properties of waterborne polyurethane acrylate emulsions with high bio‐based content

Synthesis and properties of waterborne polyurethane acrylate emulsions with high bio‐based content

A Novel Polyfunctional Polyurethane Acrylate Derived from Castor Oil-Based Polyols for Waterborne UV-Curable Coating Application.

Because of its unique molecular structure and renewable properties, vegetable oil has gradually become the focus of researchers. In this work, castor oil was first transformed into a castor oil-based triacrylate structure (MACOG) using two steps of chemical modification, then it was prepared into castor oil-based waterborne polyurethane acrylate emulsion, and finally, a series of coating materials were prepared under UV curing. The results showed that with the increase in MACOG content, the glass transition temperature of the sample was increased from 20.3 °C to 46.6 °C, and the water contact angle of its surface was increased from 73.85 °C to 90.57 °C. In addition, the thermal decomposition temperature, mechanical strength, and water resistance of the samples were also greatly improved. This study not only provides a new idea for the preparation of waterborne polyurethane coatings with excellent comprehensive properties but also expands the application of biomass material castor oil in the field of coating.

Preparation and properties of cationic waterborne polyurethane/acrylate for fluorine‐free water repellents

AbstractIn this work, cationic waterborne polyurethane/acrylate (WPUA) was synthesized for water repellent in cotton fabrics to replace fluorine‐containing finishing agents with the concerns of ecosystems and human health. First, the tertiary amines monomers, N‐methyl diethanolamine, 3‐dimethylamine‐1, 2‐propylene glycol, N,N′‐bis (2‐hydroxyethyl)piperazine, were used as chain extenders to prepare waterborne polyurethane, respectively. Long‐chain octadecyl acrylate monomers were then grafted to the waterborne polyurethane by a self‐emulsifying method. The stable WPUA suspensions of positively charged latexes were obtained and could be finished on cotton fabrics via a simple pad‐curing process. The coated cotton fabrics were capable of repelling common liquids without any penetration, and the contact angles of the treated cotton fabrics could reach 150°. The WPUA latex films also exhibited good tensile mechanical properties and thermal dimensional stability. The cotton fabric coated with the WPUA showed good laundering durability, and its static water contact angle was still maintained at 142° even after 50 times washing. This work not only highlights the structural design and preparation but also provides a feasible strategy for fluorine‐free water repellency in cotton fabrics, which has great potential application prospects for a variety of fields.

UV-curable organic silicone grafting modified waterborne polyurethane acrylate: Preparation and properties

The organosilicon grafting copolymerization waterborne polyurethane acrylate composite coating (WPUA@KH570) with high surface properties was prepared by the UV curing method from mixing silicone monomer surface-modified ZnO (Si@ZnO) as photoinitiator to waterborne polyurethane acrylate (WPUA) emulsion. The effects of the polyurethane isocyanate index (R), the addition amount of hydrophilic chain elongator DMBA (wDMBA), the ratio of PU/PA on the stability of the synthesized WPUA emulsion were explored. The properties of the WPUA@KH570 composite coatings with different contents of organosilicon surface-modified ZnO were characterized by the particle size distribution meter, FTIR, XRD, SEM, UV–Vis–NIR spectrophotometer, contact angle (CA) and water absorption rate (WAR). The results showed that when R = 1.4, wDMBA = 0.04 and PU/PA = 0.6, the WPUA emulsion had an excellent stability. When the content of organosilicon modified ZnO reached 1.5 wt%, the CA increased to 90.6°, the WAR decreased to 15.4 %, and the absorbance reached 0.5. The WPUA@KH570 composite coating could be changed from hydrophilic to hydrophobic, which can step further promoted the surface properties, water resistance and UV absorption.

The Post-Curing of Waterborne Polyurethane-Acrylate Composite Latex with the Dynamic Disulfide-Bearing Crosslinking Agent.

The development of a dynamic network for commodity polymer systems via feasible methods has been explored in the context of a society-wide focus on the environment and sustainability. Herein, we demonstrate an adaptive post-curing method used to build a self-healable network of waterborne polyurethane-acrylate (WPUA) composite latex. The composite latex was synthesized via the miniemulsion polymerization of acrylates in the dispersion of waterborne polyurethane (PU), with commercial acetoacetoxyethyl methacrylate (AAEM) serving as the functional monomer. Then, a dynamic disulfide (S-S)-bearing diamine was applied as the crosslinking agent for the post-curing of the hybrid latex via keto-amine condensation, which occurred during the evaporation of water for film formation. It was revealed that the microphase separation in the hybrid films was suppressed by the post-curing network. The mechanical performance exhibited a high reliability as regards the contents of the crosslinking agents. The reversible exchange of S-S bonds meant that the film displayed associative covalent-adaptive networks in the range of medium temperature in stress relaxation tests, and ≥95% recovery in both the stress and the strain was achieved after the cut-off films were self-healed at 70 °C for 2 h. The rebuilding of the network was also illustrated by the >80% recovery in the elongation at break of the films after three crushing-hot pressing cycles. These findings offer valuable insights, not only endowing the traditional WPUA with self-healing and reprocessing properties, but broadening the field of study of dynamic networks to polymer hybrid latex.

Preparation and Properties of UV-Curable Waterborne Polyurethane Acrylate/MXene Nanocomposite Films

In this study, waterborne polyurethane acrylate (WPUA)/MXene nanocomposite films with varying MXene loadings were fabricated using UV-curing technology, where MXene (Ti3C2Tx) was employed as a nanofiller. The microstructure and chemical structure of the WPUA/MXene nanocomposite films were examined by XRD and FTIR, respectively. The water contact angle testing demonstrated that the incorporation of MXene into the nanocomposite films led to an increase in their hydrophilic properties. The tensile strength, the elongation at break, and Young’s modulus of the WPUA/MXene nanocomposite coatings exhibited an initial increase followed by a decrease with increasing MXene loadings. Compared to the pure WPUA film, the tensile strength and elongation at break of nanocomposites with 0.077 wt% MXene loading reached their maximum values, which increased by 39.9% and 38.5%, respectively. Furthermore, the glass transition temperature and the thermal stability were both enhanced by MXene to some extent. This study introduces a novel method for utilizing MXene in UV-curable waterborne coatings.

Effects of Grafting Degree on the Formation of Waterborne Polyurethane-Acrylate Film with Hard Core-Soft Shell Structure.

Waterborne polyurethane-acrylate (WPUA) grafted with polyurethane was prepared to improve the film-forming ability of hard-type acrylic latex. To balance the film-formation ability and hardness, the WPUA latex was designed with a hard core (polyacrylate) and soft shell (polyurethane). The grafting ratio was controlled through varying the content of 2-hydroxyethyl methacrylate (HEMA) used to cap the ends of the polyurethane prepolymer. The morphologies of the latex particles, film surface, and fracture surface of the film were characterized through transmission electron microscopy, atomic force microscopy, and scanning electron microscopy, respectively. An increase in the grafting ratio resulted in the enhanced miscibility of polyurethane and polyacrylate but reduced adhesion between particles and increased minimum film formation temperature. In addition, grafting was essential to obtain transparent WPUA films. Excessive grafting induced defects such as micropores within the film, leading to the decreased hardness and adhesive strength of the film. The optimal HEMA content for the preparation of a WPUA coating with excellent film-forming ability and high hardness in ambient conditions was noted to be 50%. The final WPUA film was prepared without coalescence agents that generate volatile organic compounds.

Photo-curable waterborne polyurethane acrylates with low VOCs and low odor by devolatilization and deodorizing

In order to remove VOCs in paints and coatings as more as possible, photo-curable waterborne polyurethane acrylates (WPUAs) were synthesized and an easy process to obtain low VOCs and low odor by the devolatilization technology was investigated. It was found that VOCs contents and WPUAs odors were significantly reduced by using the deionized water as the devolatilization aid chemical. With the conditions that the temperature was 75 °C, vacuum degree was 0.085 MPa, and the added deionized water content was 3 wt%, the VOCs content of WPUA was 33.6 mg/g with odor level 2 after devolatilization. Moreover, in the process of devolatilization, the increasing temperature strengthened the mass transfer process, thus the removal efficiency of VOCs was improved. Comparison with the WPUA coatings without devolatilization, the photo-cured films of deodorized WPUA coatings showed good thermal stability and excellent mechanical properties due to most of the solvents and small molecular impurities were removed. The WPUA coatings with low VOCs not only reduced environmental pollution, but also improved their coatings quality. At the same time, the devolatilization technology had the characteristics of simplicity and efficiency. Therefore, it was suitable for industrial production of organic photo-curable coatings in order to protect both environment and people's health as much as possible.

High solid and low viscosity waterborne polyurethane acrylate with excellent anti-corrosion and anti-bacterial performances

The design and preparation of great corrosion resistance and high-solid waterborne polyurethane dispersion with low viscosity is still a challenge in the field of the polyurethane industry. Herein, we developed a simple method involving a core-shell process to prepare a core-shell structured waterborne polyurethane acrylate dispersion (WPUAD). First, isobornyl acrylate, a derivative of natural product borneol, dihydroxylated by a thiol-ene click reaction was used to prepare oil-based polyurethane acrylate as prepolymer A (core) and waterborne polyurethane acrylate as prepolymer B (shell). Then, the core-shell WPUAD was obtained by mixing and emulsifying the two prepolymer at a certain ratio. The study reveals that the core-shell structured WPUAD not only has a low viscosity (~1330 mPa.s) but also holds a high-solid content (~ 60 wt%). At the same time, the highly solid WPUAD has excellent stability with no breast breakage even after more than 1 year of storage. In addition, various electrochemical measurements, water contact angles, and water absorption tests were performed to determine the anti-corrosive properties of the WPUAD-derived coatings. The results show that the WPUA coatings exhibit significantly enhanced anticorrosion with respect to the single prepolymer B derived coatings, which is attributed to their high cross-linking density resulting from the core-shell structure and the introduction of hydrophobic isobornyl acrylate. In addition, because of the introduction of the dihydroxylated isobornyl acrylate as chain extenders, the WPUA coating has great anti-bacterial adhesion properties with an anti-bacterial efficiency of 82.3 %. We believe that our work provides a generic preparation method to obtain a commercially available high-solid WPUAD with excellent anti-corrosion properties.

Making a new bromo-containing cellulosic dye with antibacterial properties for use on various fabrics using computational research

The reaction of cyanoethyl cellulose with para-bromo diazonium chloride resulted in the creation of a novel bromo-containing cellulosic (MCPT). The dispersion stability of MCPT has been improved by its dispersion into 1% waterborne polyurethane acrylate (WPUA). TEM, particle size, and zeta potential were used to track the dispersion stability of aqueous MCPT and MCPT in 1% WPUA and particle size. The prepared MCPT has been utilized as a unique green colorant (dye) for the printing of cotton, polyester, and cotton/polyester blend fabrics using a silkscreen printing technique through a single printing step and one color system. Color improvement has been achieved by printing different fabrics with a printing paste of MCPT dispersed in 1% WPUA. The MCPT and MCPT in 1% WPUA printed fabrics were evaluated for rubbing, light, washing, and perspiration fastness, UV blocking activity, and antibacterial activity. These findings were established through structural optimization at the DFT/B3LYP/6-31 (G) level and simulations involving several proteins.

Biomimetic high water adhesion superhydrophobic surface via UV nanoimprint lithography

Imitating nature and comprehending its workings is a means for human beings to advance the development of functional materials. In this study, UV nanoimprint lithography technology was utilized to successfully replicate the micro-nano hierarchical structure (micro-papillae and nano-wax tube crystals) present on the surface of the natural fresh lotus leaf. A series of UV-curable waterborne polyurethane acrylate (UV-WPUA) surfaces with special wetting and superhydrophobic properties were obtained. The polydimethylsiloxane negative stamp with lotus leaf’s structure was obtained through a stamp replica molding method, and then the UV-WPUA resin covered with the negative stamp was exposed to 172 nm Xe2* excimer and medium-pressure mercury lamps to mimic the micro-nano hierarchical structure of the lotus leaf. The UV-WPUA surfaces displayed high water adhesion superhydrophobic properties, with a water contact angle reaching 160.8° and water adhesive force of 140.0 μN, and exhibiting excellent self-cleaning performance. The results indicate that higher the UV intensity, the more accurately the surface replicates the micro-nano hierarchical structure of the lotus leaf, resulting in larger water contact angle and higher adhesive force. This study paves the way for the advancement of functional surfaces through the simulation of natural materials.

A new UV‐curable biodegradable waterborne polyurethane‐acrylate based on natural rubber blended with cassava starch

AbstractAn ecofriendly UV‐curable biodegradable waterborne polyurethane acrylate (WPUA) was synthesized using hydroxy telechelic natural rubber (HTNR), gelatinized cassava starch (GCS) hexamethylene diisocyanate, hydroxymethyl propionic acid and 2‐hydroxyethyl acrylate and Darocur 1173 (photo‐initiator) for coating, adhesive applications, and so forth. WPUA thus prepared with a total solid content of about 20% had a good storage stability with a pot‐life of 3 months. The UV‐curable WPUA/GCS films showed superior photosensitivity with an irradiation time of 60 s. With increasing GCS content of the WPUA/GCS films, its transparency increased and surface gloss decreased. Scanning electron microscopic micrographs indicated good miscibility with strong interactions between WPUA and GSC in the matrix leading to high tensile strength and surface free energy with enhanced thermal degradation. Increasing the GCS content up to 75 wt% in the film accelerated its degradation under weathering aging, and showed complete disintegration in soil after 7 days. This work provided a new environmentally friendly pathway to prepare WPUA based on HTNR and GCS with good biodegradability.

Waterborne polyurethane acrylate emulsion with dangling chain structure: Simultaneously showing wide damping temperature range and excellent hydrophobic performance

AbstractWaterborne polyurethane (WPU) damping material has been drawing much attention in academic field because of its low toxicity compared with polyurethane (PU) damping material. In order to expand the application range of WPU damping materials, it is necessary to further improve the hydrophobicity and damping properties of WPU. A novel dangling chain polyol‐n (DCP‐n, n expressed as average molecular weight of MPEG) was synthesized from methoxypolyethylene glycol (MPEG), isophorone diisocyanate (IPDI) and 1,1,1‐tris (hydroxymethyl) propane (TMP). Subsequently, a series of dangling chain‐n‐waterborne polyurethane acrylate (DC‐n‐WPUA, n expressed as average molecular weight of MPEG) emulsions were synthesized using DCP‐n as the chain extender. The increase of DCP‐n length will fill in free volume, hinder the entry of water molecules. Therefore, improve the hydrophobic performance. In addition, the increase of DCP‐n length will lead to more intermolecular friction, which can increase the dissipation of energy, and improves the damping performance of DC‐n‐WPUA. The test results show that the hydrophobicity of DC‐n‐WPUA film is improved, and the maximum static water contact angle can reach 110.6°. Dynamic mechanical analysis testing data showed that DC‐500‐WPUA has the best damping performance, and its effective damping temperature range was 77.9°C (−32.0 ~ 45.9°C). The carbamate group on DCP‐n will produce hydrogen bonds to restrict the movement of the chain segments, and the hydrogen bond breakage requires more energy. This ameliorates the thermal stability and mechanical properties of DC‐n‐WPUA. Thus, the initial modulus of DC‐n‐WPUA larger than the initial modulus of WPUA. Therefore, the DC‐n‐WPUA have the potential to be applied to hydrophobic damping coatings in the future.

Preparation of functionalZnOnanoparticles and their application asUVphotosensitizer and reinforcing agent for waterborne polyurethane acrylate composite coating

AbstractFunctional inorganic ZnO nanoparticles (ZnO NPs) have been designed and prepared, used as UV photosensitizers and reinforcing agents applied to waterborne polyurethane acrylate (WPUA) composite coating. The ZnO NPs are modified by the silane coupling agent, and the WPUA@ZnO NP composite coatings photoinitiated with different ZnO NP contents are prepared, their structure and properties are characterized by FTIR, XRD, SEM, BET, TG, and pencil hardness tester. The UV absorption of the inorganic photosensitizer ZnO NPs and the organic photosensitizer 1‐hydroxycyclohexyl phenone (184) in the composite coating is tested and analyzed separately by DRS UV‐3600 spectrophotometer. Three fabric‐based materials (cotton, PET, and PP) are dipped into the WPUA@184 composite emulsions and WPUA@ZnO NP composite emulsions, and their mechanical properties, water absorption and water contact angle (WCA) are tested. The results show that the absorbance of the WPUA@ZnO NP composite coating is 40.28% higher than that of the WPUA@184 composite coating. Compared with the PP‐WPUA@184 coatings, the stress of the PP‐WPUA@ZnO NP coatings increases by 41.19% and the strain increases by 34.39%. The water absorption of the cotton and PET coatings decreases under the three conditions. Their hydrophilicity and hydrophobicity are changed, and the fabric‐based coatings can be tuned for interfacial properties.

Effects of aminopropyl-terminated polydimethylsiloxane on structure and properties of waterborne polyurethane-acrylate

To achieve a good balance between mechanical properties and water resistance of the waterborne polyurethane (WPU) film, the hydroxylethyl acrylate (HEA) terminated waterborne polyurethane-acrylate (WPUA) emulsion was prepared by chain extension of 3,6-dioxa-1,8-octanedithiol (BOODT) and modification of aminopropyl-terminated polydimethylsiloxane (APT-PDMS). The effects of APT-PDMS on the microphase separation structure and the performance of WPUA film were investigated by varying the molar ratio of APT-PDMS to HEA. The introduction of APT-PDMS caused an increase in the content of hydrophobic groups, which could induce the rearrangement of the PDMS chain segments on the surface of WPUA during film formation. The rearrangement enhanced the surface hydrophobicity of WPUA, also improved the phase separation between hard and soft segments. The former was beneficial to obtaining better water resistance, while the latter was conducive to improving mechanical properties. However, the decrease in cross-linking degree will limit the mechanical properties and the water resistance with the increase in APT-PDMS/HEA molar ratio. The optimal balance between mechanical properties and water resistance can be achieved when the APT-PDMS/HEA molar ratio is 0.25. This work provides a feasible scheme for the industrial production of WPUA emulsions.

Preparation and Properties of UV and Aziridine Dual–Cured Polyurethane Acrylate Emulsion

For the UV–curable waterborne polyurethane acrylate (WPUA) emulsion, the free carboxylic groups in the molecular chains introduced by hydrophilic monomers are the inherent disadvantage. We prepared UV and aziridine dual–cured WPUA (UV/AZ–WPUA) emulsion that the carboxylic groups can be crosslinked by the trifunctional aziridine crosslinking agent, trimethylolpropane tris(2-methyl-1-aziridinepropionate) (Sac–100). The effects of Sac–100 content on the gel fraction, tensile properties, hardness, wear resistance, water resistance, and surface morphology of the cured films and coatings were investigated. The results show that, with the increase of the Sac–100 content, the gel fraction, tensile strength, elongation at break, and toughness of the films increase first and then decrease and the wear weight loss and water absorption ratio gradually decrease; in addition, Sac–100 also has an effect on the surface roughness of the coatings. Through comprehensive evaluation, it is considered that the optimum Sac–100 content is 4 wt% in UV/AZ–WPUA system. With the optimum Sac–100 content, the gel fraction of the coating film is 89.78 wt%, the tensile strength is 34.58 MPa, the elongation at break is 343.64%, the toughness is 65.08 MJ/m3, the wear loss is 4.7 mg, and the equilibrious water–absorption ratio is 11.63 wt%. Compared with the UV–cured film without Sac–100, the tensile strength, toughness, and hardness of the dual–cured films increase by 155.4%, 129.3%, and 25.7%, respectively, and the water absorption ratio decreases by 27.1%.

Preparation and Properties of Novel Modified Waterborne Polyurethane Acrylate

A series of novel modified waterborne polyurethane acrylate (WPU-EA) emulsions were prepared with isophorone diisocyanate (IPDI), polycarbonate diol, 2,2-bis-hydroxymethyl-propionic acid (DMPA), 1,4-butanediol (BDO), epoxy acrylate (EA), and pentaerythritol triacrylate (PETA). The structure of WPU-EA was confirmed by FTIR and 1H NMR spectroscopy. The effects of different dosages of epoxy acrylate on the cured film were investigated by tensile properties, dynamic mechanical analysis and thermogravimetric analysis. The results indicate that with increasing content of epoxy acrylate, the average particle size of the emulsion gradually increases. With the rise in epoxy acrylate concentration from 0%, 3.0%, 6.0% to 9.0%, the gel fraction of the cured film increases from 83.7%, 92.5%, 93.0% to 93.6%, respectively, and the glass transition temperature rises from 90.3 °C, 107.5 °C, 141.9 °C to 146.6 °C. The tensile strength and the thermal stability of the cured film increases, and the elongation at break decreases. Moreover, the WPU-EA emulsions were sprayed on polycarbonate sheets and exhibited the advantages of high hardness, better gloss and good adhesion, which is promising for the application of plastic coatings.

Preparation of Polyurethane/Acrylate Composite Emulsion for Inkjet Printing

Water-borne polyurethane/acrylate (WPUA) emulsion was prepared through emulsion polymerization between vinyl terminated waterborne polyurethane (WPU) and methyl methacrylate (MMA) in this research. Thermogravimetric Analysis (TGA), transmission electron microscopy (TEM), contact angle analysis, and particle size distribution analysis were employed to investigate the performance of the prepared emulsion and coatings with various content of MMA content. The results demonstrated that the thermal resistance, water resistance, and hardness of the prepared WPUA coatings were enhanced by the introduction of the MMA monomer. The contact angle (CA) and particle size of WPUA emulsion increased with the increase of MMA content. Meanwhile, the water-borne inkjet printing ink was prepared using WPUA emulsion as binder resin, and the printing test result showed that the prepared inkjet ink has good printability and color rendering, indicating that WPUA emulsion has great application prospects in the field of inkjet printing.

Waterborne polyurethane‐acrylate‐polyaniline: Interfacial hydrogen bonding for enhancing the antistatic, damping, and mechanical properties

AbstractDamping coatings can convert kinetic energy into other forms of energy for consumption and have been widely used for vibration and noise reduction in rail trains, aerospace, automobile industry, and other fields. However, many aspects of damping coating such as, damping, water resistance, heat resistance, mechanical properties and antistatic properties require further improvement. In this study, a low‐cost conductive polyaniline (PANI) with a simple preparation method was dispersed in N‐methyl pyrrolidone and added to waterborne polyurethane‐acrylate (WPUA) hybrid latexes. The interfacial hydrogen bonding increases the interaction force between molecular chains, effectively improve the water resistance, heat resistance, damping, and mechanical properties of WPUA, and endowed WPUA with antistatic properties. Among them, PANI was used as an antistatic medium to be synthesized by chemical oxidation and doped with dodecylbenzene sulfonic acid, and the matrix polymer WPUA was the used of hydroxyethyl methacrylate (HEMA) to combine polyacrylate with waterborne polyurethane (WPU) by chemical bonds. The waterborne polyurethane‐acrylate‐polyaniline (WPUA‐PANI) films were investigated using dynamic light scattering , contact angle measurements , dynamic mechanical analysis, Fourier‐transform infrared spectroscopy (FTIR), digital highresistance meter and other characterization methods. It was concluded that the base latex has good stability, and when the PANI dispersion content was 35%, the comprehensive performance of the WPUA‐PANI films were the best, in which the maximum water contact angle was 106.8°, the tensile strength was increased from 0.7 MPa to 2.3 MPa, the effective damping temperature range (Tanδ ≥ 0.3) was increased from 50 °C to 87 °C, and the resistivity was reduced from 6.41E + 7 Ω·cm to 1.38E + 4 Ω·cm, which had better antistatic properties. This study will promote the development and application of damping coatings.

Waterborne Polyurethane Acrylates Preparation towards 3D Printing for Sewage Treatment.

Conventional immobilized nitrifying bacteria technologies are limited to fixed beds with regular shapes such as spheres and cubes. To achieve a higher mass transfer capacity, a complex-structured cultivate bed with larger specific surface areas is usually expected. Direct ink writing (DIW) 3D printing technology is capable of preparing fixed beds where nitrifying bacteria are embedded in without geometry limitations. Nevertheless, conventional bacterial carrier materials for sewage treatment tend to easily collapse during printing procedures. Here, we developed a novel biocompatible waterborne polyurethane acrylate (WPUA) with favorable mechanical properties synthesized by introducing amino acids. End-capped by hydroxyethyl acrylate and mixed with sodium alginate (SA), a dual stimuli-responsive ink for DIW 3D printers was prepared. A robust and insoluble crosslinking network was formed by UV-curing and ion-exchange curing. This dual-cured network with a higher crosslinking density provides better recyclability and protection for cryogenic preservation. The corresponding results show that the nitrification efficiency for printed bioreactors reached 99.9% in 72 h, which is faster than unprinted samples and unmodified WPUA samples. This work provides an innovative immobilization method for 3D printing bacterial active structures and has high potential for future sewage treatment.