Dimethylol Butanoic Acid Research Articles

Influence of Pentaerythritol Core and Dimethylol Butanoic Acid Monomer-Based Aliphatic Hyperbranched Polyester on the Tribonegative Performance of Polyvinylidene Fluoride

Influence of Pentaerythritol Core and Dimethylol Butanoic Acid Monomer-Based Aliphatic Hyperbranched Polyester on the Tribonegative Performance of Polyvinylidene Fluoride

Green waterborne synthesis of hemocompatible polycarbonate–polyether polyurethanes

Polyurethane (PU) is a family of biomedical elastomers with promising applications. In this study, we describe the synthesis of a novel waterborne PU with high solid content and low viscosity. The soft segment of the PU consists of polycarbonate diol (PCDL) and polytetramethylene ether glycol. Dimethylolbutanoic acid is used as a chain extender. To stabilize the emulsion in the synthetic process, nonionic groups (polyoxyethylene styrenated phenyl and polyoxyethylene tridecyl ethers) are used as surfactants. PUs with good hydrophilicity and proper hemocompatibility were successfully synthesized using this approach. The chemical composition of the PU was adjusted by changing the soft-to-hard segment ratio. The effects of this composition ratio on the crystallization properties of PU were characterized using differential scanning calorimetry, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, attenuated total reflectance infrared spectroscopy, thermogravimetric analysis, alternating magnetic field, and contact angle measurements. Film casts from PUs prepared in this study showed good mechanical properties, including Young’s modulus (0.66–48 MPa), tensile strength (11.7–30.9 MPa), and strain at break (173%–579%). Moreover, introducing PCDL in the soft segment during preparation improved the microphase separation and reduced the water contact angle of the films, which enhanced the hydrophilicity of the PU. Our findings demonstrate the potential of the new waterborne PU formulation to significantly improve the performance and durability of biomaterials and blood-contacting devices. Furthermore, this formulation meets the required hemolytic standards, which supports its suitability for medical applications.

A novel method for the synthesis of solvent‐free and high‐solid‐content waterborne polyurethanes by introducing a small amount of polyethylene glycol

AbstractIn the study, the synthesis process involved the reaction of dimethylolbutyric acid and polytetramethylene ether glycol 1000 (PTMG1000) with hexamethylene diisocyanate (H12MDI), taking advantage of their mutual dissolution at high temperatures. The chain‐extension reaction with 1,4‐butanediol (BDO) was successfully conducted without the use of organic solvents. The emulsification reaction was carried out using the polyurethane prepolymer at 60% solids content, along with aqueous dispersions of polyethylene glycol (PEG) with varying molecular weights and amounts as interfacially active agents. Fourier transform infrared spectroscopy analysis suggested potential hydrogen bonding interactions between the PEG molecular chain and the polyurethane chain. Rheometer analysis demonstrated a significant reduction in viscosity with the addition of 1–5 wt.% PEG, accompanied by an increase in average particle size. This phenomenon was attributed to the formation of a hydrophilic lubrication layer of PEG around the water‐based polyurethane (WPU) microcells. Among them, WPU films containing 4 wt.% PEG4000 not only exhibited soft properties with a mechanical elongation rate exceeding 2000% but also showed excellent storage stability. The addition of long‐chain PEG facilitated the formation of a lubrication layer between the microcells, contributing to spatial stabilization and reducing particle aggregation at high solids content. It is noteworthy that this solvent‐free process, without any organic solvents, together with the adjusted PEG content, successfully synthesized waterborne polyurethanes with low viscosity and high solids content. This provides a new sustainable and environmentally friendly method for the future production of waterborne polyurethanes.

Synthesis and properties of biodegradable waterborne polyurethane modified as castor oil

A series of biodegradable waterborne polyurethane (WPU) based on polycaprolactone diol and castor oil is synthesized through the process of the polyaddition reaction. Biodegradable WPUs are designed by using polycaprolactone diol and 4,4′- methylene dicyclohexyl diisocyanate as the main domain of urethane, dimethylol butanoic acid as the anionic internal emulsifier and trimethylamine as the neutralizing agent. Castor oil is introduced as a key component to induce or maximize the biodegradability and biocompatibility of a WPU series. The biodegradable ability of WPUs are changed by the control of Castor oil content and molecular weight (MW). The biodegradation of a WPU series prepared in this study is analyzed in field emission scanning electron microscopy through visual modifications in bio-enzyme evaluation. The effects of Castor oil and MW on the physical properties are evaluated using gel permeation chromatography (GPC), universal test machine (UTM), dynamic light scattering (DLS), differential scanning calorimetry (DSC), and field emission scanning electron microscopy (FE-SEM). The WPU with high level of MW and Castor oil shows enough enhancement in tensile strength and Young's modulus, ranging from 12.28 to 23.47 MPa and from 0.04 to 0.137 MPa, respectively. SEM results point to a significant microphase biodegradation of a WPU series by bio-enzymes. It can be an environmental-friendly candidate to apply various biofields.

Construction of Mechanically Reinforced Thermoplastic Polyurethane from Carbon Dioxide-Based Poly(ether carbonate) Polyols via Coordination Cross-Linking.

Using carbon dioxide-based poly(propylene ether carbonate) diol (PPCD), isophorone diisocyanate (IPDI), dimethylolbutyric acid (DMBA), ferric chloride (FeCl3), and ethylene glycol (EG) as the main raw materials, a novel thermoplastic polyurethane (TPU) is prepared through coordination of FeCl3 and DMBA to obtain TPU containing coordination enhancement directly. The Fourier transform infrared spectroscopy, 1H NMR, gel permeation chromatography, UV−Vis spectroscopy, tensile testing, dynamic mechanical analysis, X-ray diffraction, differential scanning calorimetry, and thermogravimetric analysis were explored to characterize chemical structures and mechanical properties of as-prepared TPU. With the increasing addition of FeCl3, the tensile strength and modulus of TPU increase. Although the elongation at break decreases, it still maintains a high level. Dynamic mechanical analysis shows that the glass-transition temperature moves to a high temperature gradually along with the increasing addition of FeCl3. X-ray diffraction results indicate that TPUs reinforced with FeCl3 or not are amorphous polymers. That FeCl3 coordinates with DMBA first is an effective strategy of getting TPU, which is effective and convenient in the industry without the separation of intermediate products. This work confirms that such Lewis acids as FeCl3 can improve and adjust the properties of TPU contenting coordination structures with an in-situ reaction in a low addition amount, which expands their applications in industry and engineering areas.

Synthesis and Characteristics of Eco-Friendly 3D Printing Material Based on Waterborne Polyurethane.

Photo-cured 3D architectures are successfully printed using the designed waterborne polyurethane-acrylate (WPUA) formulation. A WPUA series is synthesized in the presence of polycaprolactone diol (PCL) and 4,4′-methylene dicyclohexyl diisocyanate (H12MDI) as the soft segment part, dimethylolbutanoic acid (DMBA) as the emulsifier, and triethylamine (TEA) as the neutralizer, as a function of prepolymer molecular weight. The compatibility of WPUA and the photo-activating acryl monomer is as a key factor to guarantee the high resolution of 3D digital light processing (DLP) printing. The optimized blending formulations are tuned by using triacrylate monomers instead of diacrylate derivatives. For the high-accuracy and fine features of 3D DLP printing, WPUA are designed to be a suitable molecular structure for a 385 nm wavelength source, and the target viscosity is achieved in the range from 150 to 250 Cp. Photo-cured 3D architectures based on WPUA exhibit good flexural strength and high resolution.

Synthesis of waterborne polyurethane ink binder with high T‐peel strength and its application in biaxially oriented polypropylene film printing

AbstractIn order to improve adhesion properties of waterborne polyurethane (WPU) inks on biaxially oriented polypropylene (BOPP) films, herein, a liquid polyester polyol BY3003 with long‐branched aliphatic chains was used to prepare WPU latexes suitable for BOPP films printing. The application of BY3003 made the surface tension of the prepared latexes not more than 43 mN/m, while that of traditional WPU latex exceeded 55 mN/m. Accordingly, the T‐peel strength of the inks made from these latexes was all above 0.8 N/15 mm. In addition, post chain extension degree, dimethylol butyric acid content, and NCO/OH molar ratio also had significantly effect on latex and film properties of WPU, especially on the T‐peel strength of the corresponding inks. By optimizing these factors, a WPU latex with surface tension as low as 39.6 mN/m and adhesion fastness over 95% on BOPP film were obtained, and the T‐peel strength of its corresponding ink was up to 2.05 N/15 mm, which is the highest value recorded in the literature as far as we know.

Synthesis and properties of waterborne polyurethane dispersions for surface coatings on poly(vinyl chloride)

Recently, conventional solvent-typed polyurethanes are subject to many regulations due to emission of organic volatile compounds(VOCs) and researches have been focused on eco-friendly waterborne polyurethane dispersions(WPUDs) as an alternative of conventional solvent-typed ones causing poor working environment. PVC is widely used because of low price and good heat and fire resistance. To develop eco-friendly coatings on poly(vinyl chloride) (PVC), various WPUDs were synthesized by combination of polyol such as polyester, polycaprolactone, polyether or polycarbonate, hydrophilic compounds (dimethylol butanoic acid, DMBA), and reactive silicone. The structure and properties of synthesized WPUDs were characterized by FT-IR, particle size, contact angle, surface energy, tensile strength, elongation, and adhesion strength. Also, their particle sizes decreased while tensile strengths increased with increasing DMBA content. Surface energy and contact angle of WPUDs were strongly affected by the content of hydrophobic reactive silicone. The optimum properties of WPUDs were obtained by controlling their compositions, polyol, hydrophilic compound, and reactive silicone.

Synthesis of blocked waterborne polyurethane with 3,5‐dimethylpyrazole for industrial application in digital inkjet printing

ABSTRACTIn this article, a series of blocked waterborne polyurethanes (BWPUs) were synthesized by isophorone diisocyanate, polyols, dimethylol butanoic acid (DMBA), and 3,5‐dimethylpyrazole. BWPUs were applied to digital inkjet printing of textiles. The successful synthesis and deblocking of BWPU were confirmed by Fourier transform infrared spectroscopy and differential scanning calorimetry. The colorfastness was improved by deblocking the terminal NCO groups at 140 °C, which could react with fiber. This article presented a characterization method of filtering rate to evaluate the fluency of inkjet printing. Besides, the digital microscope was used to investigate the pigment transferred to the white test cloth. In the end, we chose poly(ethylene glycol adipate) 2000 as the polyol, 1,4‐butanediol as the chain extender, 1.6 as the NCO/OH molar ratio, and 4% as the mass fraction of DMBA. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47765.

Aqueous anionic polyurethane dispersions from castor oil

In this study, dimethylol propionic acid (DMPA) and dimethylol butanoic acid (DMBA) were employed to synthesize the castor oil-based waterborne polyurethane dispersions (PUDs). The effects of these two emulsifier and their contents on the properties of the PUDs as well as their films were investigated systematically. The results show that as the emulsifiers contents increase, the particle size and zeta potential of the PUDs decrease while the tensile strength of the resulting PU films increase but thermal stability, water and chemical resistance decrease. The PUDs from DMBA exhibit smaller particle size than those from DMPA and the films from the former show higher tensile strength, higher elongation at break but lower thermal stability, lower water resistance. This work provides a new way to synthesize environmental friendly bio-based waterborne polyurethanes whose properties can be tuned according to their application, such as coating, ink, leather, styling products and so on.

Synthesis of UV-curing waterborne polyurethane-acrylate coating and its photopolymerization kinetics using FT-IR and photo-DSC methods

Environmentally friendly waterborne polyurethane-acrylate (WPUA) oligomers and ultraviolet curing WPUA films (UV-WPUA) were prepared. The thermal stability, solvent-resistance and mechanical properties of the films were investigated. FT-IR and photo-DSC methods were used to investigate the photopolymerization kinetics of the UV-WPUA films. The results showed that UV-curing films offered the optimum combination of properties when the polyether polyol (NJ-330), isophorone diisocyanate (IPDI), hydroxyethyl methyl acrylate (HEMA) and dimethylolbutanoic acid (DMBA) were used as the raw materials and the mass ratio of oligomer: monomer butyl acrylate (BA): photoinitiator was fixed at 66:30:4. Reaction kinetics of different photoinitiators systems were calculated by Kissinger equation and Crane equation, thus providing a theoretical guidance for the optimization of diluent and photoinitiator in UV-curing coating industry.

Chemical hybridization of waterborne polyurethane with β-cyclodextrin by sol-gel reaction

Abstract A series of waterborne polyurethane (WPU)/β-cyclodextrin (β-CD) chemical hybrids were synthesized from polypropylene glycol (PPG400), dicyclohexylmethane-4,4′-diisocyanate (H 12 MDI), dimethylol butanoic acid (DMBA), 3-isocyanatepropyltriethoxysilane (ICPTES), and β-CD. The ICPTES-terminated WPU prepolymers were chain extended via a sol-gel reaction by using β-CD as a biodegradable multifunctional crosslinker at various β-CD equivalence ratios (ICPTES:β-CD = 1:0.5, 1:1, 1:1.5, and 1:2). The thermal, mechanical, and surface properties of the WPU/β-CD dispersion cast film were investigated, with biodegradation experiments carried out in α-amylase enzyme solution. The glass transition temperature ( T g), particle size, Young’s modulus, and hardness of the dispersion cast film increased up to an equivalence ratio of 1:1.5 owing to effective migration of β-CD molecules into WPU and crosslinking via the sol-gel reaction. However, at higher ratios, most of these parameters decreased owing to aggregation of β-CD.

Synthesis and properties of novel water‐dispersible polyisocyanates

ABSTRACTA series of novel water‐dispersible polyisocyanates (WDPs) were synthesized with hexamethylene diisocyanate isoxyanurates (HDI trimer), dimethylol butanoic acid (DMBA), polyethylene glycol monomethyl ether (MPEG‐600) and 1,4‐cyclohexanedimethanol (CHDM) as materials. Two‐component waterborne polyurethane (2K‐WPU) films based on WDPs were prepared and characterized by ultraviolet‐visible spectrophotometer, thermogravimetric analyzer (TGA), scanning electron microscopy (SEM), and surface contact angle measurement. The effects of molar ratios of DMBA/MPEG and CHDM/MPEG and their amounts on properties of WDPs including the water dispersibility, storage stability, films hardness, and water resistance were also investigated. The results showed that the introduction of CHDM could efficiently improve the storage stability, the hardness and water resistance of 2K‐WPU films due to the rigid cyclic structure and hydrophobicity property of CHDM. It was found that WDPs had excellent storage stability, and the 2K‐WPU displayed short tack‐free times, high hardness, good water resistance, excellent surface appearance and gloss with 3:7:3 of the molar ratio of DMBA/MPEG/CHDM. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44735.

Waterborne Polyurethane/Acrylics Interpenetrating Networks Polymer:Preparation,Characterization and Application for antipilling coating materials

Aqueous polyurethane dispersions with C=C double bonds were synthesized by using Isophorone diisocyanate, Polyether diol 218, polyether-tribasic alcohol 310 and dimethylolbutanoic acid without any organic solvents. Then waterborne polyurethane-acrylic hybrid emulsion interpenetrating network were prepared with the method of pre-emulsification semi-continuous. Based upon the FT-IR, DSC, TG and particle size analysis, the experimental results showed that polyurethane with C=C double bond and acrylate has good compatibility and exhibits phase separation morphology with interpenetrating networks. Thermal stability and emulsion stability is good. Anti-pilling grade of different fabrics rise two or three levels after finishing by using waterborne polyurethane and acrylic ester interpenetrating networks polymer.

Preparation and property of waterborne UV‐curable chain‐extended polyurethane surface sizing agent: Strengthening and waterproofing mechanism for cellulose fiber paper

ABSTRACTWaterborne UV‐curable polyurethane (UWPU) dispersions with different hydrophilicity and functionalities were prepared by varying the content of dimethylol butanoic acid (DMBA) and pentaerythritol triacrylate (PETA). And linear and cyclic chain extenders with different functionalities were also incorporated into the UWPU backbone, including isophorone diamine (IPDA), diethylene triamine (DETA), and ethylene diamine (EDA). Effects of DMBA content, PETA content, photoinitiator content, UV curing time, chain extender on the properties of UWPU dispersions and films, as well as the properties of the unsized and sized paper were investigated. The water resistance and mechanical properties of sized paper were greatly relied on the particle size, the molecular weight, the croslinking density, and penetrability of UWPU. UWPU dispersion chain extended with IPDA (IPDA‐UWPU) displayed smaller particle size than that of UWPU. The paper sized with IPDA‐UWPU was endowed with best water resistance, tensile strength, folding strength and surface strength. XPS depth analysis revealed that IPDA‐UWPU exhibited better penetrability into the paper substrate than UWPU. SEM and AFM demonstrated that the smoothness of sized paper was improved, and the bond strength between fibers was enhanced. The obtained UWPU could be directly used as an effective and fast drying surface sizing agent for cellulose fiber paper. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42354.

Preparation and properties of castor oil/pentaerythritol triacrylate-based UV curable waterborne polyurethane acrylate

Abstract Castor oil (CO)/pentaerythritol triacrylate (PETA)-based UV curable waterborne polyurethane acrylate (UV-WPUA) was prepared by using isophorone diisocyanate (IPDI), poly(caprolactone diol) (PCL) and dimethylolbutyric acid (DMBA) as the main materials. A series of emulsions and films with different content of CO were obtained. The infrared spectra, together with the nuclear magnetic resonance spectroscopy, demonstrated the presence of CO and PETA in the UV-WPUA chains. The surface roughness of the curing film was measured by atomic force microscope. In addition, the effects of CO content on particle size, thermal properties, glass transition temperature and tensile performance of the emulsions and films were investigated. With the content of CO increasing from 1.72 to 8.58 wt%, the particle size of the UV-WPUA emulsion increased and the particle size distribution gradually widened. The appearance of the emulsions transformed from blue transparent into opaque and the stability decreased gradually. Water resistance, glass transition temperature for soft segment and thermal performance of the films were improved. The tensile strength of the films firstly increased and then decreased.

Waterborne polyurethane elastomer using renewable polyols

A series of waterborne polyurethane (WPU) elastomers were synthesized from isophorone diisocyanate, polycaprolactone diol (PCL), 1,3-propanediol produced from a glucose fermentation process (Bio-PDO), 1,4-butanediol, and dimethylolbutanoic acid as a function of Bio-PDO/PCL composition. With the addition and increasing amount of Bio-PDO, particle size of dispersion, hardness, water swelling, initial modulus, and stress at break decreased, while contact angle with the water drop of the dispersion cast film increased. The PCL WPU showed a single-step thermal degradation at about 370°C, while those of Bio-PDO-containing WPUs showed two step degradations at about 350 and 400°C suggesting the soft segment–hard segment phase separation.

Preparation and Characterization of Aqueous Polyurethane Polyol Used in Waterbore Two-Component Polyurethane Coating

Aqueous polyurethane(PU) polyols were synthesized from polyester polyol, toluene diisocyanate(TDI), dimethylolbutyric acid (DMBA) and diethanolamine(DEA). The structure of PU polyol and resulting polyurethane film were confirmed by the Fourier Transform Infrared Spectroscopy (FT-IR). The effects of NCO/OH and DMBA content on the particle size of PU polyol and resulting polyurethane films, which formed by the mixture of PU polyol and water-dispersible polyisocyanate, was investigated by dynamic light scattering analysis, dynamic mechanical analysis and measurement of the mechanical properties.The results show the increase in DMBA content or NCO:OH ratio may be used to decrease the particle size of aqueous polyurethane polyol, increase the Tg for two-component aqueous PU film and maybe adjust the mechanical properties of resulting film.

Synthesis and properties of silanized waterborne polyurethane/graphene nanocomposites

A series of silanized waterborne polyurethane (WPU)/graphene oxide (GO) chemical hybrids were synthesized from polycaprolactone diol, isophorone diisocyanate, dimethylol butanoic acid, and (3-aminopropyl) triethoxysilane with GO as multifunctional crosslink as well as reinforcing filler. With the addition of GO, dispersion size greatly decreased due to the increased water phase viscosity, while it increased after chain extension reaction due to the migration of GO into the PU particles. The GO covalently bonded to WPU via the sol–gel type reaction augmented contact angle, glass transition temperature (Tg), hardness, and Young’s modulus of the cast film up to 1 %. However, the effects were less pronounced at high content (1.5 %) due to the agglomeration of GO particles.

Preparation, characterization of UV‐Curable Waterborne Polyurethane‐Acrylate and the application in metal iron surface protection

ABSTRACTHydroxyethyl methyl acrylate (HEMA) capped waterborne polyurethane‐acrylate (WPUA) oligomer was firstly prepared from isophorone diisocyanate (IPDI), polyether polyol (NJ‐220), dimethylolbutanoic acid (DMBA), HEMA via in‐situ and anionic self‐emulsifying method. Ultraviolet (UV) curable WPUA coating was obtained from HEMA‐capped oligomer, butyl acrylate (BA) and multifunctional acrylates (TPGDA) as reactive diluents, and Darocur 1173 as photoinitiator. The physical properties of WPUA oligomers, such as particle size, apparent viscosity, and surface tension were investigated. Some mechanical properties of UV‐WPUA films, such as contact angles, thermal properties, and solvent (water, HCl, NaOH, NaCl, and ethanol) resistance of UV‐WPUA coating films were measured. The surface morphologies were measured by scanning electron microscope and atomic force microscope. The surface free energy of the UV‐cured film was calculated from contact angle measurements using the Lewis acid–base three liquids method. The specific UV‐WPUA coating was selected to protect the iron materials that observed the effect of the protection. The results indicate that the prepared UV‐WPUA coating has excellent protective behavior to metal iron materials and may offer some contributions to protect iron cultural relics. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3142–3152, 2013