PROPERTIES AND MORPHOLOGY OF UNSATURATED POLYESTER/ACRYLATE-TERMINATED POLYURETHANE/ORGANO-MONTMORILLONITE NANOCOMPOSITES

Unsaturated polyester resin （UPR）/acrylate-terminated polyurethane （ATPU）/organo-modified montmorillonite （OMMT） nanocomposites were prepared by the in situ intercalative polymerization method. Samples were prepared by the sequential mixing, i.e. mixture of the ATPU and styrene （S） and OMMT were prepared in the first step; UPR was then added to the pre-intercalates of ATPU/S/OMMT. Results indicate that the mechanical properties and thermal properties of UPR/ATPU/OMMT nanocomposites greatly depend on the amount of ATPU and OMMT. Results show that the addition of ATPU could increase the impact strength of UPR/ATPU composites, but the tensile strength, flexural strength and heat resistance of the materials are obviously decreased. When the weight ratio between UPR, ATPU and OMMT were 82：15：3, the impact strength and heat distortion-temperature of nanocomposite were greatly improved, meanwhile there was little change for other properties of the nanocomposites. The synergistic enhancement effects of ATPU and OMMT on the composites were observed. The structures and morphology of the composites were investigated by X-ray diffraction, scanning electron microscopy and transmission electron microscopy.

Preparation and Surface Properties of Silicon-Containing Waterborne Polyurethane Functionalized with Fluorine-Containing Acrylate and Micro-Nano Silica

In order to prepare hydrophobic waterborne polyurethane coatings with better performances, the silicon-containing waterborne polyurethane（SiWPU） with functional chain extender hydroxyethyl acrylate（HEA） was prepared first, and then a series of silicon＆fluorine-containing polyurethane/acrylate（FSiPUA） emulsions were obtained with flourine containing acrylic monomer by seed emulsion polymerization, introducing micro-nano SiO2 into FSiPUA emulsion to make the final hybrid emulsion. The properties of Si WPU, FSiPUA and SiO2/FSiPUA were investigated by fourier transform infrared spectra（FTIR）, transmission electron microscope（TEM）, Scanning Electron Microscope（SEM） and some other analytical methods. The results revealed that FSiPUA emulsion particles possessed composite core-shell structure and FSiPUA films with suitable ratio performed better than Si WPU films in hardness, water resistance and solvent resistance. The SiO2/FSiPUA films with micro-nano dual roughness structure showed a water contact angle of 136° with good resistance to acid and alkali.

MODIFIED ULTRAVIOLET-CURABLE WATER DISPERSIBLE POLYURETHANE-ACRYLATES

Three kinds of UV-curable self-emulsified polyurethane-acrylate (PUA) prepolymer, i.e., conventional, chain extended and grafted PUAs, were prepared. The relatively small particle size of the PUA dispersions indicates that the PUA prepolymers exhibit sufficient aqueous dispersibility. The PUA prepolymers can substantially lower the interfacial tension of water. Chain-extended PUA dispersions exhibit pseudoplastic behavior and thixotropy to a greater extent than do their conventional counterpart. The chain-extended and grafted PUA photocure to higher conversion than do the conventional PU equivalent. The results of DSC measurement suggest that there exists phase mixing between the hard and the soft segment phases for the PUAs based on PEG 400 that is the comparatively short soft segment in the prepolymer. For the PUA prepolymers based on PEG having higher M-n values, chain-extending and grafting could impede the phase separation between the hard and the soft segment domains. The adhesion, impact strength and flexibility of the photocured films were tested.

UV-curing of hyperbranched polyurethane acrylate-polyurethane diacrylate/SiO_2 dispersion and TGA/FTIR study of cured films

UV-curable hyperbranched polyurethane acrylate-polyurethane diacrylate/SiO2 dispersion(HBPUA-PUDA/SiO2) was prepared with isophorone diisocyanate(IPDI),hyperbranched polyester Boltorn H20(H20),hydroxy-ethyl acrylate(HEA),polyethyleneglycol(PEG-200) and nano-SiO2.The UV curing kinetics of the films was investigated by FTIR.The results show that the curing speed of the films increases with the adding of nano-SiO2 and decreases with the adding of PUDA due to the slower chain movement.The thermal stability of the HBPUA-PUDA/SiO2 films was studied by using thermogravimetric analysis coupled with Fourier transform infrared spectroscopy(TGA/FTIR).The results show that all films exhibit two degradation stages located at about 320 and 440 °C corresponding to the degradation for hard segments of urethane-acrylate and the degradation for soft segment and polyester core.In addition,the results from the analysis of TGA/FTIR also indicate that the decomposition temperature of HBPUA-PUDA/SiO2 film is 15 °C higher than that obtained for pure polymer.The degradation mechanism was proposed according to TGA/FTIR results.

Influence of Initiator on Synthesis and Properties of Polyurethane-acrylate Hybrid Emulsion

The prepolymer polyurethanes （PUs） based on isophorone diisocyanate （IPDI）, poly（propylene glycol） （PPG）, 1,4-butanediol （BDO） and dimethylopropionic acid （DMPA） were synthesized at 75-80 ℃ for 7-8 hours, using dibutyltin dilauate （DBTDL） as catalyzer, and polyurethane-acrylate hybrid emulsion was prepared after methyl methacrylate （MMA） was polymerized, using potassium persulfate and azobisisobutyronitrile （AIBN） as initiator, respectively. The influences of these factors such as the kind of initiator, the feed method of initiator and the addition of initiator on properties of polyurethane-acrylate were studied. The FTIR and GPC of aqueous polyurethane were analyzed. The FTIR spectra show that the degree of microphase-separate between the soft segments and rigid segments is high. The analysis of molecular weights stated that molecular weights increased most significantly after amine was added. The experimental results reveal that the appearance of emulsion is excellent, the film is harder and the water absorption radio of the film is less when oil-solubility AIBN is used as initiator. The semi-continuous can increase the molecular weight of polymer and the optimum amount of the initiator was 3% for MMA.

Preparation, morphology and mechanical properties of acrylate-modified polyurethane/unsaturated polyester resin graft-IPNs

Acrylate modified polyurethane resin was first synthesized, and interpenetrated with unsaturated polyester resin to form IPNs and gradient IPNs which cured at room temperature. The polymerization process was traced by an IR spectroscopy technique and the simultaneous interpenetrating techniques were determined. The morphology of these IPNs were estimated by TMA and TEM methods. The results indicated that large amount of interpenetrating and entanglement make T g  linked up effectively, and domains between two phases can be in nanometre ranges, which changed with composition ratios. The mechanical properties results showed that IPNs varied from elastomeric to plastic materials. It was noteworthy that, with the introduction of modified groups and the formation of graft construction in IPNs, the miscibility in the systems was improved a lot. These further led to the improved mechanical properties of IPNs with elastomer reinforced and plasticizer toughened as well. The reinforced miscibility between the networks can apparently change mechanical property especially for the gradient ones when the materials are elongated.

Lithium bis(trifluoromethanesulfonyl)imide blended in polyurethane acrylate photocurable solid polymer electrolytes for lithium-ion batteries

The increased demand of electronic devices promotes the development of advanced and more efficient energy storage devices, such as batteries. Lithium-ion batteries (LIBs) are the most studied battery systems due to their high performance. Among the different battery components, the separator allows the control of lithium ion diffusion between the electrodes. To overcome some drawbacks of liquid electrolytes, including safety and environmental issues, solid polymer electrolytes (SPEs) are being developed. In this work, a UV photocurable polyurethane acrylate (PUA) resin has been blended with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) up to 30 wt% LiTFSI content to reach a maximum ionic conductivity of 0.0032 mS/cm at room temperature and 0.09 mS/cm at 100 ℃. Those values allowed applying the developed materials as photocurable SPE in Swagelok type Li/C-LiFePO_(4) half-cells, reaching a battery discharge capacity value of 139 mAh.g^(−1) at C/30 rate. Those results, together with the theoretical studies of the discharge capacity at different C-rates and temperatures for batteries with LiTFSI/PUA SPE demonstrate the suitability of the developed photocurable SPE for LIB applications.

Hyperbranched Polyurethane Acrylate Applied to UV Curable Flame Retardant Coatings

UV curable hyperbranched prepolymers based on amine-ester, ester-amide and ether-amide started with AB_2-type monomers have been prepared by the authors. A series of work on allyl ether maleate hyperbranched polyesters for UV curing coatings by Hult and his colleagues has been reported. However, the UV cured films from those materials are all flammable when attached to fire without addition of flame retardants.

Preparation and Characterization of Two-component Waterborne Polyurethane Comprised of Water-soluble Acrylic Resin and HDI Biuret

A two-component waterborne polyurethane(2K-WPU) was prepared by mixing water-soluble acrylic resin and hexamethylene diisocyanate biuret, and then diluted for phase inversion with water. Compared with water-soluble acrylic resin, the phase inversion of 2K-WPU occurs at lower water content. It is indicated by TEM that 2K-WPU parti-cles show a core-shell structure, in which HDI biuret is encapsulated by hydrophilic acrylic resin. 2K-WPU emulsion with HDI biuret has larger particle size and narrower distribution index, while for 2K-WPU emulsion with HDI iso-cyanurate, the latex not only has large particle size, but also has two-peak distribution. FTIR shows that the reaction be-tween HDI biuret and acrylic resin can complete in 12h. In addition, studies on effect of composition of acrylic resin on performance of 2K-WPU show that narrowing the polar difference between water-soluble acrylic resin and HDI biuret and improving the miscibility of two components are the key to prepare the transparent and high gloss films with high crosslinking density.

Synthesis and properties of UV curable polyurethane acrylates based on two different hydroxyethyl acrylates

Two kinds of UV curable polyurethane acrylate oligomers(PUPA and PUCA) were synthesized via the addition reaction between isophorone diisocyanate(IPDI) and polyethylene glycol monoacrylate(PEA6) or polycaprolactone modified hydroxyethyl acrylate(PCLA2).The structures of PUPA and PUCA were characterized by Fourier transform infrared spectroscopy(FT-IR),1H nuclear magnetic resonance(1H NMR),gel permeation chromatography(GPC) and differential scanning calorimeter(DSC),and the thermal stability and dynamic mechanical thermal properties of their cured films were measured by thermogravimetric analysis(TGA) and dynamic mechanical analysis(DMA),respectively.The viscosity of the oligomers and mechanical properties of the cured films were also studied.The results show that both oligomers have narrow molecular weight distribution.The viscosity of PUPA is 2.310 Pa.s at 25 °C,while that of PUCA is up to 3.980 Pa.s.The UV cured PUPA and PUCA films have homogeneous phase structure,and the PUCA film shows higher glass transition temperature and storage modulus.Furthermore,the PUCA film possesses better mechanical properties than PUPA,while the latter shows better alkali resistance.

Use of the Newly Synthesized Aqueous Polyurethane Acrylate Binders for Printing Cotton and Polyester Fabrics

The use of the four new synthesized polyurethane acrylate binders in the pigment print paste for screen printing cotton and polyester fabrics and pigment fixation through the polymerization process of the binder by using the thermofixation technique as well as the UV curing technique was studied. The effect of changing time and temperature of thermofixation, and the time of UV curing on the color strength, and prints fastness properties were also studied. The results showed that, the newly synthesized polyurethane acrylate binders could be successfully used for pigment fixation on cotton and polyester using the two fixation techniques and in general their prints possessed better color strength values as compared to those obtained upon using the selected commercial binders.

Synthesis of a Novel Core-shell Type Acrylic-polyurethane Hybrid Emulsion Containing Siloxane and Fluorine as well as Water and the Oil Resistances of Cured Film

Siliconated polyurethane （Si-PU） was synthesized using isophorone diisocyanate （IPDI）, hydroxybutyl-terminated polydimethylsiloxane （PDMS）, polytetramethylene ether glycol （PTMG）, polypropylene glycol （PPG）, 1,6-hexanediol （HDO）, dimethylol propionic acid （DMPA） and triethylamine （TEA）. Based on butyl acrylate （BA）, 2, 2, 2-trifluoroethylmethacrylate （TFEMA） and Si-PU as a seed emulsion, a novel core-shell type acrylic-polyurethane hybrid emulsion, containing siloxane and fluorine （F-Si-PU）, was prepared by seeded emulsion polymerization. The contents of siloxane and fluorine were determined according to the feed ratio. Fourier transform infrared spectroscopy （FTIR） was used to identify the chain structures of Si-PU and F-Si-PU. Investigation of transmission electron microscopy （TEM） confirmed the core-shell structure of F-Si-PU emulsion. Measurement results of water contact angle and the swelling ratio in water and n-octane for cured film showed that the water and the oil resistances for F-Si-PU had been significantly improved at a suitable content of fluorine and siloxane.

Preparation and Properties of Two-Component and Double-Crosslinking Waterborne Polyurethane-Acrylic Dispersions

In this paper, isophorone diisocyanate (IPDI), polyethylene glycol (PEG), dimethylolpropionic acid (DMPA) and internal crosslinking agent trimethylolpropane (TMP) were used to prepare waterborne polyurethane. And then double-crosslinked polyurethane-acrylic composite aqueous dispersion was prepared in which polyacrylate was adopted to modify waterborne polyurethane and some special external crosslinking agents were added including silicone and trifunctional aziridine. The influence of the amounts of internal and external crosslinking agents, emulsifier, initiator on the particle size, particle size distribution, viscosity, molecular weight, as well as water adsorption ratio were studied.

Part 1: Synthesis and Evaluation of Novel Nano Scale Powdered Polyurethane Acrylate Binders

Some new an aqueous polyurethane acrylate (waterborne binder) based on polyethylene glycol with different M. wt. mixed with polyol were carried out. Seven different polyurethane acrylate co-polymers were prepared aiming at substituting the two hydroxyl groups of polyethylene glycol (6000, 12,000 and 20,000 g/mol) and two primary hydroxyl groups of polyol through their reaction with corresponding calculated amounts of either isophorone diisoyanate or toluene diisocyanate and caped the remaining isocyanate group with either hydroxy ethyl acrylate or hydroxy propyl methacrylate to get on the polyurethane acrylate polymers [PUA]. From DSC measurement the result of Tg of synthesized PUA are in range from -8.78℃ to 36.4℃. So they can classify as soft binders. The infrared spectra, rheological properties, viscosity measurement, the weight average molecular weight, of the synthesize binders were investigated.

Influence of Ageing with UV Radiation on Physicochemical Properties of Acrylic-Polyurethane Coatings

Investigated systems of acrylic-polyurethane coatings consisted of three kinds of coatings: base coat (acrylic), intermediate (polyurethane) and top coat (acrylic);each made up of two layers. Mean thickness of the coating system was equal (145 ± 1) μm. In time of accelerated UV ageing, electromagnetic radiation was emitted of wave length in the range (300 - 400) nm which was progressively inducing a destruction of coatings chemical structure, especially photooxidation and photolysis of coating material. Carried out X-ray investigations revealed increased contents of oxygen in aged coatings due to their photooxidation which resulted in increased tendency of coating microfragments to chip off from surface layer with the ageing time flow. The hardness increase of UV aged coatings was also observed which intensified their surface layer brittleness. This contributed to their thickness decrease by more than 10% after 2016 h of ageing. Photodestruction of UV aged coatings was documented as well by characteristics obtained during investigations carried out with DMA method use. A noticeable physical destruction of the coatings was observed in the form of silver cracks, etchings and grooves in surface layer as well as craters extending also into interlayer. Processes of physical and chemical destruction undergoing in aged coatings influenced roughness profile change and coatings surface topography shaping. After 2016 h of UV ageing, the roughness parameters (Ra, Rz, Rt) increased several times. Long-lasting UV radiation influence on the surface of investigated acrylic-polyurethane coating systems contributed to their decorativeness loss. Microscopic examinations revealed colour change (yellowing) of blue pigment contained in polyurethane interlayer. Decline in coating gloss was also observed as the result of surface roughness increase.

桐油对聚氨酯-丙烯酸酯紫外光固化树脂性能的影响

将异氟尔酮二异氰酸酯(IPDI)、聚己二酸新戊二醇酯二醇(PNA,Mn=1000)作为主要原料,丙烯酸羟乙酯(HEA)作为封端剂,制备了聚氨酯丙烯酸酯(PUA)。将得到的PUA与不同添加量的桐油混合均匀,制备了一系列紫外光固化树脂。利用红外光谱表征了固化过程,测试了紫外光固化膜的硬度、附着力、漆膜耐冲击性能、耐酸碱性、耐醇性和耐水性。结果表明,当桐油的添加量为10%时,光固化树脂的综合性能较好,固化膜硬度达到5 H,附着力为0级,韧性及耐溶剂性较好,树脂表面60°光泽度<20 GU,在玻璃包装涂层中具有较广泛的应用前景。

Synthesis and characterization of yellow water-borne polyurethane using a diol colorant as extender

A novel and facile method toward a series of yellow water-borne polyurethane was developed by using an intrinsically colored diol in this paper.The yellow aqueous dispersion PCLD-HENA-PU was synthesized based on isophorone diisocyanate(IPDI), polycaprolactonediol(PCLD) and 2,2-dimethylol propionic acid(DMPA) using a yellow diol N,N-bis(2-hydroxyethyl)-4-nitroaniline (HENA) as a chain extender.Due to the complete reaction of OH group in colorant HENA with NCO group in diisocyanate,a series of stable yellow p...

蓖麻油基光敏树脂的合成及其UV-LED固化无影胶的性能

以蓖麻油、异佛尔酮二异氰酸酯、丙烯酸羟乙酯为原料,通过无溶剂法合成的一种蓖麻油基聚氨酯丙烯酸酯(CO-PUA)作为光敏单体。将自制的CO-PUA、活性稀释剂、硅烷偶联剂、附着力促进剂、光引发剂以及四(3-巯基丙酸)季戊四醇酯(PETMP)按比例混合制得一系列UV-LED固化无影胶,并考察了PETMP的添加量对无影胶性能的影响。结果表明:引入PETMP的UV-LED固化无影胶具有巯基-烯“点击化学”的反应特性,消除了氧阻的危害,无影胶固化完全。当PETMP的添加量为0.5 g时,具有最佳黏结性能,以有机玻璃-有机玻璃、有机玻璃-不锈钢、玻璃-不锈钢为搭接基材测得黏结拉伸剪切强度分别为2.44 MPa、5.06 MPa和5.70 MPa。

Synthesis and Crystal Structure of (Z)-Methyl-3-methoxy-2-{2-[(4-(E-3-p-tolylacryloyl)phenoxy)methyl]phenyl}acrylate

The title compound,（Z）-methyl-3-methoxy-2-{2-[（4-（E-3-p-tolylacryloyl）phenoxy）-methyl]phenyl}acrylate,was synthesized and determined by X-ray single-crystal diffraction. The crystal belongs to the triclinic system,space group P1 with a = 8.0157（8）,b = 12.5748（13）,c = 13.3768（14） ,α = 64.770（2）,β = 75.720 （2）,γ = 89.784（2）°,μ = 0.085 mm-1,Mr = 442.49,V = 1174.1（2） 3,Z = 2,Dc = 1.252 g/cm3,F（000） = 468,T = 294（2） K,R = 0.0603 and wR = 0.1498 for 2644 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the single crystal contains strong non-classical hydrogen bonds. The preliminary bioassay showed that the title compound exhibits inhibitory activity against the Pseudoperoniospora cubensis and Rhizoctonia solani at the test concentration of 200 mg/L.