Tung based reactive diluents for alkyd systems: Film properties

Reactive diluents were prepared from tung oil via a Diels–Alder reaction with three different dienophiles: methacryloxypropyl trimethoxysilane (TOMAS), 2,2,2-trifluoroethyl methacrylate (TOF) and triallyl ether acrylate (TOTAE). The reactive diluents were mixed with a long oil soya alkyd, a metal drier package, and a wetting agent; and then cured. Formulations were prepared as a function of reactive diluent type and wt%. Tensile, thermomechanical, and coatings properties were evaluated after curing the films. The addition of two reactive diluents, TOMAS and TOTAE, improved the tensile strength and tensile modulus of the alkyd. The addition of the diluents, however, did not significantly change the elongation at break compared to the alkyd in any of the systems. Also, the addition of TOMAS and TOTAE increased both the crosslink density and glass transition temperature of the alkyd. Basic film properties including hardness, solvent resistance, impact resistance, adhesion, and gloss were not adversely affected by the introduction of any of the tung oil based diluents.     

Synthesis of UV-curable tung oil and UV-curable tung oil based alkyd

Two UV-curable tung oil-based resins were synthesized via a Diels–Alder cycloaddition. An UV-curable tung oil (UVTO) was prepared from bodied tung oil and trimethylolpropane trimethacrylate (TMPTMA). An inhibitor, phenothiazine, was added to avoid homopolymerization of TMPTMA. The UV-curable tung oil alkyd (UVTA) was prepared from the monoglyceride process and then reacted with TMPTMA via the Diels–Alder reaction similar to the UVTO. The UVTO and UVTA were characterized by ¹H NMR, ¹³C NMR, and MALDI-TOF mass spectroscopy. The UVTO and UVTA were formulated with a free radical reactive diluent, tripropylene glycol diacrylate (TPGDA) and photoinitiator Irgacure 2100. Photo differential scanning calorimeter (Photo-DSC) was used to investigate curing kinetics of the UVTO and the UVTA. Both the UVTO and UVTA were photocurable with the UVTA formula exhibiting a faster curing speed than the UVTO.     

无机型人造石表面紫外光固化涂膜研究

以KH-550为打底液对无机型人造石表面进行预处理,然后以紫外光固化涂料罩光.讨论了低聚物和活性稀释单体的组成、消泡剂种类和KH-550的用量对人造石表面紫外光固化涂膜性能的影响.结果表明,以质量分数为3%的KH-550对人造石表面进行预处理后,按低聚物55%,活性稀释单体40%,光引发剂和助剂分别为4%和1%的质量分...     

Sucrose octaesters as reactive diluents for alkyd coatings

Sucrose octasoyate (SS8) was investigated as a reactive diluent for a medium oil alkyd (MOA). SS8, which is derived from sugar and soybean oil, is 100% biobased, nontoxic, and biodegradable. As a result of its unique molecular architecture, it was expected that SS8 would be an excellent reactive diluent for alkyd coatings. The experiment conducted basically involved the incremental replacement of the MOA with SS8, while maintaining essentially equivalent solution viscosity. The properties of cured coatings were determined using industry standard methods. In general, it was found that SS8 could be used to reduce volatile organic compound content of the coatings, while also reducing drying time (i.e., tack-free time), increasing solvent resistance, and increasing impact resistance. Of the properties measured, the only cured film property that was negatively affected by the use of SS8 was the König pendulum hardness. However, the reduction in König pendulum hardness was only observed when the amount of MOA replaced by SS8 was greater than 10 wt%. Overall, these initial results suggest that SS8 is a very good reactive diluent for alkyd coatings.     

Synthesis and evaluation of tetra(2,7-octadienyl) titanate as a reactive diluent for air-drying alkyd paints

Environmental regulations are forcing the reformulation of many decorative and protective coatings systems. In particular, air-drying solventborne alkyd paints need to meet increasingly stringent emission limits and often must be reformulated with suitable exempt solvents or reactive diluents to achieve volatile organic compound (VOC) reduction. In the research summarized in this article, a new reactive diluent, tetra(2,7-octadienyl) titanate, was synthesized and evaluated in alkyd formulations for VOC reduction and property enhancement. A soy-based long-oil alkyd resin; a soy-based high-solids, long-oil alkyd resin; and a linseed-based, high-solids long-oil alkyd resin were evaluated in combination with the new reactive diluent at weight percentages ranging from 10% to 50%. Characterization included measuring viscosity, film dry times, and film performance of the reactive diluent formulations in comparison to neat alkyd resins used as control. The tetra(2,7-octadienyl) titanate formulations consistently exhibited reduced viscosities and dry times as a function of concentration. The resulting films were harder and more thoroughly cured than the control systems.     

Design and incorporation of reactive diluents for air-drying high solids alkyd paints

The development of air-drying solvent borne trade paints with solvent content below that of current solids levels will necessitate reformulation using reactive diluents. The current lack of suitable reactive diluents for air-drying systems has prompted this investigation. This paper highlights some emerging aspects of the design of reactive diluents, in particular the importance of inclusion of the correct balance of sites for both initiation and coupling reaction stages into an alkyd system together with the concept of functionality as a tool to predict performance. Also reported is a new class of reactive diluents based on fumarates and succinates of octadienol (referred to as the OFS class of reactive diluents). A detailed study on the cure and performance of this class of compounds is reported. A combination of conventional and refined analytical techniques have given new insights into the mechanism of cure of these reactive diluents as well as a measurement of incorporation into the drying paint film. The findings of this performance study have confirmed the suitability of the reactive diluent design and allowed its further refinement. OFS reactive diluents have thus been found to achieve full chemical incorporation whilst maintaining high performance of the paint.     

高生物基含量光固化涂料的制备及其性能研究

环氧化大豆油丙烯酸酯(AESO)已大规模用于UV固化涂料中,但目前同时获得高生物基含量以及优异机械性能的大豆油基光固化涂料依然是一个很大的挑战。文中设计并合成了异山梨醇甲基丙烯酸酯(ISDMA)作为光固化活性稀释剂。使用流变仪研究了ISDMA对AESO稀释性的影响。将ISDMA与AESO混合制备了一系列生物基UV固化涂料,并对这些涂料的热机械性能、力学性能和涂层基本性能进行了评估。结果表明:ISDMA对AESO表现出良好稀释性的同时,可以有效地提高固化涂层的玻璃化转变温度(T_g)、储能模量和硬度。     

Properties of UV-curable polyurethane acrylates for primary optical fiber coating

Studies have been made on the effects of the chemical structure of reactive urethane acrylate prepolymers and diluents (reactive monomers) and overall composition of the prepolymer/diluent on the properties of the UV-curable polyurethane acrylates for primary optical fiber coating. We prepared several urethane acrylate prepolymers from two different isocyanates, 4,4′-dicyclohexylmethane diisocyanate (HMDI) or isophorone diisocyanate (IPDI), and two different polyols, polybutadiene diol (PBD) or polypropylene oxide diol (PPG), and 2-hydroxyethyl acrylate (HEA) with dibutyl tin dilaurate as a photoinitiator. UV-curable coating materials were formulated from the prepolymers and 2,2-dimethyl 2-phenyl acetophenone as a photoinitiator with one of four different diluents such as 1-vinyl 2-pyrrolidone (VP), lauryl methacrylate (LMA), acrylic acid 2-ethyl hexyl ester (AEHE), and acrylic acid n-butyl ester (ABE). It was found that AEHE is the desirable diluent in the formulation of the primary fiber-coating material. The desirable composition of PBD, when mixed PBD/PPG diols are used, should be about 50 wt % for optimum formulation. Most of the urethane acrylate prepolymers prepared in this study could be applied in the formulation of primary optical fiber coating and exhibited good properties of buffer functions, including low glass transition temperature, low modulus even at low temperature, say, below ?40°C, high refractive index, and low viscosity. © 1992 John Wiley & Sons, Inc.     

紫外光固化涂料用聚酰亚胺的合成研究

使用均苯四甲酸二酐、3,3'-二甲基-4,4'-二氨基二环己基甲烷、聚醚胺、马来酸酐等合成了可光固化的半脂环族聚酰亚胺,并用FT-IR、NMR、UV-Vis等进行了表征。结果表明:马来酸酐的双键成功引入到聚合物中,形成了酰亚胺化聚合产物,且加入聚醚胺能显著改善溶解性。聚合物的紫外吸收波长与紫外光灯源波长相匹配,可在紫外光照射下固化。采用自合成的聚酰亚胺、184和活性稀释剂配制的UV涂料,其热稳定性良好,在玻璃上的附着力为1级,铅笔硬度为5H。     

UV-curable coating on plastic substrates: dynamic mechanical thermal analysis and Fourier transform infra-red analysis of the interfacial layer

The coating of a plastic substrate (polycarbonate sheets) with different uv-curable system was investigated. Systems based on an epoxy-acrylate resin (bisphenol-A-diglycidyl-ether-diacrylate) or on bisphenol-A-diethoxy-diacrylate were used in the presence of different reactive diluents. Pull-off experiments indicated that the presence of a reactive diluent able to dissolve or swell the polycarbonate matrix increased the adhesion properties; poor adhesion values were obtained by using reactive diluents which did not dissolve the polymer. When vinyl-pyrrolidone (VP) was used asa reactive diluent, Fourier transform infra-red analysis indicated that the VP diffused ino the polycarbonate matrix. Dynamic mechanical thermal analyses performed on thin films of polycarbonate attributable to the two polymeric phases. In the presence of diluent, the tan regions attributable to the two polymeric phases. In the presence of VP diluent, the tan σ peak of the coating phase was broader, thus suggesting the presence of a transition layer between the two phases.     

石墨烯光固化涂料的制备及防腐性能研究

为了提高光固化涂料的耐腐蚀性,将不同质量分数的石墨烯添加到光固化涂料中,制备了石墨烯复合光固化防腐涂层。对不同含量石墨烯复合光固化防腐涂层的硬度、耐冲击性、附着力等物理性能进行测试,并通过极化曲线、电化学阻抗谱等对其电化学性能进行了研究。最后,采用盐雾试验对不同石墨烯添加量的光固化涂层的防腐性能进行了评价。结果表明：当石墨烯的添加量为 0.1%时,涂层的硬度、耐冲击性以及附着力等物理性能得到显著增强,此时涂层的腐蚀电位最高,腐蚀电流密度最低,具有优异的耐腐蚀性能。     

Synthesis of Tung‐Oil‐Based Reactive Diluents

Three new reactive diluents were prepared from tung oil using a Diels‐Alder reaction. The dienophiles were methacryloxypropyl trimethoxysilane (MAS), 2,2,2‐trifluoroethyl methacrylate (TFM) and triallyl ether acrylate (TAEA). The chemical structures were evaluated using ¹H NMR, ¹³C NMR, FT‐IR, GPC and MALDI‐TOF‐MS. Spectra evidence (NMR, MS) indicated that a six‐member ring were formed in all three reactions indicating a Diels‐Alder adduct. The reactive diluents were formulated with a soya‐based alkyd to evaluate viscosity reduction and drying time. The viscosity of alkyd was reduced up to 70% using the reactive diluents. The drying time for the autoxidative reactive diluents with alkyds were 1.8‐1‐7 times faster than alkyd alone.

     

Effects of NCO/OH Ratio and Reactive Diluent Type on the Adhesion Strength of Polyurethane Methacrylates for Cord/Rubber Composites

A series of dual curable polyurethane methacrylate-based oligomers were synthesized by changing the NCO:OH ratio and then were included in adhesive formulations using trimethylolpropane trimethacrylate and tricyclodecane dimethanol diacrylate (TCDDA) as reactive diluents. The effects of NCO:OH ratio and reactive diluent type on the structural properties of UV-cured free films and adhesion properties between polyester cord/rubber surfaces were studied. The highest adhesion strength of the 103?N?cm^?1 was obtained when the NCO:OH ratio was set as 4 and the TCDDA was used as a reactive diluent.     

改性环氧树脂的固化与稀释增韧研究

研究了改性环氧树脂的固化、稀释增韧效果。探讨了不同种类的固化剂及活性稀释剂对改性环氧树脂的冲击强度、拉伸强度及维卡软化点等性能的影响。研究结果表明,在固化剂9032和活性稀释剂的共同作用下,能制得室温固化型增韧环氧树脂,且其具有较高的强度和耐热性。     

Synthesis and characterization of uv-curable acrylated urethane prepolymers,I. Effects of reactive diluents and relative humidity on physical properties

A UV-curable acrylated urethane prepolymer was synthesized from tolylene-2,4-diisocyanate (TDI), a polyether polyol (Arcol 1131) and endcapped with 2-hydroxyethyl methacrylate (HEMA) by addition reaction in the presence of dibutyltin dilaurate as catalyst. UV curing was performed with either diethylene glycol diacrylate or thiodiethylene glycol diacrylate as reactive diluent. The effects of reactive diluent types, their concentrations and the humidity of environment on mechanical properties of cured films were investigated. Changes in the tensile strength, elongation and Young's modulus values of the cured films upon addition of reactive diluents with different concentrations were related to the effect of the diluent on the crosslinking density of cured films. The increase of relative humidity from 50 to 95% caused a decrease of tensile strength and Young's modulus values of cured films. It is proposed that the decrease of these physical properties in high relative humidity is due to the formation of hydrogen bonding in polymer chains caused by water molecules.     

紫外光固化封底涂料的研制

研制了一种用于表面粗糙的水泥板、木板等建筑材料的快速封底处理的紫外光固化涂料,该涂料组成为:预聚物55份(质量份,下同)、稀释单体40份、光引发剂3份、助剂2份、填料35份。所得涂料流平性好,不需要添加流平剂,可形成均匀的涂层;其成膜固化速度快,固化膜具有较强的附着力,且耐酸性、耐碱性、耐盐性好;同时该涂料有较好的防沉降性、贮存稳定性和施工性。     

Properties of UV-curable polyurethane acrylates using nonyellowing polyisocyanate for floor coating

UV-curable polyurethane acrylates for poly(vinyl chloride) (PVC) floor coating were prepared using nonyellowing polyisocyanates. The effects of the chemical structure of the polyisocyanates and hydroxyacrylates, and the compositions of the prepolymer/diluent on the properties of the UV-curable polyurethane acrylates were investigated. Several different urethane acrylate prepolymers from four different polyisocyanates, isophorone diisocyanate (IPDI) adduct, hexamethylene diisocyanate (HDI) adduct, HDI biuret, and HDI isocyanurate, and two different hydroxyacrylates, hydroxyapropyl acrylate (HPA), polycaprolactone modified hydroxyethylhexylacrylate (PCMHEA). UV-curable coating materials were formulated from the prepolymers and 1-hydroxycyclohexylphenyl ketone as a photoinitiator with polyethylene glycol diacrylate (PEGDA) as a diluent. The polyurethane acrylates prepared with HDI isocyanurate and the equimolar mixture of HPA and PCMHEA showed balanced coating properties such as tensile properties, hardness, weatherability, and good adhesion. The dynamic mechanical studies showed the properties of those polyurethane acrylates were well correlated with their glass transition temperature behaviors. It was also found that the adhesion was best as a PVC floor coating with the appropriate viscosity (below 150 P at 25°C) when 35% PEGDA as a diluent was used. © 1996 John Wiley & Sons, Inc.     

新型UV固化可剥性金属涂料的合成及性能研究

选用乙醇为溶剂,偶氮二异丁腈(AIBN)为引发剂,引发邻苯二甲酸二烯丙酯(DAP)聚合。聚合工艺为DAP100g,乙醇30g,AIBN2g,反应温度为80℃,反应时间约4h。反应过后,DAP的收率达29.7%,聚合物是可溶的预聚体。预聚体的凝胶色谱、红外谱图及碘值都显示其具备进一步交联固化的潜力。然后,以合成的邻苯二甲酸二烯丙酯预聚体(P-DAP)为主要成膜物,二缩三丙二醇二丙烯酸酯(TPGDA)为活性稀释剂,双(2,4,6-三甲基苯甲酰基)苯基氧化膦(BAPO)为光引发剂,制备出新型的紫外光固化可剥性涂料。固化后的涂层具有良好的柔韧性、硬度、耐水、耐酸碱、耐汽油的性能,并且可剥性较好。     

新型UV固化木器涂料的合成及性能研究

乙醇为溶剂,偶氮二异丁腈(AIBN)为引发剂,引发邻苯二甲酸二烯丙酯(DAP)聚合.聚合工艺为饥饿滴加法加入反应原料DAP、乙醇、AIBN,反应温度为85℃,反应时间约4 h.反应收率约34%,聚合物是可溶的预聚体.预聚体的凝胶色谱、红外光谱图及碘值都显示其具备进一步交联固化的潜力.然后,以合成的邻苯二甲酸二烯丙酯预聚...