辅助材料

UV固化涂料用含氟超支化聚酯丙烯酸酯添加剂 以含氟异氰酸酯改性超支化聚酯Boltorn H20制备含氟超支化聚酯丙烯酸酯（FHPA）,并用1H-NMR谱和FTIR光谱分析其特点。以测量接触角的方法测试了FHPA作为添加剂的UV固化涂膜的水油湿润性。     

超支化水性聚氨酯乳液的制备及性能研究

以顺丁烯二酸酐改性的超支化聚酯Boltorn H20、聚四氢呋喃2000和异佛尔酮二异氰酸酯为主要原料合成了超支化水性聚氨酯乳液,研究了改性超支化聚酯Boltorn H20的合成,以及改性超支化聚酯中羧基含量、初聚—NCO/—OH物质的量比、催化剂用量等对制备水性聚氨酯的影响,并探讨了亲水基团含量、乳化温度、中和度等因素对乳液及涂膜性能的影响,进一步使用傅里叶红外和热重分析分别对超支化聚氨酯涂膜的结构和热稳定性能进行了表征及测试。结果表明,在不加催化剂,初聚—NCO/—OH物质的量比为2∶1,亲水基团含量为2.05%的条件下,合成得到的含固量为30%的超支化水性聚氨酯乳液稳定性好。由此得到的超支化聚氨酯薄膜的耐水性和热稳定性较好。     

含氟超支化聚氨酯丙烯酸酯低聚物的制备及其性能研究

采用全氟聚醚(PFPE)、异氟尔酮二异氰酸酯(IPDI)、甲基丙烯酸羟乙酯(HEMA)、超支化聚酯(H302)等制备了含氟超支化聚氨酯丙烯酸酯低聚物(HFUA),并通过FTIR(傅里叶红外光谱)表征了其结构。讨论了HFUA改性比例、含氟超支化聚合物用量和主体树脂种类对UV固化涂层的水/油接触角、吸水率、力学性能的影响。     

马来酸酐改性超支化聚酯及在紫外光固化涂层中的应用

以马来酸酐改性末端为羟基的超支化聚酯,得到链段中含大量不饱和双键的超支化马来酸酯,分析表征了不同改性度的超支化马来酸酯黏度、热稳定性及Tg的变化。以超支化马来酸酯为预聚物应用于紫外光固化涂层,考察了改性度对光固化膜附着力、冲击强度、柔韧性、硬度及耐溶剂性能的影响。实验表明,超支化马来酸酯是一种低黏度、热稳定性好、Tg易调节的高分子材料。当改性度为80%时,光固化涂层性能最佳,其光固化时间可达3 s,膜附着力为1级,耐冲击强度为4.8 N.m,柔韧性>7 cm,硬度达5H,同时具有优良的耐溶剂性能。     

马来酸酐改性超支化聚酯及其在紫外光固化涂层中的应用

以马来酸酐改性末端为羟基的超支化聚酯,得到链段中含大量不饱和双键的超支化马来酸酯,分析表征了不同改性度的超支化马来酸酯黏度、热稳定性及Tg的变化。以超支化马来酸酯为预聚物应用于紫外光固化涂层,考察了改性度对光固化膜附着力、冲击强度、柔韧性、硬度及耐溶剂性能的影响。实验表明,超支化马来酸酯是一种低黏度、热稳定性好、Tg易调节的高分子材料。当改性度为80%时,光固化涂层性能最佳,其光固化时间可达3s,膜附着力为1级,耐冲击强度为48kgf.cm,柔韧性>7cm,硬度达5H,同时具有优良的耐溶剂性能。     

含氟超支化聚酯的合成及其性能研究

利用十三氟辛酸对超支化聚酯进行端基改性,得到了含氟超支化聚酯。采用傅里叶变换红外光谱仪、差示扫描量热分析仪等对聚合物进行了表征和分析。结果表明:十三氟酸成功接枝到超支化聚酯上,含氟超支化聚酯的玻璃化转变温度为-20.5℃,含氟超支化聚酯溶液在固含量高达70%时仍具有较低的黏度,该聚合物成膜性好,涂膜的附着力为1级,柔韧性为1 mm,铅笔硬度2 H,抗冲击强度4.9 J/cm2,与水的接触角为105°,具有良好的表面疏水性。     

可UV固化的超支化聚酯改性聚氨酯丙烯酸酯的合成

采用两步法合成了可UV固化的超支化聚酯改性聚氨酯丙烯酸酯(HBUA),优化了合成条件,采用FT-IR对HBUA进行表征,并测试了其UV固化漆膜的综合性能。结果表明,合成HBUA的最佳反应条件是以质量分数0.5%的二月桂酸二丁基锡为催化剂,将相同摩尔数的异氟尔酮二异氰酸酯和甲基丙烯酸羟乙酯在35℃反应2.5 h,然后加入适量的超支化聚酯H20在70℃条件下反应3.0 h,UV固化HBUA漆膜与PUA漆膜相比具有更高的硬度和更好的耐磨性。     

超支化聚酯——乙二醇——水体系相行为和相关性质

分别在298.2 K、303.2 K、308.2 K、313.2 K和318.2 K温度下实验测定了超支化聚酯Boltorn H20—乙二醇—水、Boltorn H30—乙二醇—水和Boltorn H40—乙二醇—水体系的相行为以及Boltorn H20—乙二醇—水体系的密度、粘度和电导率数据。根据以上数据初步探讨了体系内分子间相互作用。研究结果表明,超支化聚酯Boltorn H聚合物(H20、H30和H40)—乙二醇—水三元体系中均存在着“最低临界共溶温度”。这三种超支化聚酯在当前体系中的相行为类似。Boltorn H20—乙二醇—水三元体系中,随着温度升高,体系中分子热运动的增强也导致密度和粘度降低而电导率增大。随着抗溶剂水的添加,氢键减弱导致密度降低,而氢键减弱和水分子在该体系中的“稀释”作用导致粘度降低。体系电导率随着Boltorn H20浓度的增大表明Boltorn H20是该体系中的主要电荷载体。     

超支化聚酯的改性及紫外光固化涂层性能研究

以丙烯酸为端基改性剂,采用溶液法对超支化聚酯进行改性,制备出可紫外光固化的端乙烯基超支化聚酯(VHBP)。采用FT-IR、1H-NMR、DSC和乌氏黏度计分别对产物的结构、玻璃化转变温度和特性黏数进行表征。将VHBP作为聚氨酯丙烯酸酯(PUA)的交联剂,研究了PUA/VHBP体系紫外光固化涂层的摆杆硬度、柔韧性、耐冲击性和附着力等性能,并与传统的聚氨酯丙烯酸酯/环氧丙烯酸酯(PUA/EA)紫外光固化涂层进行对比。结果表明,FT-IR、1H-NMR证实超支化聚酯的端基经丙烯酸改性后由羟基转化为双键基团,改性程度可达88.7%,改性后玻璃化转变温度和特性黏数均降低。在PUA中加入VHBP后涂层的摆杆硬度大幅提高,随着VHBP含量的增加,PUA/VHBP体系涂层的摆杆硬度逐渐增大,柔韧性保持不变,在VHBP含量较高时耐冲击性和附着力略有降低。VHBP含量为10%和20%时PUA/VHBP紫外光固化涂层具有良好的综合性能。对于PUA/EA体系,虽然加入EA后涂层的摆杆硬度也略有提高,但在相同组分比例时摆杆硬度均低于PUA/VHBP体系,EA含量较高时涂层的柔韧性、耐冲击性和附着力均降低。以VHBP作为交联剂改性PUA,所得到的紫外光固化涂层综合性能优于传统的PUA/EA涂层。     

超支化聚氨酯丙烯酸酯的合成及其固化膜性能

以合成的甲苯-2,4-二异氰酸酯.丙烯酸羟丙酯(TDI.HPA)单体对超支化聚酯(HBPE)进行端羟基改性,得到超支化聚氨酯丙烯酸酯(HBPUA)。研究了反应温度、时间对产物游离—NCO含量的影响,通过摆杆硬度、附着力、柔韧性、冲击强度等测试研究了活性单体的种类及用量对固化膜性能的影响,并采用FT-IR及TG对HBPE,HBPUA及其固化膜进行了表征和分析。结果表明,合成HBPUA的最佳条件为:n(2,4-TDI):n(HPA):n(HBPE)=6:6:1,反应温度70℃,反应时间3 h,催化剂二月桂酸丁基锡(DBTDL)用量为总质量的0.6%;TDI.HPA的合成反应温度35℃,反应时间2.5 h,DBTDL用量为总质量的0.4%。采用己二醇二丙烯酸酯为活性单体并控制其质量分数为20%时,超支化聚氨酯丙烯酸酯涂膜的力学性能、热稳定性较好。     

Fluorinated hyperbranched polyester acrylate used as an additive for UV curing coatings

The fluorinated hyperbranched polyester acrylate (FHPA) was synthesized by modifying the hyperbranched polyester Boltorn H20 with fluorinated isocyanate, and characterized with ¹H NMR and FTIR spectroscopic analysis. The water and oil wettability of the UV cured film with FHPA as an additive was investigated by measuring the contact angle. The results showed that an extremely low concentration of FHPA, even below 0.1 wt%, resulted in efficient decrement of the surface tension of UV cured film to 10–15 mN/m, and thus makes the film highly hydrophobic and oleophobic. The film with FHPA addition was stable in acidic and neutral solutions, and still had good water repellency after immersion in a pH 1 solution for several days. The X-ray photoelectron spectroscopic analysis confirmed that the film surface was enriched with fluorinated species. Moreover, the molecule with the highest average number of perfluoroalkyl groups had the highest tendency to aggregate at the surface of the UV cured film.     

Preparation and characterization of UV-curable hyperbranched polyurethane acrylate

A series of UV-curable hyperbranched polyurethane acrylate (HBPUA) oligomers were synthesized with isophorone diisocyanate (IPDI), hyperbranched polyester Boltorn H20 (HBP) and hydroxy-ethyl acrylate (HEA). The structure of HBPUA oligomers was characterized by Fourier transform infrared (FTIR) spectroscopy, ¹H nuclear magnetic resonance (¹H-NMR) spectroscopy, and gel permeation chromatography (GPC). The UV-curing kinetics of HBPUA films with Darocur 1173 were investigated, and their heat resistance and mechanical properties (including hardness, adhesion force, flexibility, and impact strength) were measured. The results show that the HBPUA oligomers have superior photosensitivity and the percent conversion of C=C reaches 81% when radiation time is 43 s. The heat resistance of the cured films decreased slightly with the increase in the content of the urethane-acrylate terminal group. Moreover, the mechanical properties of the cured films were influenced by the content of the OH group in HBP that reacted with the first NCO group of IPDI. When the content was 60%, the cured film had excellent overall properties. The hardness, flexibility, adhesion force, and impact strength were 4 H, 2 mm, 0 grade, and 47 kg cm, respectively.     

Preparation of waterborne hyperbranched polyurethane acrylate/LDH nanocomposite

A series of novel waterborne hyperbranched polyurethane acrylate (WHPUA)/layered double hydroxide (LDH) nanocomposites based on hyperbranched aliphatic polyester Boltorn H20 (H20) and MgAl-LDH were successfully synthesized by in situ polymerization approach. The MgAl-LDH was firstly modified by sodium dodecyl sulfate (SDS) through the coprecipitation method, and then grafted by isophorone diisocyanate (IPDI), forming a complex with NCO groups at the surface and interlayer of LDH (LDH-DS-NCO). The residual hydroxyl groups after modification with succinic anhydride were crosslinked by the semi-adduct of IPDI reacted with HEA, and LDH-DS-NCO, followed by a neutralization reaction with triethylamine. The resulting water dispersible hyperbranched polyurethane acrylate WHPUA/LDH hybrid oligomer was then exposed to a medium pressure mercury lamp, forming a partially exfoliated WHPUA/LDH nanocomposite in the presence of a fragmental photoinitiator. The chemical structure, crystal configuration, morphology of WHPUA/LDH nanocomposite were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, and high resolution transmission electron microscopy. The experimental results indicated that both the intercalated and exfoliated structures were formed in the UV cured polymer/LDH nanocomposite. The TGA results showed that the thermal stability was improved. Moreover, the pencil hardness was greatly increased, and the flexibility remained at an acceptable level for the UV cured polymer/LDH nanocomposites.     

以生物基二聚脂肪酸制备聚氨酯丙烯酸酯树脂及其性能研究

为了减缓石油资源消耗,利用可再生二聚酸制备聚氨酯丙烯酸酯。将二聚脂肪酸(DA)与乙二醇(EG)以不同的物质的量比缩合制得3种不同羟值的聚酯二元醇(A-1、A-2、A-3),再依次通过与甲苯二异氰酸酯(TDI)、丙烯酸羟乙酯(HEA)反应引入丙烯酸酯基团,从而制得3种可光固化的聚氨酯丙烯酸酯树脂(B-1、B-2、B-3)。利用傅立叶变换红外光谱(FT-IR)对原料及合成产物进行了结构表征;采用实时红外分析(RT-IR)研究了不同条件下树脂的光固化性能;采用万能试验机、差示扫描量热仪(DSC)、热重分析仪(TGA)分析测试了固化膜的力学性能、玻璃化转变温度和热稳定性;同时测试了固化膜的接触角及铅笔硬度等。结果表明:随着二聚酸含量的升高,所制得的聚酯二元醇黏度和数均相对分子质量增大,羟值降低。最终所制备的聚氨酯丙烯酸酯树脂固化膜的热稳定性和附着力基本相同,但随着羟值含量的降低,软段部分增加,双键含量降低,交联密度下降,导致固化膜铅笔硬度、吸水率降低,柔韧性增加。     

Dual‐curable unsaturated polyester inorganic/organic hybrid films

An unsaturated polyester, based on maleic anhydride, 1,6‐hexanediol, and trimethylol propane, was formulated with tetraethylorthosilicate (TEOS) oligomers and a coupling agent to prepare inorganic/organic hybrid films. TEOS oligomers were prepared through the hydrolysis and condensation of TEOS with water, and 3‐(triethoxysilyl)propylisocyanate was used as the coupling agent between the organic and inorganic phases. The hybrid materials were cured by moisture via sol–gel chemistry and by the UV curing of unsaturated polyesters. To compare the properties of the moisture‐cured inorganic/organic hybrid films, a conventional 2K polyurethane system was also prepared. The tensile, adhesion, abrasion, and fracture toughness properties were investigated as functions of the coupling agent and relative amount of UV cure versus thermal cure. Although no difference could be observed in the tensile properties, the abrasion resistance, fracture toughness, and adhesion were enhanced by the incorporation of TEOS oligomers into polyurethane films. Also, the abrasion resistance, fracture toughness, and tensile properties were increased with both moisture and UV exposure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 115–126, 2006     

Synthesis and characterization of APTMS/melamine cured hyperbranched polyester-epoxy hybrid coatings

An epoxy-terminated hyperbranched polyester (EPHBP) was prepared by the reaction of hyperbranched polyester (HBP) and epichlorohydrin (EPH). Herein, we have synthesized a new kind of highly epoxy ended branched polyester to enhance the chemical bonding at the interfaces and to reduce the melt viscosity. The structural investigation of the hyperbranched polyesters was carried by spectroscopic techniques such as nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FTIR) while molar masses were determined using gel permeation chromatography (GPC). The effect of the content of hexamethoxy methyl melamine (HMMA) and 3-amino propyltrimethoxysilane (APTMS) mixture on the thermal, mechanical and interfacial properties of EPHBP resins were also studied. The thermal, dynamic mechanical and mechanical properties of the heat cured coating films were also investigated. The combined analysis of the results indicate that the introduction of APTMS results in the enhancement of the thermal stability, glass-transition temperature (T_g), storage modulus, tensile strength and contact angle of the cured films. The improvement in properties depends on the APTMS content of the cured films. The cured films have also shown higher elongation at break due to the use of HMMA and presence of unmodified epoxide groups which indicates good flexibility and toughness of the coating films.     

高性能水性UV固化聚氨酯的合成与性能研究

用环氧丙烯酸酯(EA)、羟基硅油合成了环氧/有机硅改性水性光固化聚氨酯乳液(WPU);研究了EA、羟基硅油、亲水扩链剂二羟甲基丁酸(DMBA)的用量,中和度和硅烷偶联剂的添加量对乳液和涂膜性能的影响。用红外光谱和接触角测量仪对树脂进行表征。结果表明:通过EA、羟基硅油改性的水性光固化聚氨酯涂膜的硬度高、附着力强、耐水性较好,克服了未改性水性光固化聚氨酯的缺点。当EA用量为4%、羟基硅油为2%、DMBA为8%、中和度为80%、硅烷偶联剂的添加量为1%时,水性光固化聚氨酯乳液的综合性能较好,树脂接触角大大提高。