Lu Kun-Tsung, Chang Jing-Ping
Department of Forestry, National Chung Hsing University, 250, Kuo-Kuang Rd., Taichung 402, Taiwan.
Polymers (Basel). 2020 Mar 16;12(3):663. doi: 10.3390/polym12030663.
In this study, the antimicrobial agents of mono(hydroxyethoxyethyl)phthalate (M(HEEP)) with different metal of M = Zn, Mn, Pb, and Ca were synthesized from diethylene glycol (DEG), phthalic anhydride (PA), and divalent metal acetates including calcium acetate, zinc acetate, manganese acetate, and lead acetate, respectively. The waterborne urethane oil (WUO) dispersions synthesized from linseed oil, diisocyanates (hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI)), dimethylolpropionic acid at NCO/OH molars of 0.9, by acetone processing method were described as in our previous report. The M(HEEP) antimicrobial agents as well as the commercial nanosilver powder were added into WUO dispersions as the antimicrobial coatings. The effects of various antimicrobial agents and dosages (0.0, 0.2, 0.6, 0.8, 1.0, 2.0, and 4.0 phr) on antimicrobial activity of WUO films against gram-negative bacterium of , gram-positive bacterium of , brown-rot fungus of , and white-rot fungus of were assessed. In addition, the film properties of the best antimicrobial WUO coatings were also examined. The results showed that the antimicrobial agents of mono(hydroxyethoxyethyl) phthalate M(HEEP) (M = Zn, Mn, Pb, and Ca) powders should certainly be synthesized by FTIR, H-NMR, C-NMR, and energy-dispersive X-ray spectroscopy (EDS) identifications and the yields of them were 43-55%. The results also revealed that the WUO film synthesizing with HDI films containing Zn(HEEP) of 2.0 phr and Pb(HEEP) of 0.4 phr had the best antibacterial activity for and , respectively. The IPDI films containing Zn(HEEP) of 1.0 phr had the best antibacterial activity for both and For antifungal activity, the WUO film synthesizing with HDI films containing Pb(HEEP) of 0.8 phr and Zn(HEEP) of 2.0 phr as well as IPDI films containing Mn(HEEP) of 0.2 phr and Zn(HEEP) of 4.0 phr had the best performances against and , respectively. Comparing with commercial nanoAg powder, the Zn(HEEP) and Pb(HEEP) had a superior antifungal efficiency for and , while it had a slightly inferior efficiency in the antibacterial activity for and . On the properties of WUO films, adding metal-containing antimicrobial agents could slightly enhance the thermal stability, but lowered the gloss of all films, however, the value increased for HDI film and decreased for IPDI film. In addition to this, they had no significant difference in the film properties including hardness, impact resistance, bending resistance, adhesion, mass retention, and light-fastness between the WUO films with and without adding antimicrobial agents.
在本研究中，分别由二甘醇（DEG）、邻苯二甲酸酐（PA）和包括醋酸钙、醋酸锌、醋酸锰和醋酸铅的二价金属醋酸盐合成了金属M分别为锌（Zn）、锰（Mn）、铅（Pb）和钙（Ca）的单（羟乙氧基乙基）邻苯二甲酸酯（M(HEEP)）抗菌剂。如我们之前的报告所述，通过丙酮处理法，由亚麻籽油、二异氰酸酯（六亚甲基二异氰酸酯（HDI）和异佛尔酮二异氰酸酯（IPDI））、二羟甲基丙酸在NCO/OH摩尔比为0.9的条件下合成了水性聚氨酯油（WUO）分散体。将M(HEEP)抗菌剂以及商用纳米银粉添加到WUO分散体中作为抗菌涂层。评估了各种抗菌剂及其用量（0.0、0.2、0.6、0.8、1.0、2.0和4.0 phr）对WUO薄膜针对革兰氏阴性菌、革兰氏阳性菌、褐腐真菌和白腐真菌的抗菌活性的影响。此外，还研究了最佳抗菌WUO涂层的薄膜性能。结果表明，单（羟乙氧基乙基）邻苯二甲酸酯M(HEEP)（M = Zn、Mn、Pb和Ca）粉末抗菌剂确实应通过傅里叶变换红外光谱（FTIR）、氢核磁共振（H-NMR）、碳核磁共振（C-NMR）和能量色散X射线光谱（EDS）鉴定来合成，其产率为43 - 55%。结果还表明，合成的含有2.0 phr Zn(HEEP)和0.4 phr Pb(HEEP)的HDI薄膜的WUO薄膜分别对[具体革兰氏阴性菌]和[具体革兰氏阳性菌]具有最佳抗菌活性。含有1.0 phr Zn(HEEP)的IPDI薄膜对[具体革兰氏阴性菌]和[具体革兰氏阳性菌]均具有最佳抗菌活性。对于抗真菌活性，合成的含有0.8 phr Pb(HEEP)和2.0 phr Zn(HEEP)的HDI薄膜的WUO薄膜以及含有0.2 phr Mn(HEEP)和4.0 phr Zn(HEEP)的IPDI薄膜分别对[具体褐腐真菌]和[具体白腐真菌]具有最佳性能。与商用纳米银粉相比，Zn(HEEP)和Pb(HEEP)对[具体褐腐真菌]和[具体白腐真菌]具有更高的抗真菌效率，而在对[具体革兰氏阴性菌]和[具体革兰氏阳性菌]的抗菌活性方面效率略低。关于WUO薄膜的性能，添加含金属抗菌剂可略微提高热稳定性，但会降低所有薄膜的光泽度，不过，HDI薄膜的[具体性能指标]值增加，IPDI薄膜的[具体性能指标]值降低。除此之外，添加和未添加抗菌剂的WUO薄膜在包括硬度、抗冲击性、耐弯曲性、附着力、质量保留率和耐光性等薄膜性能方面没有显著差异。
