UV固化水性超支化聚氨酯丙烯酸酯的制备、结构与性能研究
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摘要
水性光固化体系因结合了水性树脂和光固化技术两者的优点，具有环保（无稀释剂、无VOC）、适用性广（适于各种涂装设备、易清洗）、产品性能好（附着力好、软硬程度适宜）等特点，成为涂料工业发展的必然趋势。水性聚氨酯丙烯酸树脂（WPUA）由于综合性能较好，是当前UV固化水性基体树脂中研究最多、应用最广的体系。但线型WPUA树脂中普遍存在的固含量不高、粘度过大以及交联密度不够、硬度和耐热性能不理想等问题也成为了其继续发展的障碍。
超支化聚合物因其独特的三维球形多分枝结构，而具有外围官能度高、反应性强、粘度低、溶解性好等众多特性，可将其应用于UV固化WPUA体系，以缓解线型WPUA体系高固含与低粘度间的矛盾，提升整个体系的性能。但目前对UV固化水性超支化聚氨酯丙烯酸酯体系研究的还很少。本论文便是以此为主要思路，通过分子设计的方式，以超支化聚酯（HBP）为核，通过对其外围端羟基进行不同程度的亲水化及丙烯酸酯化改性，制得了一系列稳定性好、固含量高，且粘度适宜的水性超支化聚氨酯丙烯酸酯分散液（WHBPUAD），并将其应用于UV固化体系，得到的固化膜硬度高、柔韧性好，力学性能优良。论文主要的研究内容和成果包括如下四点。
第一：以超支化聚酯为中心核，先采用马来酸酐（MA）对其部分端羟基进行亲水化改性，得到亲水改性物（B-H20-MA），再以异佛尔酮二异氰酸酯（IPDI）及丙烯酸羟乙酯（HEA）的加成产物（IPDI-HEA）对其剩余的端羟基进行丙烯酸酯化改性，通过控制不同的改性程度，制备了一系列羧基含量及C=C双键含量不同的WHBPUAD。采用FTIR、1H-NMR、GPC及DSC等分析测试手段表征了WHBPUAD的分子结构，并通过红外监控及化学滴定的方法考察了温度、时间、催化剂种类及催化剂用量等因素对各步反应转化率的影响。结果表明，温度及催化剂用量对反应影响很大，各步最佳的反应条件为：以4wt.%的4-二甲氨基吡啶（DMAP）为催化剂，50℃下反应5h，利用B-H20的端羟基及MA的酸酐基团之间的单酯化反应制得亲水改性物B-H20-MA；以0.5wt.%的二月桂酸二丁基锡（DBTDL）为催化剂，35℃下反应2.5h制得含异氰酸酯基团的加成物IPDI-HEA；最后以0.5wt.%的DBTDL为催化剂，由IPDI-HEA和B-H20-MA在70℃下反应5h制得WHBPUAD。不同组成产物的玻璃化转变温度差别不大，均在30℃左右；相对分子量与设计的理论值基本相符，但要小于理论值，分子量分布随硬段结构的增加而加宽。
第二：以激光粒度分析仪和旋转流变仪为主要测试手段，考察了体系的各项稳定性指标，研究了固含量、亲水基团含量及中和度等诸多因素对WHBPUAD体系分散性及流变性的影响，通过Cross、Krieger-Dougherty（K-D）等模型方程对体系的流变曲线进行了模拟，得到了拟合方程，求得了最大体积分数φm，并通过拟合参数的标准化处理得到了不同固含量时粘度的主曲线。研究表明：WHBPUAD有着良好的稳定性，可避光保存一年以上。体系分散性良好，分散液粒径基本在100nm以下，随着亲水基团含量及中和度的增加而增大。WHBPUAD体系为非牛顿流体，具有剪切变稀现象，且随着固含量、亲水基团含量及中和度的增加而更为明显；体系较线型WPUA粘度明显更低，随着固含量和中和度的增加及亲水基团含量的降低而呈增大趋势。通过K-D方程得到该体系的φm为0.71。另外，幂律、Cross及Carreau三种流动方程均可较好对WHBPUAD体系流动行为进行描述，但后两者描述的更为准确。
第三：通过FTIR实时监控的方法，研究了WHBPUAD体系的UV固化过程，考察了影响UV固化过程和固化膜力学性能的因素，并对其干燥过程进行了研究。结果表明：结构中亲水基团含量增加会显著延长干燥脱水所需时间，但80℃下2min足以干燥脱除WHBPUAD湿膜中大部分的水，结合所选引发剂综合考虑，得到适宜的干燥脱水条件为：50℃下真空干燥2～10min。FTIR监控表明，固化历程受C=C双键浓度和体系粘度的双重控制，在光引发剂Darocur1173用量为4wt.%时，WHBPUAD8-8有着最快的光固化速率R max
P和最高的最终转化率τf，其值分别为71mmol·g-1s-1及93%。固化膜力学性能优良，附着力为0级、冲击强度55kg.cm，柔韧性为1mm，固化膜硬度随初始C=C双键浓度增大，WHBPUAD12-4硬度最高，摆杆硬度值为0.7。
第四：以热重分析（TG）为测试手段，研究了不同组成对WHBPUAD热稳定性的影响，得到了分解各步的热分解动力学方程。另外，同时应用热重-红外光谱联用仪（TGA-FTIR）及热裂解气相色谱-质谱联用仪(Py-GC/MS)测试技术，对WHBPUAD的热裂解过程进行了研究，并给出了其可能的热裂解机理。结果表明：固化膜热稳定性良好，在170℃前无明显失重，不同组成样品有着相似的分解历程，都经历四个明显的分解阶段。应用Horowitz-Metzger法求得的各阶段热分解活化能很好的反映了WHBPUAD分子结构同本体热性能间的关系，结构中软段含量越高时，热分解活化能也越高，样品整体热稳定越好。WHBPUAD可能的热裂解历程是，第一阶段为外围酯键的断裂，裂解溢出的气体主要为CO2、MA及三乙胺（TEA）；第二阶段为硬段的裂解，主要溢出为CO2和HEA；第三阶段为软段的断裂，溢出的气体主要为CO2、HEA、IPDI及小分子的不饱和醇、不饱和酸、酯等；第四阶段为分子内核，即B-H20的裂解，裂解产物比较复杂，主要由杂环类化合物、烯醛类化合物，烯醇类化合物，烯烃类化合物及丙烯酸（酯）类及衍生物组成。
The UV curable waterborne coating has both the advantages of waterborne coating andUV curable coating, such as environmental, wide applicability, good performance of film, etc.It becomes an inevitable trend of coating. At present, waterborne polyurethane-acrylate(WPUA) coating has attracted more and more attentions due to their good comprehensiveperformance. However, the shortcomings of common linear waterborne polyurethane-acrylate(LWPUA), including relatively high viscosity, low solid content and crosslinking density, aswell as insufficient hardness and thermal properties, limit its future applications.
Hyperbranched polymer (HBP) has many attractive features, such as low viscosity, highsolubility and reactivity, good compatibility, owing to its possesses a kind of uniquespherical-multibranched structure. Therefore, HBP can be applied to prepare UV-curablewaterborne polyurethane-acrylate coatings in order to relieve the contradiction between thesolid content and viscosity of LWPUA. However, there are few references about HBP used asprepolymer in the system of UV-curable WPUA at present. In this work, a series ofUV-curable waterborne hyperbranched polyurethane acrylate dispersions (WHBPUAD) wereprepared by endcapping of the hyperbranched ester with different number of hydrophilic andacrylic groups by the special design of the polymer structure. The dispersion has good storagestability, higher solid content, relatively lower viscosity, and the UV cured film had excellentcomprehensive performance such as higher hardness, good flexibility and thermal stability.The main research contents and results are listed as following:
Firstly, a series of UV-curable waterborne hyperbranched polyurethane acrylatedispersions were prepared by a three-step procedure based on isophorone diisocyanate (IPDI),hyperbranched polyester (HBP), maleic anhydride (MA) and2-hydroxyethyl acrylate (HEA).The structure of WHBPUADs was characterized by Fourier transform infrared spectroscopy(FTIR),1H nuclear magnetic resonance spectroscopy (1H-NMR), differential scanningcalorimeter (DSC) and gel permeation chromatography (GPC). The effects of the types ofcatalysts and their concentrations, reaction temperature and time on the conversion werestudied by FTIR and chemical titration. The results showed that the target production wasobtained successfully and the optimal condition was that the isocyanate adduct of IPDI/HEA(Prepolymer I) was prepared with0.5wt.%DBTDL as catalyst at5℃for150min；Prepolymer II was prepared by mono-esterification reaction from HPB and MA with4wt.%DMAP as catalyst at50℃for300min; and then the Prepolymer II reacted with Prepolymer Iat70℃for300min to prepare WHBPUA. The glass transition temperatures (Tg) of WHBPUAD with different raw materials' proportion were about30℃, which were close witheach other. The trend of relative molecular mass was agree with that of the theoretical valuebut all were lower in quantity, and the molecular weight distribution (MWD) became broadwith the hard segment content increase.
Secondly, laser particle size analyzer and rotational rheometer were used to investigatethe stability, the dispersity and the steady rheological behaviors of WHBPUADs. The effectsof many factors including solid content, concentration of hydrophilic groups, and degree ofneutralization on the dispersity and rheological behaviors were studied. The flow curves ofWHBPUADs were fitted mathematically by using Cross model, Carreau model,Krieger-Dougherty (K-D) equation and so on. The maximum volume fraction (m) and themaster curve of the different solid content were obtained. It was found that WHBPUAD wasquite stable which could store for at least1year in the dark. Meanwhile, the system havegood dispersibility. Most of the particle diameters were less than100nm, and increased withthe concentration of hydrophilic groups and degree of neutralization. The WHBPUAD is anon-Newton pseudoplastic fluid with shear thinning characteristic. The shear thinningphenomenon becomes more obvious with the increase in solid content, concentration ofhydrophilic groups, and degree of neutralization. The viscosity of WHBPUAD was lower thanthat of the linear waterborne polyurethane acrylate (LWPUA). At the same shear rate, theviscosity of WHBPUAD increased with increasing solid content and degree of neutralizationbut decreased with increasing concentration of hydrophilic groups. The value of mwas0.71which was obtained by the K-D equation. The Cross model, Carreau model and Power modelequation all could be used to fit the rheological behavior of WHBPUAD, but the later was lessaccurate.
Thirdly, the photopolymerization kinetics of WHBPUAD was monitored by FTIR. Thedrying process and the influences of molecular structure on the photopolymerization kineticsand properties of WHBPUAD films were discussed. The results showed that most water ofthe wet film could be remove within2minutes at the temperature of80℃and theconcentration of hydrophilic groups could significantly prolong the drying time. Based on theproperties of the selected photoinitiator, the suitable drying condition was at50℃for2to10minutes under a vacuum. The results of FTIR showed that the double bond conversion (τ) andphotopolymerization rate (Rp) were affected by the concentration of double bond andviscosity of WHBPUADs. The UV-curable systems with higher double bond concentrationand lower viscosity led to higher τ and Rp. The maximum τ and Rpcould reach to93%and71 mmol·g-1s-1, respectively. UV-cured films were found to exhibit superior mechanicalproperties. It shows that all of the coating formulations passed the tests of adhesion with0grade, impact with50kg.cm, and flexibility tests with1mm mandrel, respectively. Thependulum harnesses were improved with the increase of double bond concentration.WHBPUAD12-4has the best mechanical properties with the maximum pendulum harnessesof0.70%.
Fourth, the effect of different ingredient on the thermal stability of WHBPUAD filmswas studied by TG, and the kinetic parameters and dynamical equations of the thermaldecomposition of WHBPUAD were obtained. Then, the pyrolytic process of WHBPUAD wasstudied by TGA-FTIR and Py-GC/MS. The possible pyrolysis mechanism was studied. Theresults indicated that the WHBPUAD films had good thermal stability without obvious weightloss peaks before170℃. All the WHBPUAD films with different ingredient had similarprocesses of thermal decomposition, which appeared four obvious weight loss regions. Theresults of thermal decomposition activation energy which obtained by the Horowitz-Metzgerequation could well reflect the relationship between the intrinsic thermal stability and themolecular structure. The sample with higher proportion of soft segment in the structure wouldhave higher thermal decomposition activation energy and thermal stability. The possiblepyrolysis mechanism was as following: in the first step of degradation, the peripheral esterbonds of the WHBPUAD molecule were broken and the mainly evolved gases were CO2, MAand TEA. In the second step, its degradation was resulted from the hard segment and thedegradation products involved CO2and HEA; In the third step, the degradation was related tothe soft segment and the mainly degradation products were CO2, HEA, IPDI, unsaturatedalcohol, unsaturated acid, ester and so on; Finally, for the fourth degradation stage, a muchmore complex mixture of products was identified, including heterocyclic, olefinic aldehyde,enol, olefin, acrylic, acrylate and their derivatives, most probably originating from the core ofB-H20.
超支化聚合物因其独特的三维球形多分枝结构，而具有外围官能度高、反应性强、粘度低、溶解性好等众多特性，可将其应用于UV固化WPUA体系，以缓解线型WPUA体系高固含与低粘度间的矛盾，提升整个体系的性能。但目前对UV固化水性超支化聚氨酯丙烯酸酯体系研究的还很少。本论文便是以此为主要思路，通过分子设计的方式，以超支化聚酯（HBP）为核，通过对其外围端羟基进行不同程度的亲水化及丙烯酸酯化改性，制得了一系列稳定性好、固含量高，且粘度适宜的水性超支化聚氨酯丙烯酸酯分散液（WHBPUAD），并将其应用于UV固化体系，得到的固化膜硬度高、柔韧性好，力学性能优良。论文主要的研究内容和成果包括如下四点。
第一：以超支化聚酯为中心核，先采用马来酸酐（MA）对其部分端羟基进行亲水化改性，得到亲水改性物（B-H20-MA），再以异佛尔酮二异氰酸酯（IPDI）及丙烯酸羟乙酯（HEA）的加成产物（IPDI-HEA）对其剩余的端羟基进行丙烯酸酯化改性，通过控制不同的改性程度，制备了一系列羧基含量及C=C双键含量不同的WHBPUAD。采用FTIR、1H-NMR、GPC及DSC等分析测试手段表征了WHBPUAD的分子结构，并通过红外监控及化学滴定的方法考察了温度、时间、催化剂种类及催化剂用量等因素对各步反应转化率的影响。结果表明，温度及催化剂用量对反应影响很大，各步最佳的反应条件为：以4wt.%的4-二甲氨基吡啶（DMAP）为催化剂，50℃下反应5h，利用B-H20的端羟基及MA的酸酐基团之间的单酯化反应制得亲水改性物B-H20-MA；以0.5wt.%的二月桂酸二丁基锡（DBTDL）为催化剂，35℃下反应2.5h制得含异氰酸酯基团的加成物IPDI-HEA；最后以0.5wt.%的DBTDL为催化剂，由IPDI-HEA和B-H20-MA在70℃下反应5h制得WHBPUAD。不同组成产物的玻璃化转变温度差别不大，均在30℃左右；相对分子量与设计的理论值基本相符，但要小于理论值，分子量分布随硬段结构的增加而加宽。
第二：以激光粒度分析仪和旋转流变仪为主要测试手段，考察了体系的各项稳定性指标，研究了固含量、亲水基团含量及中和度等诸多因素对WHBPUAD体系分散性及流变性的影响，通过Cross、Krieger-Dougherty（K-D）等模型方程对体系的流变曲线进行了模拟，得到了拟合方程，求得了最大体积分数φm，并通过拟合参数的标准化处理得到了不同固含量时粘度的主曲线。研究表明：WHBPUAD有着良好的稳定性，可避光保存一年以上。体系分散性良好，分散液粒径基本在100nm以下，随着亲水基团含量及中和度的增加而增大。WHBPUAD体系为非牛顿流体，具有剪切变稀现象，且随着固含量、亲水基团含量及中和度的增加而更为明显；体系较线型WPUA粘度明显更低，随着固含量和中和度的增加及亲水基团含量的降低而呈增大趋势。通过K-D方程得到该体系的φm为0.71。另外，幂律、Cross及Carreau三种流动方程均可较好对WHBPUAD体系流动行为进行描述，但后两者描述的更为准确。
第三：通过FTIR实时监控的方法，研究了WHBPUAD体系的UV固化过程，考察了影响UV固化过程和固化膜力学性能的因素，并对其干燥过程进行了研究。结果表明：结构中亲水基团含量增加会显著延长干燥脱水所需时间，但80℃下2min足以干燥脱除WHBPUAD湿膜中大部分的水，结合所选引发剂综合考虑，得到适宜的干燥脱水条件为：50℃下真空干燥2～10min。FTIR监控表明，固化历程受C=C双键浓度和体系粘度的双重控制，在光引发剂Darocur1173用量为4wt.%时，WHBPUAD8-8有着最快的光固化速率R max
P和最高的最终转化率τf，其值分别为71mmol·g-1s-1及93%。固化膜力学性能优良，附着力为0级、冲击强度55kg.cm，柔韧性为1mm，固化膜硬度随初始C=C双键浓度增大，WHBPUAD12-4硬度最高，摆杆硬度值为0.7。
第四：以热重分析（TG）为测试手段，研究了不同组成对WHBPUAD热稳定性的影响，得到了分解各步的热分解动力学方程。另外，同时应用热重-红外光谱联用仪（TGA-FTIR）及热裂解气相色谱-质谱联用仪(Py-GC/MS)测试技术，对WHBPUAD的热裂解过程进行了研究，并给出了其可能的热裂解机理。结果表明：固化膜热稳定性良好，在170℃前无明显失重，不同组成样品有着相似的分解历程，都经历四个明显的分解阶段。应用Horowitz-Metzger法求得的各阶段热分解活化能很好的反映了WHBPUAD分子结构同本体热性能间的关系，结构中软段含量越高时，热分解活化能也越高，样品整体热稳定越好。WHBPUAD可能的热裂解历程是，第一阶段为外围酯键的断裂，裂解溢出的气体主要为CO2、MA及三乙胺（TEA）；第二阶段为硬段的裂解，主要溢出为CO2和HEA；第三阶段为软段的断裂，溢出的气体主要为CO2、HEA、IPDI及小分子的不饱和醇、不饱和酸、酯等；第四阶段为分子内核，即B-H20的裂解，裂解产物比较复杂，主要由杂环类化合物、烯醛类化合物，烯醇类化合物，烯烃类化合物及丙烯酸（酯）类及衍生物组成。
The UV curable waterborne coating has both the advantages of waterborne coating andUV curable coating, such as environmental, wide applicability, good performance of film, etc.It becomes an inevitable trend of coating. At present, waterborne polyurethane-acrylate(WPUA) coating has attracted more and more attentions due to their good comprehensiveperformance. However, the shortcomings of common linear waterborne polyurethane-acrylate(LWPUA), including relatively high viscosity, low solid content and crosslinking density, aswell as insufficient hardness and thermal properties, limit its future applications.
Hyperbranched polymer (HBP) has many attractive features, such as low viscosity, highsolubility and reactivity, good compatibility, owing to its possesses a kind of uniquespherical-multibranched structure. Therefore, HBP can be applied to prepare UV-curablewaterborne polyurethane-acrylate coatings in order to relieve the contradiction between thesolid content and viscosity of LWPUA. However, there are few references about HBP used asprepolymer in the system of UV-curable WPUA at present. In this work, a series ofUV-curable waterborne hyperbranched polyurethane acrylate dispersions (WHBPUAD) wereprepared by endcapping of the hyperbranched ester with different number of hydrophilic andacrylic groups by the special design of the polymer structure. The dispersion has good storagestability, higher solid content, relatively lower viscosity, and the UV cured film had excellentcomprehensive performance such as higher hardness, good flexibility and thermal stability.The main research contents and results are listed as following:
Firstly, a series of UV-curable waterborne hyperbranched polyurethane acrylatedispersions were prepared by a three-step procedure based on isophorone diisocyanate (IPDI),hyperbranched polyester (HBP), maleic anhydride (MA) and2-hydroxyethyl acrylate (HEA).The structure of WHBPUADs was characterized by Fourier transform infrared spectroscopy(FTIR),1H nuclear magnetic resonance spectroscopy (1H-NMR), differential scanningcalorimeter (DSC) and gel permeation chromatography (GPC). The effects of the types ofcatalysts and their concentrations, reaction temperature and time on the conversion werestudied by FTIR and chemical titration. The results showed that the target production wasobtained successfully and the optimal condition was that the isocyanate adduct of IPDI/HEA(Prepolymer I) was prepared with0.5wt.%DBTDL as catalyst at5℃for150min；Prepolymer II was prepared by mono-esterification reaction from HPB and MA with4wt.%DMAP as catalyst at50℃for300min; and then the Prepolymer II reacted with Prepolymer Iat70℃for300min to prepare WHBPUA. The glass transition temperatures (Tg) of WHBPUAD with different raw materials' proportion were about30℃, which were close witheach other. The trend of relative molecular mass was agree with that of the theoretical valuebut all were lower in quantity, and the molecular weight distribution (MWD) became broadwith the hard segment content increase.
Secondly, laser particle size analyzer and rotational rheometer were used to investigatethe stability, the dispersity and the steady rheological behaviors of WHBPUADs. The effectsof many factors including solid content, concentration of hydrophilic groups, and degree ofneutralization on the dispersity and rheological behaviors were studied. The flow curves ofWHBPUADs were fitted mathematically by using Cross model, Carreau model,Krieger-Dougherty (K-D) equation and so on. The maximum volume fraction (m) and themaster curve of the different solid content were obtained. It was found that WHBPUAD wasquite stable which could store for at least1year in the dark. Meanwhile, the system havegood dispersibility. Most of the particle diameters were less than100nm, and increased withthe concentration of hydrophilic groups and degree of neutralization. The WHBPUAD is anon-Newton pseudoplastic fluid with shear thinning characteristic. The shear thinningphenomenon becomes more obvious with the increase in solid content, concentration ofhydrophilic groups, and degree of neutralization. The viscosity of WHBPUAD was lower thanthat of the linear waterborne polyurethane acrylate (LWPUA). At the same shear rate, theviscosity of WHBPUAD increased with increasing solid content and degree of neutralizationbut decreased with increasing concentration of hydrophilic groups. The value of mwas0.71which was obtained by the K-D equation. The Cross model, Carreau model and Power modelequation all could be used to fit the rheological behavior of WHBPUAD, but the later was lessaccurate.
Thirdly, the photopolymerization kinetics of WHBPUAD was monitored by FTIR. Thedrying process and the influences of molecular structure on the photopolymerization kineticsand properties of WHBPUAD films were discussed. The results showed that most water ofthe wet film could be remove within2minutes at the temperature of80℃and theconcentration of hydrophilic groups could significantly prolong the drying time. Based on theproperties of the selected photoinitiator, the suitable drying condition was at50℃for2to10minutes under a vacuum. The results of FTIR showed that the double bond conversion (τ) andphotopolymerization rate (Rp) were affected by the concentration of double bond andviscosity of WHBPUADs. The UV-curable systems with higher double bond concentrationand lower viscosity led to higher τ and Rp. The maximum τ and Rpcould reach to93%and71 mmol·g-1s-1, respectively. UV-cured films were found to exhibit superior mechanicalproperties. It shows that all of the coating formulations passed the tests of adhesion with0grade, impact with50kg.cm, and flexibility tests with1mm mandrel, respectively. Thependulum harnesses were improved with the increase of double bond concentration.WHBPUAD12-4has the best mechanical properties with the maximum pendulum harnessesof0.70%.
Fourth, the effect of different ingredient on the thermal stability of WHBPUAD filmswas studied by TG, and the kinetic parameters and dynamical equations of the thermaldecomposition of WHBPUAD were obtained. Then, the pyrolytic process of WHBPUAD wasstudied by TGA-FTIR and Py-GC/MS. The possible pyrolysis mechanism was studied. Theresults indicated that the WHBPUAD films had good thermal stability without obvious weightloss peaks before170℃. All the WHBPUAD films with different ingredient had similarprocesses of thermal decomposition, which appeared four obvious weight loss regions. Theresults of thermal decomposition activation energy which obtained by the Horowitz-Metzgerequation could well reflect the relationship between the intrinsic thermal stability and themolecular structure. The sample with higher proportion of soft segment in the structure wouldhave higher thermal decomposition activation energy and thermal stability. The possiblepyrolysis mechanism was as following: in the first step of degradation, the peripheral esterbonds of the WHBPUAD molecule were broken and the mainly evolved gases were CO2, MAand TEA. In the second step, its degradation was resulted from the hard segment and thedegradation products involved CO2and HEA; In the third step, the degradation was related tothe soft segment and the mainly degradation products were CO2, HEA, IPDI, unsaturatedalcohol, unsaturated acid, ester and so on; Finally, for the fourth degradation stage, a muchmore complex mixture of products was identified, including heterocyclic, olefinic aldehyde,enol, olefin, acrylic, acrylate and their derivatives, most probably originating from the core ofB-H20.
引文
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