高性能颜料的技术现状和创新动向(续)

高性能颜料是一类重要的有机颜料,由于它们性能优异、制造特殊、安全低毒、适应性强,因此近年发展迅速。文中详细阐述了该类颜料的技术现状和安全性,指出了它们的创新动向即新颖结构颜料的开发,现有颜料的技术改进,喷墨墨水和滤色片用颜料的开发,光·电子功能性颜料的开发。     

高性能颜料的技术现状和创新动向

高性能颜料是一类重要的有机颜料,由于它们性能优异、制造特殊、安全低毒、适应性强,因此近年发展迅速。文中详细阐述了该类颜料的技术现状和安全性,指出了它们的创新动向即新颖结构颜料的开发,现有颜料的技术改进,喷墨墨水和滤色片用颜料的开发,光.电子功能性颜料的开发。     

有机颜料开发的新动向

有机颜料是一类重要的着色剂。本文综述了近年的开发动向，除了开发新结构颜料外，重点放在现有颜料的改良，新的有机颜料诱导体与固溶体颜料的合成上。它们对促进有机颜料的发展具有重要的价值。     

有机颜料商品化技术的发展和应用

有机颜料是一种几乎不溶解的有色微粒状物质,化学合成的有机颜料不是最终的具有实用性的商品,为了把它们转化为具有很好应用特性的微细分散体形式的商品,有机颜料必须进行商品化处理,因此有机颜料的分散性与分散稳定性成了有机颜料商品化处理后的突出性能要求.文中阐述了有机颜料商品化技术包括颜料化技术(特别是颜料表面处理剂)和预分散化技术(特别是微细分散技术、挤水转相技术与新颖载体树脂等)及其相应的有机颜料商品形态的发展和应用,并指出近年有机颜料商品化技术获得了很大的发展和预分散型颜料在有机颜料发展中起着越来越重要的作用.     

尚未开发的颜料用中间体

该文着重介绍了高性能有机颜料中的偶氮缩合类颜料、异吲哚啉酮和异吲哚啉类颜料合成中所必须的中间体,特别是国内尚未开发的一些中间体的合成.这些中间体的合成工艺不比CLT酸复杂,但它们的开发成功却对发展高性能有机颜料有较大的促进.     

含铅颜料代用品的开发进展

含铅颜料是主要的铅污染源。介绍了国外含铅颜料代用品的开发情况,它们是新型无毒防锈颜料、正确调整的有机颜料、金红石型混相颜料、钒酸铋黄、稀土颜料和安全黄。     

有机颜料工业新技术进展

综述了有机颜料的新的化学结构类型,应用特性,新的合成工艺与新技术及其进展,DPP类颜料向更好的应用性能和新的剂型发展;苯并咪唑酮-二噁嗪类颜料是将两种结构引入到同一分子中以获得更高的着色强度和稳定性。新的颜料化技术可获得纳米级颜料或隐型颜料,在水介质压力下颜料化技术,等离子溅射表面改性技术,微波照射合成工艺等成为有机颜料工业新技术进展过程中的开发热点。本文提出了有机颜料新型发色体系的开发、表面改性、专用助剂等六个值得关注的技术问题和包括有机颜料结构、粒径大小及分布、颗粒表面极性在内的“核心技术”(S&PPP)概念。有41篇参考文献。     

塑料着色用新型有机颜料

近年国内外塑料工业发展很快，使其着色的新型有机颜料也随之发展。本文阐述了各种新型有机颜料的结构和性能，它们适用于不同类型颜料的着色，对颜料工业的发展具有重要的价值。     

塑料用新型有机颜料的开发

综述了近年来开发的各种新型塑料用有机颜料的状况和特点,它们对有同颜料工业的产品结构调整和新品种的开发具有重要的指导价值。     

国外有机颜料工业的发展

国外有机颜料年产量约16～18万吨,市场贸易总额约28亿美元,生产集中在西欧、美国和日本。有机颜料技术开发的趋势是:现有颜料的高性能化;开发新型颜料,如含新型骨架的氮杂甲川偶氮颜料、苯并咪唑酮系偶氮黄和橙色颜料、缩合多环异吲哚啉酮和1,4-二酮并吡咯系颜料;研究颜料中间体的新合成技术;扩大有机颜料用途。     

哌嗪类有机胺脱除二氧化硫性能及机理探讨

选择哌嗪（PZ）及其衍生物N,N'-双（2-羟乙基）哌嗪（BHEP）、N,N'-双（2-羟丙基）哌嗪（HPP）、1-（2-羟乙基）-4-（2-羟丙基）哌嗪（HEHPP）、1-（2-羟乙基）哌嗪（HEP）5种哌嗪类有机胺作为SO₂吸收剂,采用动态法在填料塔中吸收模拟烟气中的SO₂并对吸收剂进行热再生。4次循环吸收解吸实验结果表明：有机胺的碱性与位阻效应共同决定其脱硫性能。PZ的pK_a最大,对SO₂有较大的吸收容量,首次饱和吸收容量高达0.8428mol/mol,但难解吸且再生能耗高,首次解吸率仅为78.9%,4次循环后饱和吸收容量下降了54.3%,循环吸收能力较差;HEP吸收效果次于PZ,其解吸性能较PZ有所提高;双羟基哌嗪类二胺的pK_a最小,饱和吸收容量相对较低,平均不低于0.4mol/mol;解吸率高,平均保持在95%以上,且再生能耗低、稳定性好,其中HEHPP的脱硫性能介于BHEP和HPP之间。因此,双羟基哌嗪可作为新型高效脱硫剂。     

Hypophosphatasia: A Unique Disorder of Bone Mineralization

Hypophosphatasia (HPP) is a rare genetic disease characterized by a decrease in the activity of tissue non-specific alkaline phosphatase (TNSALP). TNSALP is encoded by the ALPL gene, which is abundantly expressed in the skeleton, liver, kidney, and developing teeth. HPP exhibits high clinical variability largely due to the high allelic heterogeneity of the ALPL gene. HPP is characterized by multisystemic complications, although the most common clinical manifestations are those that occur in the skeleton, muscles, and teeth. These complications are mainly due to the accumulation of inorganic pyrophosphate (PPi) and pyridoxal-5′-phosphate (PLP). It has been observed that the prevalence of mild forms of the disease is more than 40 times the prevalence of severe forms. Patients with HPP present at least one mutation in the ALPL gene. However, it is known that there are other causes that lead to decreased alkaline phosphatase (ALP) levels without mutations in the ALPL gene. Although the phenotype can be correlated with the genotype in HPP, the prediction of the phenotype from the genotype cannot be made with complete certainty. The availability of a specific enzyme replacement therapy for HPP undoubtedly represents an advance in therapeutic strategy, especially in severe forms of the disease in pediatric patients.     

Promoting effect of crystallization on the foaming behavior in polypropylene homopolymer/polypropylene block copolymer blends

Polypropylene (PP) is a kind of semi‐crystalline polymer so it is hard to foam with supercritical carbon dioxide (SCCO₂). We used polypropylene block (PP‐B) copolymer as a modifier to improve the crystallization behaviors and foaming performance of polypropylene homo polymer (HPP). HPP, PP‐B, and a series of HPP/PP‐B blends were characterized by differential scanning calorimeter (DSC), X‐ray diffraction, and polarized optical microscope. Results show that both the crystallization behaviors and melt strength have influence on the cell structure. The crystallization temperature of PP‐B is about 7°C higher than that of HPP and that the crystallization behavior of HPP/PP‐B blends is similar to that of PP‐B. Much denser and smaller size spherulites are observed in PP‐B and HPP/PP‐B blends than in HPP, and the crystal structure is unchanged after blending. Scanning electron microscope results show that much more uniform, smaller cells can be obtained for the HPP/PP‐B blends. The crystal nuclei formed earlier can act as physical crosslink points, increasing the melt strength and improving dramatically the cell structure and morphology of the HPP/PP‐B blends. Furthermore, the best cell structure and morphology was achieved for HPP/PP‐B blends with the ratio of 70/30 under the same foaming conditions. POLYM. ENG. SCI., 56:1175–1181, 2016. © 2016 Society of Plastics Engineers     

Synthesize and Characterization of Flame Retardant Copolyesters PET/Phosphorus Compound

The aim of this study was to achieve a fiber‐grade poly(ethylene terephthalate) (PET) with flame retardancy properties. Flame retardant copolyesters based on ethylene glycol, terephthalic acid, and 3‐(hydroxyphenyl phosphinyl) propionic acid (HPP), as a flame retardant comonomer, were synthesized in presence of antimony trioxide catalyst at laboratory and semi‐industrial scales. At first, copolyesters with the lowest amount of flame retardant comonomer were synthesized at laboratory scale in a one‐pot reactor setup. In the second stage, flame retardant PET was synthesized in semi‐industrial pilot with HPP (PET‐HPP). The obtained copolyesters demonstrated almost identical intrinsic viscosities and other characteristics such as PET. Fourier transform infrared spectroscopy (FTIR), 1H‐NMR spectroscopy, and RMS test were performed. Flame retardancies were evaluated by a limiting oxygen index (LOI) test. The results indicated that the presence of FR significantly improved the flame retardancy and thermal stability of PET‐HPP. LOI values increased from 28% (PET) to 33 (PET‐HPP) (at laboratory scale) and 44% (at semi‐industrial scale). Differential scanning calorimetry analysis showed that the HPP polyester chain had a higher flexibility compared to PET, due to lower glass transition temperature. The effect of adding FR with regard to the thermal stability of PET‐HPP was investigated via thermogravimetric analysis. The physical properties of both the polymers are similar and suitable for textile application. J. VINYL ADDIT. TECHNOL., 25:262–270, 2019. © 2018 Society of Plastics Engineers     

染颜料行业发展综述

本文简要介绍了中国染、颜料行业的基本特征及上下游企业的关系。通过＂十一五＂期间的产量及进出口等数据,详细说明了染、颜料行业在近五年的发展状况。同时,重点介绍了有机颜料中的高性能颜料（HPP）,尤其是苯并咪唑酮类高性能颜料的地位及发展概况,并给出行业发展的趋势分析。     

N,N’-二(2-羟丙基)哌嗪的合成及其在烟气脱硫工艺中的应用

利用无水哌嗪和环氧丙烷合成了N,N’-二(2-羟丙基)哌嗪(HPP),利用红外光谱对其进行了表征,利用滴定法计算出HPP的共轭酸的pKa1和pKa2值,通过热重分析仪研究了HPP的半盐溶液与SO2的反应行为和SO42-在湿法烟气脱硫中对HPP挥发损失的影响。结果表明,HPP的合成反应是按照反应物的化学计量比进行的,且工艺过程简单,得到的产物纯度较高。HPP的共轭酸的pKa1和pKa2分别为3.8和8.2。SO42-能够有效的抑制HPP的挥发,可以作为烟气脱硫工艺中HPP半盐溶液的阴离子。     

Flame retardant polyesters. I. Phosphorous flame retardants

Commercially available two types of phosphorous flame retardants (FRs) for polyester were compared from the viewpoint of chemical reactivity, reaction mechanism, and byproduct formation. 3‐(Hydroxyphenyl phosphinyl) propanoic acid (HPP) and 9,10‐dihydro‐9‐oxa‐10‐2,3‐dicarbonylpropyl)‐10‐phosphophenanthrene‐10‐oxide (DI) were used as a main chain type and a pendant type, respectively. HPP and DI showed different behavior with ethylene glycol (EG). More acidic HPP reacted with EG spontaneously and then produced esterified terminal hydroxy end group reacted with EG to form terminal diethylene glycol (DEG) end group. But the composition in the HPP solution was not varied for a long time below the esterification temperature. Contrast to HPP, DI showed normal esterification procedure. DI esterified with EG to form DI ester of EG, and DEG formation is not distinct. The difference of reactivity and DEG formation is caused by the difference of acidity in EG solution. For production of phosphorous containing polyester, it is desirable that HPP is introduced into the reactor in the mere solution state and DI in the esterified state. In addition, for production of polyester having the same phosphorous content in commercial scale, it is more beneficial to apply HPP than DI because of low input of FR due to low molecular weight. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Exploring the roles of molecular structure on the β-crystallization of polypropylene random copolymer

To investigate effects of molecular structures on β-crystallization of polypropylene random copolymer (PPR), PPR-A and PPR-B with similar molecular weight and distribution but significantly different polymorphic behavior were used. Wide-angle X-ray diffraction (WAXD), Fourier transform infrared spectroscopy (FT-IR), solvent fractionation combined with successive self-nucleation and annealing (SSA) and Gel Permeation Chromatography (GPC) were applied. Results revealed that after addition of same amount of β-nucleating agent (β-NA), large amount of β-phase is obtained in PPR-A (K _β  = 0.603), while no β-phase can be seen from PPR-B; Structure characterizations revealed that they have similar molecular weight but different total amount and distribution of ethylene comonomer: the total content of ethylene comonomer of PPR-A is higher compared with PPR-B, but its ethylene comonomer distribution is less uniform. In this way, PPR-A possesses high molecular weight high isotactic fraction, which cannot be seen from PPR-B due to its more uniform comonomer distribution. Therefore, the presence of highly isotactic PP (HPP) is the key factor in β-crystallization of PPR. For verification, HPP with low or high molecular weights are respectively added into β-nucleated PPR-B. Results revealed that HPP was effective in enhancing β-crystallization of PPR-B; higher molecular weight of HPP was more favorable and more effective.     

高刚性薄壁专用树脂的结构与性能

采用凝胶渗透色谱、差式扫描量热仪、万能拉伸机、升温淋洗分析仪等分析了高刚性薄壁注塑专用树脂HPP1850的分子结构、并与同类产品进行了对比。结果表明:高刚性薄壁专用树脂HPP1850分子链结构合理,具有良好的物理机械性能,产品达到国内外先进水平。     

Improved cell morphology and thermal properties of expanded polypropylene beads by the addition of PP with a high melting point

Expanded polypropylene (EPP) beads have attracted attention in recent years due to their potential use in fabricating complex, three dimensional structures. In this study, a small amount of polypropylene (PP) with a higher melting temperature (HPP) was blended with low melting point PP (LPP) to regulate the cell morphology and thermal behavior peaks of the resulting blends. These materials were then foamed to produce EPP beads in an autoclave with CO₂ at different temperatures, producing EPP beads. The rheological, thermal, and foaming properties of the LPP/HPP blends were characterized. The melt strength and elasticity of LPP/HPP were improved because of rapid crystallization and increase in crystal number with increasing HPP content. These results were attributed to the physical crosslinks and nucleation sites provided by the HPP. These enhanced properties were leveraged to produce regular foams without through‐holes, decreased cell size, and increased cell density. Furthermore, the lower melting point decreased with increasing HPP content, producing a wider temperature range over which steam‐chest molding could occur. Thus, the addition of HPP is a facile method for regulating the cell morphology and thermal behavior of EPP. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45121.