甘油基聚酯PVC增塑剂的制备及应用研究

以甘油、六氢苯酐为原料,钛酸四正丁酯为催化剂,2-乙基己醇为封端剂,环己烷为带水剂,经脱水缩聚、减压蒸馏制备聚六氢苯酐甘油酯。探究实验得到合成聚六氢苯酐甘油酯的佳醇酸摩尔比、催化剂和封端剂用量。通过红外光谱分析(FTIR)、热重分析(TG)、高效凝胶色谱分析(GPC)等对聚酯的结构、热稳定性及平均分子量进行了表征,并将该聚酯加入到聚氯乙烯(PVC)中,按照定配方制得PVC试片。结果表明:佳反应条件是六氢苯酐、甘油的摩尔比为1.0:1.4,2-乙基己醇、六氢苯酐的的摩尔比为0.8:1.0,催化剂用量为甘油、六氢苯酐和2-乙基己醇总量的1.0%;产品酸值在1.55 mgKOH/g左右,平均分子量在4 500左右,酯化率达到99.6%;产品呈淡黄色,热稳定性良好;制得PVC试片的拉伸性能和热稳定性较高,聚酯的迁移率较低。     

环氧化环己烷邻二甲酸二辛酯的合成工艺研究

运用条件试验法,以四氢苯酐和辛醇为原料,对甲苯磺酸为催化剂经过酯化合成四氢邻苯二甲酸二辛酯,酯化反应结束后直接加甲酸、EDTA、对甲苯磺酸、双氧水等进行环氧化反应得到环氧化环己烷邻二甲酸二辛酯。本研究以对甲苯磺酸作催化剂,分别对催化剂用量、反应时间、反应温度、原料配比等反应影响因素进行分析研究,并进行工艺优化,产品收率达99%以上。     

聚己二酸二甘醇酯增塑剂的制备及其在耐油手套上的应用

以己二酸和二甘醇为原料,2-乙基己醇作为封端剂,钛酸四丁酯为催化剂,通过酯化、缩聚合成聚己二酸二甘醇酯增塑剂。考察了反应时间、醇酸物质的量比以及封端剂用量等对合成聚酯增塑剂的影响,对样品进行了红外表征及凝胶色谱分析。结果表明,反应时间为6 h,醇酸比为1.2:1,2-乙基己醇与己二酸比值为0.1时,所得到样品的酯化率高、酸值较低,粘度适中。聚己二酸二甘醇酯增塑剂应用到耐油PVC手套上,其增塑性能和耐油效果较好。     

植物油基环氧化聚甘油多酯增塑剂的合成及应用

以生物柴油的副产物粗甘油为原料,通过聚合反应得到聚合甘油;再与油酸通过酯化反应得到中间产物聚甘油不饱和脂肪酸多酯。然后在无溶剂条件下,以硫酸为催化剂进行环氧化反应得到增塑剂环氧化聚甘油多酯。考察了反应温度、反应时间、甲酸用量以及 H2O2用量对产物的环氧值的影响。同时采用了傅立叶变换红外光谱和热重分析对产物的结构和热稳定性进行表征。结果表明,最佳环氧化条件为：反应温度65℃,反应时间6 h,聚甘油不饱和脂肪酸多酯、甲酸、30％ H2O2质量比为1∶0.5∶1.2。产品的酸值为1.24 mg KOH／g,环氧值为6.4％,残留碘值为6.8 mg／100 g,具有较好的热稳定性,应用到 PVC 树脂中可有效地提高 PVC 的增塑性。     

钛络合物均相催化合成聚六氢苯酐二甘醇酯

以六氢苯酐和二甘醇为原料,钛络合物钛酸正四丁酯为催化剂合成聚六氢苯酐二甘醇酯。结果表明,钛酸正四丁酯催化合成聚六氢苯酐二甘醇酯的最佳反应条件为：醇酸摩尔比为1.1∶1,催化剂用量为0.8%（以六氢苯酐质量计）,反应温度为220 ℃,反应时间为5 h,－0.095 MPa压强下减压时间为2.5 h,减压温度为220 ℃,酯化率大于99.0%。合成产物聚六氢苯酐二甘醇酯的数均分子量M_n为14000,重均分子量M_w为15000,分子量具有窄分布物性。     

环保增塑剂环己烷1,2-二甲酸二（2-丙基庚）酯的合成及性能研究

以六氢苯酐和2-丙基庚醇为原料,钛酸四丁酯为催化剂,进行酯化反应得到环己烷1,2-二甲酸二(2-丙基庚)酯(DPHCH)增塑剂。考察了醇酸摩尔比、催化剂种类及用量、反应温度、反应时间对酯化率的影响。确定了最佳工艺条件为:醇酸摩尔比为2.8∶1,反应温度为200℃,反应时间为3 h,催化剂用量为六氢苯酐质量的1.5%。产品为无色透明油状液体,酯化率可达到99.49%。采用傅里叶变换红外光谱(FTIR)及核磁共振氢谱(1HNMR)对DPHCH结构进行表征,将DPHCH作为增塑剂制成聚氯乙烯(PVC)树脂,并进行了拉伸性能、挥发减量、热重分析,结果表明,与增塑剂DINCH、DEHCH和DOP相比,DPHCH具有优异的增塑性能及热稳定性能。     

环保增塑剂环己烷1,2-二甲酸二(2-丙基庚)酯的合成及性能

以六氢苯酐和2-丙基庚醇为原料,钛酸四丁酯为催化剂,进行酯化反应得到环己烷1,2-二甲酸二(2-丙基庚)酯(DPHCH)增塑剂。考察了醇酸摩尔比、催化剂种类及用量、反应温度、反应时间对酯化率的影响。确定了最佳工艺条件为:醇酸摩尔比为2.8∶1,反应温度为200℃,反应时间为3 h,催化剂用量为六氢苯酐质量的1.5%。产品为无色透明油状液体,酯化率可达到99.49%。采用傅里叶变换红外光谱(FTIR)及核磁共振氢谱(1HNMR)对DPHCH结构进行表征,将DPHCH作为增塑剂制成聚氯乙烯(PVC)树脂,并进行了拉伸性能、挥发减量、热重分析,结果表明,与增塑剂DINCH、DEHCH和DOP相比,DPHCH具有优异的增塑性能及热稳定性能。     

环己烷-1,2-二羧酸二异壬酯的合成工艺研究

运用条件试验法,以六氢苯酐、异壬醇为原料,直接酯化合成环己烷-1,2-二羧酸二异壬酯,分别研究了反应温度、反应时间、原料配比、催化剂用量等条件对合成反应的影响,确定了最佳工艺条件。该方法合成环己烷-1,2-二羧酸二异壬酯的最佳工艺条件是:反应温度230℃,反应时间4 h,异壬醇与六氢苯酐的摩尔比为2.8,催化剂用量为0.25%。该催化剂具有廉价易得、催化活性好、不腐蚀设备、无环境污染等优点。     

均相催化六氢苯酐与C10直链醇制备环保增塑剂及其性能

采用均相催化剂钛酸四丁酯,以六氢苯酐和C10直链醇癸醇为原料,进行酯化得到高纯度的环保增塑剂环己烷1,2二甲酸二癸酯(DIDCH)。考察了醇酸摩尔比、催化剂种类及用量、反应时间、反应温度对酯化率的影响,确定了最佳工艺条件为：醇酸摩尔比为2.8∶1,反应时间为3 h,反应温度为200 ℃,催化剂用量为六氢苯酐质量的1.5 %。产品为无色透明油状液体,酯化率可达到99.48 %。采用傅里叶变换红外光谱(FTIR)及气相质谱联用仪(GC-MS)对DIDCH结构及纯度进行表征,将DIDCH作为增塑剂应用在聚氯乙烯( PVC)中。结果表明,使用DIDCH增塑的PVC试样,热老化试验试样变黄时间为60 min,玻璃化转变温度(Tg)为-8.91 ℃,具有优异的增塑性能及热稳定性能。     

酯化缩聚法制备耐迁移二甘醇聚酯增塑剂及性能研究

以二甘醇、苯酐、异辛醇为原料,钛酸四正丁酯为催化剂,环己烷做带水剂,通过酯化、缩聚方法合成聚苯酐二甘醇酯增塑剂,采用傅里叶变换红外光谱(FTIR)、凝胶液相色谱对产物进行结构表征,探究实验得到合成聚苯酐二甘醇聚酯的最佳醇酸物质的量比、催化剂和封端剂用量、反应时间和反应温度。对合成的产品作为增塑剂制成聚氯乙烯(PVC)树脂,并进行拉伸性能、挥发减量、热重分析。结果表明,苯酐二甘醇聚酯具有耐迁移,耐挥发等优良性能,适用功能PVC制品的添加剂,具有极大的工业化开发与应用前景。     

塑化剂风波与增塑剂行业对策

介绍了塑化剂(增塑剂)风波事件、主要新型环保增塑剂的性能与应用,以及用微藻为原料制备增塑剂的设想,并对我国增塑剂行业的发展方向提出了建议。     

国内外增塑剂工业现状及发展动态

本文论述了国内外增塑剂工业的现状，分析了国外增塑剂的发展动态以及国内与增塑剂工业相关的丁辛醇工业概况，并对发展我国增塑剂生产提出几点建议。     

耐寒增塑剂的应用及发展

详细介绍了耐寒增塑剂的品种及相关应用。综述了耐寒增塑剂在近年来所取得的技术进步,展望其未来耐寒增塑剂的发展趋势。     

HPLC法测定化妆品中十六种邻苯二甲酸酯类化合物

建立了以高效液相色谱测定化妆品中十六种邻苯二甲酸酯类化合物的分析方法。采用Diamonsil C8(250×4.6 mm,5μm)色谱柱,以甲醇-乙腈-0.2%三乙胺水溶液为流动相,梯度洗脱,流速0.9 mL/min,柱温25℃,检测波长280 nm。方法的平均加样回收率均在90%～110%之间,在0.1～0.8 mg/mL范围内呈良好线性关系,相关系数均大于0.999。该方法分离效果好,灵敏度高,能够满足化妆中16种邻苯二甲酸酯类化合物的检测需要。     

端羟基聚环氧氯丙烷酯化反应研究

通过端羟基聚环氧氯丙烷(PECH)的酯化,合成了端酯基PECH,用FT-IR和NMR进行了结构表征。优化了酯化反应工艺,结果表明:以乙酸酐为酯化剂,酯化剂与羟基物质的量比为1.6;N-甲基咪唑为催化剂,催化剂质量分数为3.6%;1,2-二氯乙烷为溶剂,反应温度为80℃,反应时间为0.5h,则羟基转化率为100%,收率>94.3%。     

淀粉的热塑性研究

通过在淀粉中加入增塑剂，制备热塑淀粉，研究了3种不同淀粉－玉米淀粉，木薯淀粉和可溶性淀粉的增塑性情况，研究了甘油、乙二醇、山梨醇、聚乙烯醇4种塑剂的增塑效果，不同的淀粉品种及不同增塑剂的产品性能有所不同。在显微镜下观察到，淀粉经塑化后，次价键断裂，晶区被破坏，使淀粉具备了热塑性，可以加工成薄膜。     

增塑剂对EPDM绝热层材料性能的影响

选择了部分酯类有机化合物（癸二酸二异辛酯，邻苯二甲酸二丁酯，磷酸三苯酯）作为EPDM绝热层材料配方的增塑剂，测试了配方的力学性能，粘接性能和加速老化性能。结果表明，癸二酸二异辛酯大量使用后，EPDM绝热层材料配方的力学性能保持稳定，邻苯二甲酸二丁酯，磷酸三苯酯大量使用后力学性能降低，当癸二酸二异辛酯含量在10份以下时，EPDM绝热层的各项性能稳定。癸二酸二异辛酯是适用于EPDM绝热层材料配方的增塑剂。     

Effects of inorganic nano‐particles on plasticizers migration of flexible PVC

The influences of nano‐particles (nano‐sized CaCO₃ and nano‐sized SiO₂) on plasticizers volatility, solvent extraction stability, and exudation stability of flexible PVC were studied. The results showed that nano‐particles could reduce migration of plasticizers, thus improved the ability of anti‐migration of flexible PVC. Further more, nano‐sized SiO₂ shows excellent property than nano‐sized CaCO₃ in resistance migration of plasticizers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of plasticizer and curing system on freezing resistance of rubbers

At glass transition temperature, T_g the rubber compound becomes stiff and brittle and it loses all its rubbery characteristics. This article deals with the changes in T_g of rubber blends based on natural rubber and polybutadiene rubber of varying vinyl content having different types and content of plasticizers, different curing systems and its effect on physico‐mechanical properties to improve its freezing resistance. The plasticizers used were dioctylphthalate (DOP), tricrecylphosphate (TCP), dioctyladipate (DOA), and oil type plasticizers like parafinic oil (P#2) and aromatic oil (A#2). Among the plasticizers, when DOP and DOA content was high, an appreciable decrease of T_g was found compared to TCP. Moreover, there was a remarkable decrease of T_g using DOA plasticizer, which shows more effective on freezing resistance. However, there was not much change in T_g with oil‐type plasticizers with high oil content compared to TCP plasticizer. The effect of cross‐linking systems such as conventional sulfur vulcanization (CV), efficient sulfur vulcanization (EV), and dicumyl peroxide (DCP) and rubber blends with varying vinyl content in polybutadiene rubber were also carried out. It was found that T_g in different cross‐linking system decreased in this order: CV < EV < DCP. It reveals that DCP cross‐linking system affect more for improving freezing resistance. Physico‐mechanical properties such as tensile strength, tear strength, hardness were also measured. The ratio of initial slope (M₀) to steady‐state slope (M₁), M₀/M₁ in tensile curves of different blends were verified, which in turn related to the physico‐mechanical properties and freezing resistance of rubber compounds. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39795.     

Plasticization of poly(lactide) with poly(ethylene glycol): Low weight plasticizer vs triblock copolymers. Effect on free volume and barrier properties

In order to make poly(lactide) (PLA) suitable for food packaging applications, its toughness must be improved. In this work, the plasticization effectiveness of a low-molecular-weight plasticizer and a triblock copolymer are analyzed. For this purpose, PLA is blended with poly(ethylene glycol) (PEG) and poly(lactide-ethylene glycol-lactide) (LA-EG-LA) triblock copolymer. The obtained results show that copolymers are more effective, reducing the glass transition temperature of PLA. Although PLA/PEG blends have been widely studied in the literature, the barrier character has not been analyzed, which is of paramount importance for packaging applications. Therefore, the permeability to carbon dioxide, oxygen, and water vapor of PLA/PEG blends has been characterized observing an increase with the incorporation of PEG, which is the expected behavior. However, the incorporation of LA-EG-LA copolymers leads to permeability values that are slightly higher, similar, or even lower than PLA. Furthermore, the free volume of the samples has been analyzed in order to gain a deeper insight on the factors affecting the transport properties. Overall, this works aims to provide a better understanding towards the design of biodegradable packaging with improved properties that could be also extended to other biodegradable polymers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48868.