科技简讯

<正> △AS-Ⅰ催化合成 DOP 通过鉴定目前,邻苯二甲酸二辛酯(DOP)由硫酸和对甲苯磺酸在常压或减压下进行酯化反应制得。为了克服酸催化剂在酯化反应中存在的诸多弊端,岳阳大学化学系研制成功了非酸固体复合物催化合成 DOP新工艺,已通过省级鉴定。该工艺采用自制固体复合物 AS-Ⅰ催化剂,DOP 产率达99.2%,产品 DOP 各项指标符合国标一级品要求,具有显著的经济效益。△F-1柠檬酸专用树脂通过技术鉴定上海无机化工研究所研制的 F-1柠檬酸专用阴离子树脂日前已通过市级技术鉴定。这种树脂专用于柠檬酸阴离子交换液中去除 SO_4~=和 Cl~-,其性能达到和部分超过了目前我国引进的具有世界先进水平的美国 A-S61和德国 MP-64阴离于交换树脂的水平,具有显著的社会效益。     

新型固体催化剂（QS-6）合成DOP的研究

QS-6是一种新型DOP固体催化剂，本文研究了反应温度、反应时间和催化剂用量对酯化反应的影响，并将QS-6与钛酸四丁酯的催化性能进行比较，结果表明，QS-6的催化活性比钛酸四丁酯更高。     

活化的氧化钆、氧化镥在合成DOP中的催化作用

DOP(邻苯二甲酸二辛酯)是一种常用的、生产量较大的增塑剂。由于其综合性能较好,还被选作工业标准增塑剂,以便对其它增塑剂进行评价。目前,DOP 仍采用苯酐与α—乙基已醇在酸催化下,经酯化反应而合成,但三废量大、有副反应、且产品质量也欠佳。然而,选用非酸性催化剂生产的 DOP,不     

固体酸催化合成邻苯二甲酸二辛酯

以硫酸和二氧化钛为原料,制备固体超强酸SO42-/TiO2,并将之用于催化合成邻苯二甲酸二辛酯(DOP),探讨了影响酯化反应的因素.确定的最佳反应条件为:醇酸的量比为3.8:1,固体酸用量为反应物总质量的3.0%,反应时间为2.5 h,反应温度130-150℃,酯化率达83.7%.     

提高增塑剂装置汽提塔分离效率的探讨

10万t/a连续化增塑剂装置汽提塔的分离效率的好坏,直接影响到塔底产品的纯度,并且会影响到塔顶采出物料的组分组成,塔顶物料中辛醇和DOP（邻苯二甲酸二（2-乙基）己酯）的含量多少会直接影响到酯化系统的反应色值等指标,同时高含量的DOP物料进入酯化系统会带来能耗的增加。通过对汽提塔K830塔的技术改造,有效地解决了此问题。     

混合镨钕氧化物作为酯化催化剂的研究

酯化反应是一类重要的有机反应,在工业生产上有着广泛的应用.这类反应,传统的方法是用酸作催化剂,但易产生副反应,三废量大,且产品质量也欠佳.如增塑剂DOP的生产就是如此.为减小污染,提高产品质量,自60年代起,研究了酯化反应的非酸催化,如采用ZnO、SnO等作酯化催化剂,其效果较好,并已用于工业生产.近年来,我们首先对镧系元素的三价氧化物和     

二聚酸二丁氧基乙酯的合成与增塑性能

以二聚酸和乙二醇丁醚为原料,在催化剂钛酸四丁酯催化作用下,采用直接酯化法工艺合成了二聚酸二丁氧基乙酯。考察了原料配比、催化剂用量、带水剂用量、反应时间等因素对酯化反应的影响。结果表明：当乙二醇丁醚和二聚酸摩尔比为2.5∶1,钛酸四丁酯用量为二聚酸质量的1.0%,带水剂环己烷用量为二聚酸质量的17.5%,反应时间5h时,酯化率可达99.6%。建立了酯化反应表观动力学模型,反应速率方程为：r=9.2×10⁵e^-49.1/RTc_A。通过FTIR和¹H NMR对产物结构进行表征,并将二聚酸二丁氧基乙酯和DOP分别加入到PVC树脂中,通过溶剂铸膜法制成PVC塑料试片,对比其性能,二聚酸二丁氧基乙酯有良好的耐油、耐水抽出及热稳定性,可作为DOP的升级产品使用。     

介孔分子筛负载杂多酸催化剂催化合成邻苯二甲酸二辛酯

采用介孔分子筛负载杂多酸为催化剂,在釜式反应器内对苯酐和正辛醇的酯化反应进行了研究,考察了催化剂的活性、选择性和稳定性,结果表明,在组成适宜的催化剂和适当的反应条件下,苯酐转化率可达98%,DOP选择性可达100%,且催化剂可重复多次使用。     

环保增塑剂柠檬酸三丁酯的合成及应用

以柠檬酸和正丁醇为原料,一水合硫酸氢钠为催化剂合成了柠檬酸三丁酯(TBC);考察了影响其酯化率的因素.通过实验确定了最佳反应条件:0.1 mol柠檬酸,醇酸物质的量之比为4.8∶1,一水合硫酸氢钠是合成柠檬酸三丁酯的优良催化剂,其用量4.5g,反应时间2.5h,反应温度110 ～ 120℃,酯化率达到88.1％,产品为微黄色透明油状液体,折光率为n25D=1.443～1.445,沸点为225℃,并用红外对产品进行鉴定.通过TBC和邻苯二甲酸二辛酯(DOP)增塑聚氯乙烯(PVC)进行对比研究.结果表明,当m(TBC)∶m (PVC)=25∶100时,TBC增塑PVC材料的拉伸强度、断裂伸长率及低温性能与DOP增塑PVC材料性能相当.     

新型低温酯化催化剂

<正>近日,北京化工大学联合安阳师范学院研制出一种新型催化剂。该催化剂可提高增塑剂DOP(邻苯二甲酸二异辛酯)、DOTP(对苯二甲酸二异辛酯)的反应效率、降低反应能耗。该催化剂有两大特点:一是酯化温度低于异辛醇沸点,可解决酯化过程中异辛醇始终处于"蒸发—冷凝—回流"状态造成的能耗高、反应效率低等问题;二是催化剂在反应前     

催化酯化合成邻苯二甲酸二辛酯的新进展

介绍了邻苯二甲酸二辛酯生产现状,催化酯化反应的新型催化剂及催化剂制备方法。     

Dynamic rheological behavior and microcrystalline structure of dioctyl phthalate plasticized poly(vinyl chloride)

The dynamic rheological behavior of poly(vinyl chloride) (PVC)/dioctyl phthalate (DOP) systems were studied as a function of DOP content and melting temperature. The dynamic rheological behavior of the PVC/DOP systems was found to be remarkably affected by the DOP content. The observed curves of storage modulus (G′) versus frequency were well fitted to an empirical equation (G′ = G′₀ + Kωⁿ, where G′₀ is the low‐frequency yield value of the storage modulus, the exponent n is a dependent index of frequency, K is a constant coefficient, and ω is the angular frequency). The loss tangent and/or phase angle increased remarkably at a higher DOP content. There was an apparent critical DOP content transition where the dynamic rheological behavior of the PVC/DOP systems changed greatly. Scanning electron microscopy observations revealed the existence of a multiscale particle structure in the PVC/DOP systems. For the PVC/DOP (100/70) system, with increasing melting temperature, its dynamic rheological behavior showed an apparent mutation at about 190°C. Differential scanning calorimetry (DSC) analysis confirmed that the high elastic networks in the PVC/DOP systems were closely related to the microcrystalline structure of PVC. The transitions in the curves of the gelation degree and crystallinity versus the DOP content corresponded well to the DOP content transition in the dynamic rheological behavior. DOP could inhibit the secondary crystallite of PVC and almost had no effect on the primary crystallite of PVC. The coexistence of the microcrystalline structure of PVC and the plasticizer (DOP) resulted in high elastic networks in the PVC/DOP systems. The DSC results explained the DOP content transition and the temperature transition in the dynamic rheological behavior of the PVC/DOP systems well. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

高分子量增塑剂PPA抑制软质PVC中DOP迁移的研究

将高分子量增塑剂聚己二酸丙二醇(酯PPA)与邻苯二甲酸二辛(酯DOP)共混以抑制软质聚氯乙(烯PVC)中DOP的迁移,探讨了PPA和DOP用量对DOP的溶剂抽出率和挥发损失率以及软质PVC制品力学性能的影响。结果表明:PPA能有效抑制软质PVC样品中DOP的溶剂抽出率和挥发损失率,PPA含量越高,抑制效果越明显;当PPA/DOP=10/30时软,质PVC样品的力学性能得到了较好的保持。     

Influences of contents and molecular weights of LDPE on DOP plasticization of PVC

Influences of contents and molecular weights of low‐density polyethylene (LDPE) on dioctyl phthalate (DOP) plasticization in the poly(vinyl chloride) (PVC) plastisol (PVC/DOP/AO = 100/30/6.5) were investigated using DMA and DSC. The plasticization effects of DOP on the PVC plastisol were found to decrease with increasing LDPE content. A negligible plasticization effect of DOP on the PVC plastisol was found when the LDPE content was equal to or higher than 75 parts per 100 parts by weight of LDPE and PVC together. Based on thermal fractionation experiments, a favorable interaction between LDPE and DOP was developed during melt blending of LDPE and the PVC plastisol. The present interaction enabled the incorporation of DOP into LDPE and decreased the plasticization effects of DOP on the PVC plastisol. A further decrease in the plasticization effects of DOP on the PVC plastisol by the presence of LDPE was found with increasing LDPE molecular weights. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2548–2555, 2002     

Mechanical and barrier properties of polyvinyl chloride plasticized with dioctyl phthalate,epoxidized soybean oil,and epoxidized cardanol

Plasticized polyvinyl chloride (PVC) films were prepared by melt compounding and compression molding using epoxidized cardanol (EC), a biobased plasticizer and its plasticization effect was compared with epoxidized soybean oil (ESBO) and dioctyl phthalate (DOP). The mechanical, migration, thermal, and barrier properties of the plasticized films were compared. The effect of replacing DOP with EC on the properties of PVC films was also investigated. The tensile strength, elongation at break, tensile modulus and impact strength values of PVC/EC films were higher in comparison to PVC/DOP and PVC/ESBO films at a fixed plasticizer loading of 40 wt.%. Also, the films prepared with a mixture of DOP + EC showed higher tensile strength and elongation at break compared to that of films prepared with only DOP. The PVC/EC films showed good thermal stability and reduced oxygen transmission rate (OTR) compared to PVC/DOP films. The addition of graphene and nanoclay in the PVC/plasticizer system exhibited an increase in oxygen transmission. However, the oxygen barrier property of nano filler incorporated PVC/EC films was better than PVC/DOP films. All the films showed negligible water vapor transmission rate (WVTR).     

The effect of low levels of plasticizer on the rheological and mechanical properties of polyvinyl chloride/newsprint-fiber composites

Plasticizers play a key role in the formulation of semirigid and flexible PVC and in determining their physical properties and processability. This study examines the effects of the low phr levels of plasticizer (DOP) on the rheological and mechanical properties of rigid and semi-rigid PVC/newsprint-fiber composites. Mechanical and rheological properties of unfilled PVC compounds and PVC/newsprint-fiber composites at 45 phr were compared over the range of 0 to 15 phr of DOP plasticizer. Analyses of data using SAS procedures of ANOVA were also conducted to discern the effects of concentration of plasticizer on these properties. The following conclusions were reached: (1) DOP was relatively ineffective in improving melt flow index of the composites compared to unfilled PVC. (2) The composites were significantly inferior in tensile strength at yield and stiffer than unfilled PVC. The differences observed were roughly the same over the DOP range studied. (3) Elongation at break and toughness (break energy) were lower for the composites and were essentially independent of DOP level, whereas there was a significant improvement for unfilled PVC over the DOP range studied. (4) Impact strengths of the composites and unfilled PVC were essentially comparable up to about 11.25 phr of DOP. However, at 15 phr DOP, impact strength of the composite was far inferior to that of unfilled PVC. (5) The well-known antiplasticization effect was noted for unfilled PVC, as well as to some extent for the filled PVC.     

Effects of poly(1,2‐propylene glycol adipate) and nano‐CaCO3 on DOP migration and mechanical properties of flexible PVC

Nano‐CaCO₃ was used as nano‐scale filler and poly(1,2‐propylene glycol adipate) (PPA) was used as polymeric plasticizer in flexible poly(vinyl chloride) (PVC) sheets for the partial replacement of di(2‐ethyl hexyl) phthalate (DOP) in this paper. The effect of PPA and nano‐CaCO₃ on restraining DOP migration was evaluated via extraction tests. The results showed that the introduction of nano‐CaCO₃ can decrease the extraction rate of DOP in the PVC matrix. The tensile strength and elongation at break of CaCO₃‐1/PPA‐20/DOP‐30/PVC were similar to those of DOP‐50/PVC, and CaCO₃‐1/PPA‐20/DOP‐30/PVC exhibited the superior suppression of DOP migration compared with DOP‐50/PVC. Thermogravimetry analysis (TGA) indicated that the addition of nano‐CaCO₃ effectively improved the thermal stability of the nanocomposites. Therefore, the combination of PPA and nano‐CaCO₃ is an effective approach to suppress the migration of DOP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

聚1,2-丙二醇新戊二醇己二酸酯增塑性能的研究

将合成的聚1,2-丙二醇新戊二醇己二酸酯(简称PG-AA-NPG)聚酯增塑剂增塑PVC的试片制成复合材料,并进行耐迁移、DSC、力学性能、热稳定性能测试,分析PG-AA-NPG的综合性能,并且与加入DOP和市售聚酯增塑剂A的PVC试片进行对比.结果表明PG-AA-NPG的耐溶剂迁移性优于DOP;PVC/PG-AA-NP...     

非酸催化生产DOP酯化过程设计的热量计算

介绍在非酸催化生产邻苯二甲酸二辛酯(DOP)酯化过程设计的热量计算中 ,只利用酯化初态与终态的有关条件来进行全酯化过程的热量计算方法。该法避免传统计算方法中对许多中间状态产物的估算 ,提高了设计计算准确性 ,并为简化同类型工程设计提供一种有效的计算方法。     

The plasticizing effect on the thermal transitions of the toluenediisocyanate‐based polyurethanes monitored by thermally stimulated current technique

A liquefied curative in methylene‐bis‐orthochloroaniline/dioctyl or di‐2‐ethylhexyl phthalate (MOCA/DOP) was used as the substitute curative for the hot‐melt MOCA curative in a two‐component preparative system for the toluene diisocyanate (TDI)‐based polyurethane elastomers. The polyurethane elastomer specimens based on this liquefied curative were prepared with three different soft segments with the addition of various plasticizers. The DOP‐added specimens were evaluated by the depolarization technique in the thermally stimulated current/relaxation mapping analysis (TSC/RMA). The results were also compared with differential scanning calorimeter and dynamic mechanical analyzer on the observation on the changes in thermal transitions. Results indicated that at a low DOP content of less than 26 wt %, little disruption on the urethanic matrix was found in the TDI‐polycaprolactone (PCL)/MOCA‐DOP system. However, at a high DOP content of 47 wt %, a disruption in TDI‐poly(tetramethylene) oxide (PTMO) amorphous phase by DOP was observed. The optimum weight ratio of MOCA/DOP was found to be 1 : 2 and this liquefied solution was stable at the ambient temperature, and can be applicable for use as a curative for the preparation of the TDI‐based polyurethane elastomers at ambient temperature. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 743–761, 2000