基于异山梨醇的新型生物基增塑剂的制备及其对PVC的改性

以异山梨醇为基体,合成了不同分子结构的生物基增塑剂二丁酸异山梨酯与二丁烯酸异山梨酯,并用于聚氯乙烯(PVC)改性。对所制生物基增塑剂进行分子结构表征,考察了其对PVC力学性能和加工流动性的影响。结果表明:两种生物基增塑剂均能提高PVC的冲击强度,且二丁酸异山梨酯增塑效果优于二丁烯酸异山梨酯。每100 g PVC中增塑剂添加量均为10 g时,二丁酸异山梨酯增韧PVC的冲击强度为2.91 kJ/m~2,较参比试样(增塑剂为邻苯二甲酸二丁酯)提高了38%。     

异山梨醇基增塑剂的制备及其增塑PVC的性能

通过异山梨醇和壬酸合成一种新型生物基增塑剂—异山梨醇二正壬酸酯(SDN)来改性聚氯乙烯(PVC)树脂。研究了绿色增塑剂的增塑作用及对共混物性能的影响。SDN特有的分子结构增大了分子链间的距离,增加了聚合物的自由体积,使共混物塑性得到明显的改善。研究表明,随着SDN增塑剂添加量的增加,材料韧性增强,增塑剂的引入降低了共混物的玻璃化转变温度,改善了材料的韧性。当增塑剂的添加量为25份时,材料缺口冲击强度达到了1217 J/m,与未添加增塑剂相比,提高近40倍。扫描电子显微镜结果表明,增塑剂SDN与PVC树脂相容性良好,同时可以发现增塑剂使共混物的断裂方式由脆性断裂转变为韧性断裂。     

宁波材料所在生物基PET合成方面取得新进展

正中科院宁波材料所朱锦研究员带领的生物基高分子材料团队通过以生物基芳香单体2,5-呋喃二甲酸与乙二醇共聚,采用熔融缩聚法,制备了一系列分子结构中呋喃环含量不同的生物基芳香聚酯——聚呋喃二甲酸乙二醇酯(PEF)(又称生物基PET),其特性黏数控制在0.75~0.98 d L/g之间。TGA和DSC研究表明,生物基芳香聚酯的Tg明显提高,PEF的Tg比PET提高了18℃,熔融温度降低了40℃,强度和模量提高了40%。材料气体阻隔性测试表明,PEF的CO2阻隔性比PET提高了14.8倍,O2阻隔性比PET提高了6.8倍。由于生物基芳香聚酯     

环保型增塑剂HEXAMOLL DINCH对丁腈橡胶性能的影响

研究新型环保型酯类增塑剂环己烷1,2-二甲酸二异壬基酯(DINCH)对丁腈橡胶(NBR)性能的影响。结果表明:在增塑剂用量相同(18份)的情况下,添加增塑剂DINCH的NBR胶料的拉伸强度和拉断伸长率高于添加邻苯二甲酸二丁酯、邻苯二甲酸二辛酯、癸二酸二丁酯和癸二酸二辛酯的胶料,压缩永久变形较小;定伸应力与添加脂肪族二酸酯类的胶料相当;耐溶剂抽出性能良好,耐寒性稍优于添加邻苯二酸酯类增塑剂的胶料。     

低色度2,5-呋喃二甲酸异辛酯的合成

采用酰氯法来制备低色度2,5-呋喃二甲酸异辛酯,首先是酰氯的制备,考察了酰化试剂、温度及时间对2,5-呋喃二甲酰氯产率的影响;然后制备2,5-呋喃二甲酸异辛酯,考察了催化剂对直接酯化法制备的2,5-呋喃二甲酸异辛酯色度的影响,温度、时间对酰氯法制备的2,5-呋喃二甲酸异辛酯产率的影响,并对两种方法制备的酯的色度进行了比较。结果表明,在90℃,1.5 h条件下,以固体光气为酰化试剂时,2,5-呋喃二甲酰氯产率最高为91.9%;采用直接酯化法制备的2,5-呋喃二甲酸异辛酯色度均大于500 APAH,而酰氯法制备的2,5-呋喃二甲酸异辛酯的色度为30~40 APAH,且在90℃,1 h条件下,产率最高为98.1%。与直接酯化法相比,酰氯法具有反应温度低、醇用量少、产品色度低等优点,具有良好的工业应用前景。     

生物基2,5-呋喃二甲酸聚酯的研究进展

2,5-呋喃二甲酸聚酯是以生物质平台化合物2,5-呋喃二甲酸为主要单体的生物基聚酯。该文主要介绍2,5-呋喃二甲酸聚酯的研究进展,对2,5-呋喃二甲酸聚酯的性能、合成方法、合成用催化剂及其共聚改性研究进行对比分析和讨论。2,5-呋喃二甲酸聚酯的玻璃化转变温度、热稳定性、杨氏模量和抗拉强度与对苯二甲酸聚酯的相应性能接近。同时,2,5-呋喃二甲酸聚酯及其共聚物对CO_2、O_2和H_2O的阻隔性能优于对苯二甲酸聚酯,在许多领域是聚酯PET等材料的潜在替代物,受到了业界的广泛重视。然而,较低的断裂伸长率是2,5-呋喃二甲酸聚酯应用的瓶颈问题。共聚改性是改善2,5-呋喃二甲酸聚酯力学性能的有效方法之一,已有的共聚改性单体在改善2,5-呋喃二甲酸聚酯的断裂伸长率时使共聚物的杨氏模量和玻璃化转变温度大幅下降,合成具有较高断裂伸长率、较高杨氏模量和较高玻璃化转变温度的2,5-呋喃二甲酸聚合物是国内外学者亟待解决的难题,也是2,5-呋喃二甲酸聚酯共聚改性领域的重要研究方向。     

增塑剂

PVC用芳香酸醋增塑剂的制备,增塑剂双（3，5，5-三甲基已基）苯二甲酸酯的制备.     

环境友好型增塑剂对软质PVC光稳定性能的影响

主要研究了六种增塑剂在软质聚氯乙烯(PVC)中的应用效果,及含增塑剂的软质PVC在紫外光老化前后的性能变化。含环己烷二酸酯类增塑剂(Hexamoll dinch)的增塑PVC在添加紫外线吸收剂UV326后表现出优异的耐紫外光能力,老化1000 h后色差值最小,仅为2.29。含聚酯类高分子增塑剂的PVC样品具有最高的拉伸强度(18.3 MPa)和撕裂强度(64.1 k N/m)。含癸二酸二辛酯(DOS)的增塑PVC样品的拉伸强度(12.7 MPa)和撕裂强度(46.3 k N/m)最低,但断裂伸长率最高(393%)。含邻苯二甲酸二(2-丙基庚)酯(DPHP)、邻苯二甲酸二辛酯(DOP)和邻苯二甲酸二异壬酯(DINP)的三种增塑PVC样品的力学性能差别不大。在添加UV326后,环保型增塑剂DPHP增塑的PVC样品的耐紫外光性能增强。     

开发前景看好的几种塑料增塑剂新产品

（1）高分子类增塑剂。除国内已有的聚酯类增塑剂外,还有聚己二酸二丁酯、聚辛二酸二丁酯等经改性后的高分子增塑剂。乙烯-S02共聚物、乙烯-CO共聚物、EVA-CO共聚物等都是PVC的优良高分子增塑剂;和PVC相容的一些高分子化合物,它们的分子结构中不含酯基、羰基,     

HBr-MgBr2催化己糖二酸脱水环合制备2，5-呋喃二甲酸的研究

2,5-呋喃二甲酸（2,5-FDCA）是生物可降解塑料聚呋喃二甲酸乙二醇酯的聚合单体,未来需求量巨大。针对己糖二酸脱水环合制备2,5-呋喃二甲酸存在的收率低问题,开展了更高选择性催化体系的构建研究,成功筛选到了两个优良的催化体系：HBr-MgBr₂、HBr-LiBr。3%（质量）HBr-6%（质量）MgBr₂催化、120℃下反应2 h,D-葡萄糖二酸单钾盐脱水环合制备2,5-FDCA收率达到84.2%。当反应底物浓度低于5%（质量）以及水含量从3.3%富集到16.5%时,2,5-FDCA的摩尔收率未见明显下降,且都可维持在80%以上。测定了100~130℃温度范围内3%（质量）HBr-6%（质量）MgBr₂催化D-葡萄糖二酸单钾盐脱水环合制备2,5-FDCA动力学数据,采用一级反应动力学拟合得到2,5-FDCA的生成反应活化能为108.9 kJ/mol、副产物生成活化能为136.6 kJ/mol。研究工作对己糖二酸脱水环合制备2,5-FDCA路线的工业化具有积极推动作用。     

Evaluating effects of biobased 2,5‐furandicarboxylate esters as plasticizers on the thermal and mechanical properties of poly (vinyl chloride)

We synthesized 2,5‐furandicarboxylate esters [i.e., dibutylfuran‐2,5‐dicarboxylate, diisoamylfuran‐2,5‐dicarboxylate, and di(2‐ethylhexyl)furan‐2,5‐dicarboxylate] and investigated their potential application as plasticizers of commercial poly(vinyl chloride) (PVC) products. Fourier transform infrared analysis, mechanical tests, scanning electron microscopy investigation, differential scanning calorimetry analysis, dynamic mechanical thermal analysis, thermogravimetric analysis (TGA), melt flow rate (MFR) measurement, and plasticizer migration measurements were used to the evaluate the comprehensive properties of the blended products. The results of the tensile tests demonstrate that the blends exhibited antiplasticization and flexible plastic characteristics at 10 and 50 phr in PVC, respectively. Moreover, flexural and impact test data indicate that the three types of blends exhibited a similar tendency: the hardness decreased continuously as the amount of plasticizer increased. Their morphology indicated that all of the plasticizers had good compatibility with PVC. The resulting glass‐transition temperature of the investigated plasticizers was lower than that of pure PVC, and reduction was largest for the plasticizer with the highest molecular weight. TGA revealed that the thermal degradation of blended polymers occurred in three stages and that all of the blends were stable up to 180°C. Finally, the MFRs of all of the specimens indicated that the addition of a higher concentration of lower molecular weight biobased esters resulted in improved fluidity, but these compounds migrated more easily from the blends. Hence, 2,5‐furandicarboxylic acid derived from biomass has potential as a plasticizer. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40938.     

P(MMA-MA)/OMMT纳米复合材料对PVC共混改性研究

通讨原位插层法制备聚(甲苯丙烯酸甲酯一丙烯酸甲酯)有机化蒙脱十「P(MMA-MA)/OMMT}纳米复合材料,并用其对聚氯乙烯(PVC)讲行共混改性。通讨扫描电镜(SEM)热失重分析(TGA)、动杰力学分析(DMA)拉伸和冲击等力学性能测试研究了共混物的两相相容性、热稳定性及力学性能。结果表明:共混体系两相间有很奸的相容性;随着纳米复合材料添加量的增加,共混体系的耐热性能、储能模量、玻璃化温度和力学性能逐渐增加。当纳米复合材料与PVC共混比达到20/100时,共混体系在10%失重率下的失重温度比纯PVC捍高了17.4℃,玻璃化温度比纯PVC捍高了4.7℃。当纳米复合材料与PVC共混比达到30/100时,体系的综合力学性能最奸,冲击强度和拉伸强度分别较纯PVC捍高了21. 1%和34.7%。     

填充剂、增塑剂对PVC轻型输送带覆盖胶性能的影响

研究了不同填充剂、增塑剂对PVC轻型输送带覆盖胶性能的影响。结果表明：白炭黑对PVC轻型输送带覆盖胶的力学性能、耐磨性能和硬度的影响最大;填充剂用量增加时,拉伸强度逐渐减小,冲击强度、硬度逐渐增大。与DOP,DCP和DOA相比,TXP的增塑效果最好;添加5份增塑剂时有反增塑现象发生．拉仲强度提高。在无毒输送带中应使用环保型环氧大豆油作为增塑剂。     

Dialkyl furan‐2,5‐dicarboxylates,epoxidized fatty acid esters and their mixtures as bio‐based plasticizers for poly(VInylchloride)

Dialkyl furan‐2,5‐dicarboxylates and epoxidized fatty acid esters (EFAE) of varying molecular weights and volatilities, as well as their mixtures, were investigated as alternative plasticizers for poly(vinylchloride) (PVC). The EFAE utilized were epoxidized soybean oil (ESO) and epoxidized fatty acid methyl ester (e‐FAME). All plasticizers were compatible with PVC, with plasticization efficiencies usually increasing with decreasing molecular weights of the plasticizers (except in the case of ESO, which was remarkably effective at plasticizing PVC, in spite of its relatively high molecular weight). In comparison with phthalate and trimellitate plasticizers, the alternatives generally yielded improved balance of flexibility and retention of mechanical properties after heat aging, with particularly outstanding results obtained using 30?50 wt % e‐FAME in mixtures with diisotridecyl 2,5‐furandicarboxylate. Although heat aging characteristics of the plasticized polymer were often related to plasticizer volatilities, e‐FAME performed better than bis(2‐ethylhexyl) 2,5‐furandicarboxylate, and bis(2‐ethylhexyl) phthalate of comparatively higher molecular weights. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42382.     

Application of new oligomeric plasticizers based on waste poly(ethylene terephthalate) for poly(vinyl chloride) compositions

In this study, chemical recycling products of waste poly(ethylene terephthalate) with oligoesters were used as new plasticizers for poly(vinyl chloride) (PVC). The preparation conditions of the dry blend mixtures of the suspension PVC containing synthesised plasticizers were similar to the conditions of the preparing mixtures with commercial plasticizers. The plasticization efficiency of PVC plasticizers was then examined by analysis of the mechanical, physical and chemical properties, as well as the thermal resistance and migration of plasticizer molecules from polymer matrix. Test results proved that compositions with synthesised oligomeric plasticizers possessed similar or better properties than those containing commercial oligomeric plasticizers and much better properties than those having monomeric plasticizers. Thermal stabilities of the proposed plasticizers were higher than those of the commercial plasticizers either monomeric (bis(2-ethylhexyl)phthalate) or oligomeric, despite the fact that the synthesised oligoesters did not contain any antioxidant. The best properties, especially low volatility, very good mechanical properties, low migration were resulted of the transesterification of the waste PET with oligoesters based on adipic acid, triethylene glycol and 2-ethylhexanol which were selected as plasticizers synthesised on the technical scale. The tested plasticized PVC compositions possessed very good tear resistance, tensile strength, decrease of weight loss after 168 h at 80 °C and low migration. Processing properties of PVC compositions containing these synthesised plasticizers confirmed their effectiveness in these compositions for extrusion process.     

Synthesis and evaluation of dioctyl 2,5-thiophenedicarboxylate as a potentially bio-based plasticizer for poly(vinyl chloride)

In this work, dioctyl 2,5-thiophenedicarboxylate (DOT), a potentially bio-based plasticizer, was synthesized and evaluated as an alternative to traditional petroleum-based plasticizers. The chemical structure of DOT was confirmed by FTIR and ¹H NMR. Besides, its plasticization effect on poly(vinyl chloride) (PVC) was investigated in detail, and dioctyl 2,5-furandicarboxylate (DOF) as well as dioctyl isophthalate (DOIP) with similar chemical structures were used as references. The DMA results showed that the glass transition temperature (T_g) of PVC/DOT, PVC/DOF, and PVC/DOIP was 45.1°C, 33.6°C, and 51.3°C, respectively, indicating that the plasticizing efficiency of DOT was better than that of DOIP but lower than that of DOF. However, the tensile test results exhibited that the elongation at the break of PVC/DOT was higher than that of PVC/DOF, which was attributed to the easy phase separation between DOF and PVC. In addition, DOT displayed the best volatility resistance and exudation resistance among the three plasticizers, attributed to its highest molecular weight. Moreover, the migration loss of DOT in non-polar solvents was much smaller than that of DOIP because of its stronger molecular polarity. In conclusion, DOT has good potential to replace traditional petroleum-based plasticizers and be used as a primary plasticizer for PVC.     

Effect of biobased plasticizers on thermal,mechanical, and permanence properties of poly(vinyl chloride)

Phthalates can be replaced by other harmless and environmentally friendly plasticizers, such as isosorbide diesters (ISB), and epoxidized sunflower oil (ESO), which has been proved an efficient stabilizer for poly (vinyl chloride) (PVC) in helping to prevent degradation during processing. Formulations based on PVC with different amounts of ISB, ESO, and di‐(2‐ethylhexyl) phthalate (DEHP) from 0 to 60 parts by weight per hundred parts of resin were realized. To make PVC flexible with partial amounts of the debated phthalates as plasticizers, we use a combination of DEHP, ISB, and ESO. Effects of these two biobased plasticizers, ISB and ESO, and their mixture with DEHP on thermal stability by measuring discoloration degrees and thermal gravimetric analysis, on mechanical properties such tensile strength, elongation at break, and hardness, were characterized. Plasticizer permanence properties of PVC compounds were studied. Studies showed that processibility and flexibility were improved by the addition of a plasticizer system (ISB, ESO, and DEHP). An increase in the content of ISB and/or ESO increased thermal and mechanical properties, whereas compositions with ternary compositions of ISB/ESO/DEHP (15/15/30) exhibited the best performance properties. J. VINYL ADDIT. TECHNOL., 20:260–267, 2014. © 2014 Society of Plastics Engineers     

PVC增塑剂偏苯三酸基聚酯的研究

采用“二步法”将偏苯三酸酐（TMA）和甘油（Gl）经酯化、缩聚反应得到环保、可生物降解的偏苯三酸聚酯（P-Gl-TMAI）。将合成的P-GI-TMAI与邻苯二甲酸（2-乙基己基）酯（DOP）分别添加到聚氯乙烯（PVC）树脂中进行塑炼实验,研究2种增塑剂与PVC树脂的相容性能、塑炼试片的力学性能以及耐迁移性能。结果表明,与DOP相比,P-Gl-TMAI与PVC的相容性较好;且前者塑炼试片的拉伸强度达18.99 MPa,断裂伸长率为454.89 %;在挥发性和抽出性试验中,P-Gl-TMAI制备的试片分别仅有3.02 %和15.31 %的质量损失率,其韧性与耐迁移性均高于DOP。     

掺级配良好再生PVC骨料混凝土的力学和吸能性能

将级配良好的再生聚氯乙烯(PVC)颗粒以不同掺量等体积替代天然细骨料后加入混凝土中制成试件,进行力学性能试验和冲击试验,得到立方体压缩强度、劈裂抗拉强度、卸载弹性模量、能量吸收率和微观结构图,用来探究不同掺量的再生PVC骨料混凝土的力学和吸能性能。结果表明,当PVC骨料掺量为0%,5%,10%,15%,20%,30%时,其混凝土压缩强度分别为49.34,52.44,45.79,46.41,45.6,43.46 MPa,劈裂抗拉强度为2.73,3.58,3.2,2.92,2.69,2.44 MPa,混凝土的压缩强度和抗拉强度均随掺量增加呈先增加后缓慢降低趋势,并且用级配良好的再生PVC颗粒替代天然细骨料加入混凝土的力学性能比单一粒径塑料颗粒优良;随PVC骨料掺量增加,混凝土脆性得到改善且延性增强;混凝土的能量吸收能力随再生PVC细骨料掺量增加呈直线增加趋势。     

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...