环氧油酸新戊二醇酯的制备及应用性能研究

以油酸和新戊二醇为原料,通过酯化反应和环氧化反应制备了新型环保增塑剂环氧油酸新戊二醇酯（ENDO）,采用红外光谱仪（FTIR）和核磁共振仪对ENDO的结构进行了表征,并通过转矩流变仪、超低温脆化试验仪、老化试验机和万能试验机测试对比了ENDO、邻苯二甲酸二辛酯（DOP）、已二酸二辛酯（DOA）或偏苯三酸三辛酯（TOTM）增塑的聚氯乙烯（PVC）样品的流变性能、低温脆化性能、耐溶剂抽出性能和耐老化性能。结果表明,本实验成功制备了预期增塑剂产品ENDO;增塑PVC混合物料扭矩由大到小对应的增塑剂为TOTM、ENDO、DOP、DOA,能耗由大到小对应的增塑剂为TOTM、ENDO、DOA、DOP;ENDO增塑PVC样品的低温脆化性能可通过-30 ℃测试;当溶剂为正己烷时,DOP、ENDO、DOA和TOTM增塑PVC样品的断裂伸长率残留率依次为88.24 %、87.99 %、1.69 %和0.71 %,当溶剂为无水乙醇时,为79.00 %、96.22 %、72.76 %和74.52 %;ENDO增塑PVC样品老化后的断裂伸长率残留率、拉伸强度变化率及热老化质量损失均小于TOTM增塑的PVC样品。     

环境友好型增塑剂增塑聚氯乙烯体系的性能表征

以传统增塑剂邻苯二甲酸二辛酯(DOP)为比较对象,研究了对苯二酸二辛酯(DOTP)、乙酰柠檬酸三丁酯(ATBC)、己二酸二辛酯(DOA)、癸二酸二辛酯(DOS)4种环境友好型增塑剂对聚氯乙烯(PVC)体系的力学性能和耐油、耐溶剂性能的影响,并采用傅里叶变换红外光谱法和差示扫描量热法对试样分子结构进行了表征。结果表明:①ATBC/PVC体系的Tg最高(-22.1℃);DOS/PVC体系的Tg最低(-65.4℃),耐寒性最佳;②ATBC、DOA、DOS增塑PVC的力学性能整体上优于DOP增塑的PVC;③在异辛烷、正己烷和ASTM 1#标准油3种萃取剂中,5种增塑剂在正己烷中的最终抽出率最大;在同一萃取剂中,ATBC的最终抽出率最小;④针对不同使用领域,DOPT、ATBC、DOA、DOS可替代DOP增塑PVC。     

生物基增塑剂HM-828性能及其对PVC性能的影响

研究了新型环保生物基增塑剂二乙酰环氧植物油酸甘油酯(HM-828)的结构及主要性能;选用环氧大豆油(ESO)、邻苯二甲酸二辛酯(DOP)、邻苯二甲酸二异壬酯(DINP)、已二酸二辛酯(DOA)、偏苯三酸三辛酯(TOTM)及HM-828为增塑剂分别制备了增塑聚氯乙烯(PVC),对添加40份增塑剂的PVC制品的动态热稳定性、热老化质量损失、拉伸性能、硬度等进行表征。结果表明:六种增塑PVC混合物料中,DOA扭矩最小,加工能耗最低;HM-828的增塑性能与DOP和DINP相近;DOP/DINP/DOA/TOTM四种物料的耐热性不及HM-828和ESO;六种增塑PVC制品的热老化质量损失为DOADOPDINPHM-828TOTMESO;其拉伸强度均大于20 MPa,断裂伸长率均大于270%;以DOP/DINP/DOA增塑PVC制品的邵氏硬度比另外三种高出7度左右。     

低挥发环保增塑剂对苯二甲酸二（2⁃丙基庚）酯的应用研究

以对苯二甲酸和2?丙基庚醇为原料,在钛酸异丙酯为催化剂的条件下制备对苯二甲酸二（2?丙基庚）酯（DPHTP）,并将DPHTP作为增塑剂用于制备聚氯乙烯（PVC）柔性薄膜,与市售DOP和DOTP进行应用性能的比较。通过傅里叶变换红外光谱和核磁共振氢谱对产物进行结构分析;通过热失重分析、拉伸测试、耐迁移测试和耐挥发性测试等比较DPHTP、DOP以及DOTP增塑的PVC薄膜在力学性能等方面的差异。结果表明,相比DOP和DOTP,DPHTP具有更低的挥发性,其增塑的薄膜有着更优异的热稳定性以及更高的体积电阻率;其中,DPHTP的加热减量为0.031 90 %,DPHTP增塑的薄膜的热失重5 %的温度为272 ℃,体积电阻率为6.5×10⁹ Ω·m;DPHTP具有更低的挥发性且可以赋予PVC材料优异的电绝缘性能,在包装材料和电线电缆行业具有广阔的开发前景。     

生物基增塑剂异山梨醇二庚酯在PVC中的应用

以异山梨醇和正庚酸为原料合成了一种生物基增塑剂异山梨醇二庚酯(SDH),并与石油基增塑剂邻苯二甲酸二辛酯(DOP)和对苯二甲酸二辛酯(DOTP)对比考察了对聚氯乙烯(PVC)的增塑性能。通过红外分析表征增塑剂与PVC分子间相互作用;通过拉伸试验与动态力学测试表征PVC试样的力学性能;通过热重分析与迁移性实验表征增塑剂的稳定性。结果表明,SDH与PVC分子间的相互作用更强;PVC/40SDH试样较同比例的DOP和DOTP增塑PVC表现出更高柔韧性,其中PVC/40SDH的断裂伸长率较PVC/40DOP和PVC/40DOTP分别提高26.29%和33.89%,玻璃化转变温度则分别降低1.67℃和4.15℃;SDH的热稳定性、挥发性和耐抽提性介于DOP和DOTP之间。SDH的综合增塑性能较优,可以替代DOP和DOTP用于PVC的增塑。     

环境友好增塑剂在PVC中的应用

选用5种国际公认的非邻苯类环保增塑剂环己烷-1,2-二羧酸二异壬酯(DINCH)、环己烷-1,2-二羧酸二异辛酯(DEHCH)、乙酰柠檬酸三丁酯(ATBC)、偏苯三酸三辛酯(TOTM)和聚己二酸丙二醇酯(PPA)增塑PVC,与目前广泛使用的邻苯二甲酸二异辛酯(DEHP)增塑的PVC在力学性能、光学性能、热稳定性、耐溶剂抽出性等方面进行对比。结果表明:TOTM增塑PVC的力学性能最佳,拉伸强度可达24. 33 MPa,断裂伸长率可达340. 29%; TOTM和PPA增塑PVC的热稳定性优于其他增塑剂增塑样品,外延起始温度分别达到了281. 80和282. 88℃; PPA耐溶剂抽出性能最佳,50份PPA增塑PVC的样品分别在去离子水、乙醇和石油醚中浸泡96 h后质量损失基本为0。     

HPVC/NBR共混物力学性能的分子模拟的研究

采用分子模拟与实验现象相结合的方法,对高聚合度聚氯乙烯(HPVC)与增塑剂,HPVC/丁腈橡胶(NBR)共混物的力学性能进行了模拟研究。结果发现:偏苯三酸三辛酯(TOTM)增塑的HPVC具有较高的拉伸强度和硬度,邻苯二甲酸二辛酯(DOP)比对苯二甲酸二辛酯(DOTP)增塑的HPVC具有较高的拉伸强度,而DOTP增塑的HPVC具有高的断裂伸长率和较小的永久变形;在HPVC/NBR共混体系中,NBR用量增加,邵氏硬度、拉伸强度以及压缩永久变形将降低,断裂伸长率先增加后降低。共混物交联后,材料的拉伸强度增加,其断裂伸长率和压缩永久变形将降低,硬度略有增加。     

光催化合成氯代甲氧基脂肪酸甲酯增塑剂的性能研究

以油酸甲酯、甲醇及氯气为原料,利用光催化合成了氯代甲氧基脂肪酸甲酯增塑剂,并对其替代DOP应用于PVC进行了性能研究。考察了增塑剂的含氯量以及与DOP复配对增塑PVC材料的力学性能的影响;测定了增塑剂的电绝缘性、增塑PVC材料的热稳定性。研究表明:氯代甲氧基脂肪酸甲酯增塑剂与DOP复配应用于PVC中具有优良的增塑性能,且能够赋予PVC制品更优异的电绝缘性及热稳定性。     

环保型增塑剂ATBC在NBR中的应用研究

研究了乙酰柠檬酸正三丁酯(ATBC)对丁腈橡胶混炼胶硫化特性和硫化胶力学性能的影响,并与增塑剂邻苯二甲酸二辛酯(DOP)的增塑性能进行了对比。结果表明,添加增塑剂ATBC能够降低混炼胶的粘度和硫化胶力学性能。与增塑剂DOP相比,添加增塑剂ATBC的硫化胶增塑效果、耐低温性能以及力学性能均较高。在实验条件下,添加增塑剂DOP的胶料热稳定性要好于增塑剂ATBC。     

聚氯乙烯热塑性弹性体的阻尼性能研究

研究了增塑剂、无机填料以及酚醛树脂对聚氯乙烯(PVC)热塑性弹性体(TPE)力学性能及动态力学性能的影响。结果表明:聚酯增塑PVC弹性体材料体系的tanδ峰值明显高于DOP、DOTP、TOTM三种增塑剂,且阻尼性能最优;随着聚酯用量的增加,PVC弹性体的tanδ峰值逐渐提高,tanδ峰逐渐向低温方向移动。PVC热塑性弹性体中加入适量无机填料可以提高其tanδ峰值;可以用酚醛树脂调整PVC弹性体阻尼材料tanδ峰所对应的温域,从而改善其阻尼性能。     

Plasticizers derived from cardanol: synthesis and plasticization properties for polyvinyl chloride(PVC)

Two natural plasticizers derived from cardanol (CD), cardanol acetate (CA) and epoxidized cardanol acetate (ECA), were synthesized and characterized by ¹H NMR and ¹³C NMR. The plasticizing effects of the obtained plasticizers on semi-rigid polyvinylchloride (PVC) formulations were also investigated. Two commercial phthalate ester plasticizers, dioctyl terephthalate (DOTP) and diisononyl phthalate (DINP), were used as controls. Mechanical and thermal properties, compatibility, thermal stability, microstructure, and workability were assessed by dynamic mechanical analysis (DMA), mechanical analysis, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and dynamic stability analysis, respectively. Results indicated that the natural plasticizer ECA had overallsuperior flexibility, compatibility, thermal stability, and workability comparable to both controls. The obtained CA and ECA have lower volatility resistance and similar extraction and exudation resistance than that of DOTP and DINP. The CA was further blended with DOTP in soft PVC films. Results of DMA, TGA and mechanicalanalysis indicated that CA can serve as a secondary plasticizer to improve the related properties of soft PVC formulations. These CD derived plasticizers show promise as an alternative to fully or partially replace petroleum-based plasticizers.     

Synthesis and application of a natural plasticizer based on cardanol for poly(vinyl chloride)

A natural plasticizer with multifunctional groups, similar in structure to phthalates, cardanol derivatives glycidyl ether (CGE) was synthesized from cardanol by a two‐step modification process and characterized by FT‐IR, ¹HNMR, and ¹³CNMR. The resulting product was incorporated to PVC (CGE/PVC), and plasticizing effect was compared with PVC incorporated with two kinds of commercial phthalate ester plasticizers bis (2‐ethylhexyl) benzene‐1,4‐dicarboxylate (DOTP) and diisononyl phthalate (DINP). Dynamic mechanical analysis and mechanical properties testing of the plasticized PVC samples were performed in order to evaluate their flexibility, compatibility, and plasticizing efficiency. SEM was employed to produce fractured surface morphology. Thermogravimetric analysis and discoloration tests were used to characterize the thermal stabilities. Dynamic stability analysis was used to test the processability of formulations. Compared with DOTP and DINP plasticized samples, CGE/PVC has a maximum decrease of 9.27% in glass transition temperature (T_g), a maximum increase of 17.6% in the elongation at break, and a maximum increase of 31.59°C and 25.31 min in 50% weight loss (T50) and dynamic stability time, respectively. The obtained CGE also has slightly lower volatility resistance and higher exudation resistance than that of DOTP and DINP. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42465.     

橡胶籽油基复合型环保增塑剂用于PVC的研究

将自制的橡胶籽油基环氧脂肪酸甲酯（EFAME）与对苯二甲酸二辛酯（DOTP）混合后,与聚氯乙烯（PVC）共混成型,考查EFAME在软质PVC中的增塑性能及其对DOTP的替代效果。利用拉力试验机、差示扫描量热仪、动态热力学分析仪及热老化烘箱对塑化体系的力学性能、加工性能、耐热性及耐久性进行分析。结果表明,复合型增塑剂可有效改善PVC制品的柔韧性、耐磨性、热性能及加工流变性;EFAME用量为20份时,PVC制品的玻璃化转变温度由0.32 ℃降低至-4.63 ℃,质量损失10 % 和50 %时的温度得到提高,热老化整体变色时间提高了4倍。     

环氧腰果酚基磷酸二苯酯增塑剂的合成及塑化PVC

以腰果酚为原料合成了环氧腰果酚基磷酸二苯酯(ECPhP),采用核磁共振氢谱和核磁共振碳谱对产物结构进行了表征,并将ECPhP与聚氯乙烯(PVC)进行共混,对共混试样的力学性能、热稳定性、相容性和加工流变性进行了分析,并对增塑剂迁移性、抽出性和挥发性损失进行了考察,研究ECPhP作为主增塑剂及辅助增塑剂的增塑效果,并与石油基增塑剂——对苯二甲酸二辛酯(DOTP)进行比较。结果表明,所合成的ECPhP增塑剂具有较好的增塑效果及热稳定性,与单独使用DOTP相比,增塑剂中ECPhP的含量由0增加到20%(占增塑剂总质量百分比)时,共混体系的玻璃化转变温度由47.16℃降低到43.94℃;10%和50％质量损失温度分别提高了10.4℃和9.5℃;断裂伸长率提高,体系柔韧性得到提高;动态热稳定时间由9.55 min延长到30.06 min,加工稳定性更好;抽出性损失降低,增塑剂在塑化体系中的稳定性得到显著提高。该腰果酚基增塑剂可作为PVC的优良辅助增塑剂使用。     

分子模拟技术应用于增塑PVC结构与性能研究

应用特定的分子模拟计算技术,研究了3种增塑剂邻苯二甲酸二辛酯(DOP)、癸二酸二辛酯(DOS)、偏苯三酸三辛酯(TOTM)对聚氯乙烯(PVC)在增塑剂吸收速度、力学性能、硬度和相对电容率等方面的影响.结果表明:分子模拟微观图可在一定程度上解释不同增塑剂在PVC力学及相对电容率等方面性能的差异,并能解释随DOP用量增加,材料力学性能变化的原因.     

Degradation kinetics of PVC plasticized with different plasticizers under isothermal conditions

The aim of the present work is to elucidate the degradation kinetics of polyvinyl chloride (PVC) plasticized with some phthalate and nonphthalate plasticizers. A PVC thermomat instrument was utilized to maintain the isothermal degradation conditions at 140 and 160°C, and to suppress the oxidative degradation by means of nitrogen flow. The conductivity measurements were performed to follow hydrogen chloride (HCl) gas which is released upon PVC degradation and trapped in water. Dehydrochlorination of plasticized PVC films occurred with activation energies of about 23–160 and 26–117 kJ mol^?1 and the isokinetic temperatures, at which the dehydrochlorination rate constants of all p‐PVC films would have the same value, were found to be 171 and 128°C for initial and linear regions of dehydrochlorination curve, respectively. Plasticizer incorporation contributes to the stability of the films particularly after the consumption of stabilizer due to the dehydrochlorination. Influence of temperature rise by 20°C on the degradation rate constant is the lowest for DINCH having p‐PVC films as 0.36 and 0.42% increment at the initial region and linear region, respectively. On the other hand, DOTP reveals greater stability than the others do since the compensation ratio of the PVC film having DOTP is greater than the other films. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41579.     

Assessment of degradation of plasticized poly(vinyl chloride) films through polyene formation under isothermal conditions

The aim of this work is to assess the degradation of flexible poly(vinyl chloride) (PVC) films produced using orthophthalate based and recently introduced nonorthophthlate plasticizers which have compliance with recent environmental regulations. The plasticized PVC films were subjected to several heat treatments at 85–160 °C up to 420 min. Ultraviolet–visible spectroscopy was utilized to follow polyene formation upon dehydrochlorination of PVC. The amount of polyenes formed exhibited difference amongst the films those plasticized with diethyl hexylphthalate, diisodecyl phthalate, dioctyl terephthalate (DOTP), and diisononyl 1,2‐cyclohexanedicarboxylic acid (DINCH). The order of polyene concentration formed at the utmost level severe heat treatment is in line with the molecular weight ranking from highest to lowest, as the films with diisodecyl phthalate > DINCH > DOTP > diethyl hexylphthalate. Discoloration assessed in terms of yellowness index revealed that the films having recently introduced plasticizers as DOTP and DINCH were competing well with the films having orthophthalate based plasticizers. Scanning electron microscopy images revealed that the longer times for gelation during their production would improve the maturation of the films although they are already coherent and strong. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46092.     

An efficient plasticizer based on waste cooking oil: Structure and application

Recently, phthalates have been continuously banned in numerous fields by many countries. Therefore, the development of sustainable and efficient plasticizers has become particularly urgent. The waste cooking oil was used as the main raw materials in this study to synthesize an efficient plasticizer (acetylated-fatty acid methyl ester-trimellitic acid ester, AC-FAME-TAE). The structure of AC-FAME-TAE was characterized by FT-IR and ¹H NMR. The performance of the poly(vinyl chloride) (PVC) plasticized by AC-FAME-TAE was tested and compared with those of the PVC plasticized with di-2-ethylhexyl phthalate (DOP) and EFAME (epoxy fatty acid methyl ester), respectively. DSC results indicated that AC-FAME-TAE had excellent plasticizing efficiency for PVC. The mechanical properties of PVC plasticized by AC-FAME-TAE were as comparable as PVC plasticized by DOP from the results of tensile test. In addition, the PVC plasticized by AC-FAME-TAE had excellent thermal stability and solvent resistance by the results of leaching test and TGA.