环保增塑剂及热稳定剂在PVC中的协同作用

以农林剩余物资源腰果酚为原料合成腰果酚基乙酸酯增塑剂(CA),并用不饱和天然油脂为原料制备多效的油脂源钙锌复合热稳定剂(OMFCTS),将其与聚氯乙烯(PVC)进行共混,通过动态力学性能,热重分析,拉伸性能测试以及静态热稳定性分析,研究其增塑效果及协同作用,并与增塑剂邻苯二甲酸二辛酯(DOP)及热稳定剂硬脂酸钙锌盐进行对比。结果表明,含有20份CA增塑剂及OMFCTS热稳定剂的PVC增塑体系的玻璃化转变温度及储能模量低于PVC/DOP增塑体系;热失重10%及50%的温度明显升高,第一最大失重速率温度和第二最大失重速率温度基本保持不变;断裂伸长率提高到了248.66%,拉伸强度降至5.84 MPa;静态热稳定时间可延长到50 min以上。综上可知,CA增塑剂及OMFCTS热稳定剂联用,可有效改善PVC共混体系的相容性、力学性能及热稳定性,提高制品的综合应用性能及环保性。     

豆油基磷–氯协同阻燃增塑剂的合成,表征和应用

使用可再生资源环氧豆油与三氯氧磷合成了豆油基磷–氯协同阻燃增塑剂。使用傅里叶变换红外光谱和核磁共振氢谱对合成产品的结构进行了分析和表征,结果表明得到了预期的产品。将该产品与聚氯乙烯(PVC)热塑共混成型制备了阻燃增塑PVC共混体系,使用热重分析仪、马弗炉、极限氧指数(LOI)仪和万能拉力试验机对阻燃增塑PVC共混体系的热稳定性能、阻燃性能及力学性能进行了表征。结果表明,合成的大豆油基磷–氯协同阻燃增塑剂对PVC具有高效的阻燃和增塑作用,当其用量从0份增加到30份时,阻燃增塑PVC共混体系的LOI从24.1%增加到33.2%,断裂伸长率从170.14%增加到260.32%,热稳定性也得到提高;合成的阻燃增塑剂的阻燃机理主要是通过促进PVC共混体系表面形成致密的炭层来阻止共混体系进一步热降解。     

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。     

无毒环保型增塑剂对聚氯乙烯性能的影响

选用了邻苯增塑剂(DOP)、柠檬酸酯类增塑剂（ATBC、ATOC）、对苯增塑剂（DOTP）、偏苯增塑剂（TOTM）及新型植物基增塑剂ID-37制备了增塑PVC材料,对所制备的PVC材料的拉伸强度、断裂伸长率、硬度、180℃热稳定性进行表征,测试结果表明,180℃静态热稳定性DOTP与TOTM最优,DOP与ID37次之,ATBC与ATOC相当。增塑剂对力学性能影响较小,对硬度差异影响较大,其中DOTP与TOTM所增塑PVC材料硬度比其余四种高约5度（邵氏A）。DSC测试结果表明,TOTM及ATBC增塑PVC的Tg相对较高,约为-22℃,其余四种较为接近,约为-25℃。     

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。     

环保增塑剂环氧腰果酚乙酸酯增塑PVC研究

首先,以腰果酚(cardanol)与乙酸酐为原料,对甲苯磺酸为催化剂,在无溶剂常温条件下合成了腰果酚乙酸酯(CA)。然后,以甲酸为催化剂双氧水为氧源合成环氧腰果酚乙酸酯(ECA)。考察了合成ECA的用量对聚氯乙烯(PVC)的热失重曲线、邵氏硬度、玻璃化转变温度、拉伸强度与断裂伸长率的影响。结果表明,随着增塑剂用量从20份增加到90份,PVC的热稳定性和断裂伸长率逐渐增加,拉伸强度、邵氏硬度以及玻璃化温度逐渐降低;与未加入增塑剂的PVC树脂及邻苯二甲酸二辛酯增塑的PVC树脂相比,所合成的ECA具有良好的增塑效果。     

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。     

生物基增塑剂异山梨醇酯的研究

以异山梨醇为原料合成了一种生物基增塑剂异山梨醇酯,通过与传统增塑剂邻苯二甲酸二辛酯(DOP)和对苯二甲酸二辛酯(DOTP)对比,考察了其聚氯乙烯(PVC)制片的应用性能。结果表明,合成的异山梨醇酯在PVC制片中具有更优良的力学性能、耐抽出性、耐挥发性及相容性,异山梨醇酯作为生物基增塑剂可替代传统增塑剂的DOP和DOTP用于PVC制品中。     

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。     

对羟基肉桂酸酯类增塑剂烷基链长度变化对PVC增塑性能的影响

以来源于可再生资源的对羟基肉桂酸为原料合成了一系列生物基增塑剂,研究了此类增塑剂烷基链长度变化对聚氯乙烯(PVC)的增塑效率、热稳定性和耐久性的影响。当对羟基肉桂酸酯类增塑剂左侧烷基碳链由9个缩短为3个,增塑PVC的玻璃化转变温度由28.7℃下降到19.0℃,断裂伸长率则由194.7%增加到237.0%。因此,缩短此类增塑剂烷基链长度可以有效地提高其增塑效率。然而,缩短增塑剂烷基链长度会导致其相对分子量降低,最终会使增塑PVC的热稳定性和耐久性变差。此外,对羟基肉桂酸酯类增塑剂的综合性能可与邻苯二甲酸二辛酯(DOP)相媲美,具有替代此类石油基增塑剂的潜力。     

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。     

生物柴油联产环氧二聚酸甲酯增塑剂新技术

以生物柴油为原料,利用生物柴油存在双键结构的特点,将部分双键组分进行二聚化及环氧化反应,形成了生物柴油联产环氧二聚酸甲酯（EDAME）新技术。在二聚化反应条件为240℃/6h下,研究了催化剂种类、油脂双键组分含量对二聚化反应程度的影响,探索了二聚化反应对生物柴油燃烧性能的影响。获得了二聚化得率为28%（硅酸铝为催化剂）的较佳结果。通过二聚化反应后生物柴油十六烷值比较,发现：二聚化反应后,未参与反应的生物柴油的十六烷值变化不大,二聚化反应不影响生物柴油燃烧性能。考察了EDAME与对苯二甲酸二辛酯（DOTP）共混对PVC的增塑效果。通过对共混塑化体系进行力学性能、热重和流变性能表征,结果表明,当EDAME的含量为20%时,断裂伸长率提高了2.62%;当EDAME全部替代DOTP时,T_i、^T₁₀和T₅₀分别提高了6.5℃、9.9℃和26.8℃,残炭量由8.7%升高到11.7%;动态热稳定时间增加,相比于单独使用DOTP,EDAME含量为20%时的平衡扭矩由3.8N·m减小到3.2N·m,从而改善了热塑材料的加工性能。由此可见,EDAME可以部分替代DOTP,作为一种环保可再生的优良辅助增塑剂使用。同时,生物柴油联产环氧二聚酸甲酯新技术有助于提高生物柴油生产线综合经济效益,具有广阔的市场推广前景。     

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.     

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.     

Preparation of epoxidized cardanol butyl ether as a novel renewable plasticizer and its application for poly(vinyl chloride)

A new type of plasticizer, epoxidized cardanol butyl ether (ECBE), was synthesized via etherification and epoxidation. Successful synthesis was confirmed from Fourier transform infrared, ¹H NMR and ¹³C NMR spectra. The obtained product was evaluated by adding it to poly(vinyl chloride) (PVC) incorporated with dioctyl phthalate (DOP). Mechanical and thermal properties of PVC blends were studied using tensile testing, thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). Processability, migration and volatility of plasticizing systems were also investigated. Tensile tests found a maximum increase of 17.8% in elongation at break. DMA results indicated that glass transition temperature shifted to lower temperature with a maximum decrease of 5.76 °C. TGA results revealed that PVC blends with higher content of ECBE had higher thermal stability; initial degradation temperature, 50% weight loss temperature and the first peak degradation temperature increased by 15.3, 14.8 and 4.1 °C, respectively. Processing time was extended from 11.56 to 59.94 min. The plasticizing performance of migration and volatility resistance were higher than those of neat DOP. © 2016 Society of Chemical Industry     

PUR-T／PVC热塑性弹性体的制备及工艺探究

以热塑性聚氨酯弹性体(PUR–T)、聚氯乙烯(PVC)为主要原材料,通过熔融共混挤出制备PUR–T／PVC共混热塑性弹性体。讨论了PUR–T／PVC共混比、增塑剂用量、挤出共混温度、螺杆转速对共混弹性体性能的影响,利用万能试验机、扫描电子显微镜、转矩流变仪、旋转流变仪等研究了弹性体的加工性能及结构。结果表明,当PUR–T／PVC共混比为70／30,增塑剂邻苯二甲酸二辛酯用量为20份,挤出温度为160℃,螺杆转速为330 r／min时,弹性体材料的综合性能最佳;共混弹性体的表观黏度小于纯PUR–T,PVC含量在20%～50%时,PVC易形成网络结构。     

Epoxidized dimeric acid methyl ester derived from rubber seed oil and its application as secondary plasticizer

A novel plasticizer epoxidized dimeric acid methyl ester (EDAMe) based on rubber seed oil was synthesized. Chemical structure of EDAMe was characterized by Fourier transform infrared (FTIR) and gel permeation chromatography (GPC). Effects of EDAMe as secondary plasticizer and its substitution of commercial plasticizer dioctyl terephthalate (DOTP) in soft poly(vinyl chloride) (PVC) films were studied. The thermal properties, mechanical properties and migration stabilities of PVC films were explored with DMA, TG, TG–FTIR, dynamic thermal stability analysis, tensile and migration tests. The results indicated that the epoxidized rubber seed oil based ester has significantly higher thermal stability than DOTP. When DOTP was substituted with 20% (m/m) EDAMe, the results of initial decomposition temperature (T_i), 10% and 50% mass loss temperatures (T₁₀ and T₅₀), and the first maximum weight‐loss temperature rate (T_P1) reached 267.2 °C, 263.5 °C, 307.3 °C and 298.9 °C, respectively. Furthermore, flexibility of the obtained PVC films enhanced significantly with the adding of EDAMe. The migration stabilities of EDAMe was also investigated and showed good migration resistance. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43668.