Synthesis of Bio-Plasticizer from Soybean Oil and Its Application in Poly(Vinyl Chloride) Films

Herein,epoxidized soybean oil methyl ester(ESOM)plasticizer was synthesized for the preparation of plasticized poly(vinyl chloride)(PVC)films by the alcoholysis and epoxidation.The chemical structure of ESOM was investigated by infrared spectrum and 1 H nuclear magnetic resonance.The effect of content of ESOM and petroleum based plasticizer di-2-ethylhexyl phthalate(DEHP)on the performance of plasticized PVC films was studied.The result showed that substituting DEHP with ESOM can improve the thermal stability of plasticized PVC films.When the weight ratio of ESOM and PVC is fixed at 1:2,plasticized PVC film presents higher elongation at break(350.8%vs.345.1%)and lower tensile strength(14.21 MPa vs.15.8 MPa)compared with PVC plasticized with DEHP.ESOM showed less weight loss than DEHP in all solvents.The excellent migration resistance of ESOM is helpful to improve stability of plasticized PVC films.In all,the obtained bio-based plasticizer will be potential to replace petroleum based plasticizer DEHP in flexible PVC materials.

Study the Influence of UV-Irradiation on the Photo Stability of Pure and Plasticized Poly (4-Vinyl Biphenyl) in Solid Films

The effect of UV irradiation and blending with phthalate and terephthalate plasticizers on the photo-stability of Poly (4-vinyl biphenyl) was studied at different intervals of irradiation time and in presence of air. The increase in irradiation time on the photodegradation of polymer thin films caused a change in the intensity and shape of the fluorescence band. It has been found that the stability of the polymer decreases with the increase of irradiation time, and to increases with the increase of the amount of added phthalate and terephthalate plasticizers, which is evidence of polymer photodegradation. The FT-IR spectra of irradiated pure and blended polymer with phthalate and terephthalate plasticizers showed a decrease in some absorption bands and increase in the other bands, this is also another factor for the occurrence of photo degradation of the irradiated polymer. The increase in the intensity of absorption of carbonyl and hydroxyl region, indicates a possible photogegradation of polymeric chains and the formation of alcohols, aliphatic ketones and to the increase in the number of (C=C) that resulted from hydrogen abstraction during chains-scission.

Influence of Annealing and Additives on the Crystallization Behavior and Properties of Poly(vinyl chloride)

Acetanilide （AC）, adipic acid （AA） and potassium hydrogen phthalate （PHP） were chosen as additives to accelerate PVC crystallization and improve its mechanical properties. The influences of the additives and annealing on the crystallization behavior, micromorphology and the tensile properties were investigated by the thermal analysis, scanning electron microscopy （SEM） and the tensile test. Based on the analysis results, it was concluded that the melting peaks ranging from 110 to 200 ℃ and 200 to 240 ℃ were caused by the fusion of the fringed micelle crystals and chain-folded crystals respectively. AC advanced the fringed micelle crystal to develop, while AA and PHP promoted obviously the chain-folded crystal to grow. The addition of the foreign additives did not change the growth pattern ofPVC crystallites, the growth of the micelle crystal was favorable at 110 ℃, and the chain-folded crystal was developed at higher temperature. For PVC/ AA and PVC/PHP, when annealed at 110 ℃, a regular nest like network was formed, the crystallinity and the crystallite size were increased as well, and as a result, the tensile strength, Young＇s modulus and the elongation at break point were improved simultaneously and greatly.

Microwave Synthesis of Inulin Acetate as Potential Bio- Based Additive for Poly(Vinyl Chloride)

The paper presents the findings of an experimental study on the microwave synthesis (MW) of inulin acetateand its possible application as bio-additive in poly(vinyl chloride) (PVC). The obtained inulin acetate has beenidentified and characterized by spectroscopic methods. Advantages of the MW compared with the conventionalsynthesis were defined. In order to evaluate possible application of the product as bio-based additive forpolymers, effect of the inulin ester on PVC behavior and characteristics has been investigated by differentialscanning calorimetry (DSC) and deformation upon extension. Experimental results show that in concentrationrange up to 30.0 wt. % the inulin ester influences positively the properties of PVC causing effect similar toplasticizing one. At concentration over 30 wt.% the ester shows more specific behavior, which will be furtherinvestigated. Conclusions about potential application of MW synthesized inulin acetate as bio-based additive forPVC have been drawn.

Chain Dynamics Heterogeneity in Plasticized Poly(vinyl butyral)(PVB) as Elucidated by Solid-State NMR

The chain dynamics heterogeneity of the poly(vinyl butyral)(PVB) plasticized by triethylene glycol bis(2-ethylhexa noate)(TEG-EH) was investigated by various solid-state NMR techniques.The plasticized PVB shows two domains in distinct molecular dynamics differences,namely,rigid and soft domains,where the latter is the plasticizer-rich domain.The time domain low field NMR was first used to investigate the dynamics heterogeneity of the plasticized PVB,and the results show the decreasing activated energy of components in the soft domain of plasticized PVB(E_a=20.2 kJ/mol) as compared with that of the pristine one(E_a=24.3 kJ/mol).Detailed dynamics heterogeneity was obtained by high-field NMR with site-specific features.The quadrupole-echo ~2H-NMR was adopted to elucidate the dynamics heterogeneity of the vinyl alcohol(VA) units,where only the hydroxyl group of VA is deuterated.The ~1H-^(13)C WISE NMR spectra show that there is not much difference in the mobility of the VB unit in PVB with and without plasticizer,whereas the glass transition temperature differed by approximately 53℃.This is further supported by Torchia's T_1 relaxation measurements.The origin of such an unusual phenomenon is attributed to the critical role of the remaining VA(~22%) in the soft domain,where the VA units locally aggregate through hydrogen bonding.Also,the existence of a mobility gradient in the VB unit has been demonstrated.Moreover,the mobility difference for VB with different stereo-geometry(meso or racemic conformation) is observed for the first time.This indicates the importance of modulating the ratio of meso over racemic VB for controlling the macroscopic perfo rmance of PVB.

聚氯乙烯塑料建材的现状和展望

综述了国外聚氯乙烯的历史、产销数据,国内聚氯乙烯塑料现状,国内建筑能耗现状及要求,塑料建材对双碳的贡献以及塑料建材的前景展望。

Antistatic PVC-graphene Composite through Plasticizer-mediated Exfoliation of Graphite

Multilayer graphene was prepared by mechanical exfoliation of natural graphite with dioctyl phthalate （DOP） as milling medium without solvent. The obtained mixture could be directly mixed with poly（vinyl chloride） （PVC） for melt-forming, with DOP acting as plasticizer and graphene acting as conductive filler for antistatic performance. The composite showed surface resistance of 2.5 ×10 6 Ω/ at 1 wt% carbon additive, significantly lower than approx. 7 wt% of raw graphite required for achieving the same level. This value is low enough for practical antistatic criterion of 3 × 10 8 Ω/ . The effect of filler addition on mechanical performance was minimal, or even beneficial for the milled carbon in contrast to the case of raw graphite.

Application of the Long-Chain Linear Polyester in Plastification of PVC

The plastification modification of poly （vinyl chloride） （PVC） with the long-chain linear polyester （LP） synthesized by linear dodecanedioic acid （DC12） or tetradecanedioic acid （DC14） with different diols is investigated. The processing characteristics, mechanical properties and extraction property of the PVC/LP blends in different solvents （xylene, cyclohexane, ethanol） were also studied in detail. All results were compared with that of the PVC plasticized with dioctyl phthalate （DOP）. The results show that the molecular weight, molecular structure and loading of LP greatly influence the mechanical properties of the PVC/LP blends. The processability and the mechanical properties of PVC plasticized by LP are comparable to those of the corresponding PVC/DOP blends. However, the PVC/LP blends posses much better migration resistance property than the corresponding PVC/DOP blends, which makes the long-chain linear polyester become a very good plasticizer candidate for PVC industry.

竹质纤维形态对聚乳酸基竹塑复合材料性能的影响

为高值化利用竹材加工剩余物资源,以聚乳酸(PLA)为基体,竹粉纤维(BF)、竹屑纤维(BS)、竹原纤维(BN)与竹浆纤维(BP)为填料,采用密炼-注塑工艺制备了四种竹塑复合材料,研究了竹质纤维种类对其结构与性能的影响。研究结果显示,BP与BN纤维长径比更大,BS中颗粒形态较多,BF与BS质地较刚硬。BF、BN与PLA共混熔体的混炼扭矩更大,PLA/BP复合材料吸水率最大。BF,BS,BN与PLA的界面相容性较好,其添加改善了复合材料的力学性能,而BP添加降低了复合材料的力学性能。与PLA相比,在纤维质量分数为30%时,PLA/BF,PLA/BS与PLA/BN复合材料拉伸强度分别提高了17.85%,13.6%,11.89%,冲击强度分别提高24.33%,18.70%,35.57%,弯曲强度分别提高19.45%,21.45%,4.99%。PLA/BF复合材料的综合力学性能最优,其次为PLA/BS复合材料,PLA/BP复合材料最差。研究可为竹塑复合材料的开发与应用提供有益参考。

灰分指标在PVC-U管材标准中的设立探讨

研究了硬聚氯乙烯(PVC-U)管材灰分指标的测定方法及其在产品标准中的应用。结果表明:在相同灼烧条件下,不同种类PVC-U管材用无机填料的失重率各不相同。不能只依据灰分推导PVC-U管材的填充材料用量和力学性能变化。以灰分指标为代用指标缺乏可靠性,灰分限量值设定无法提升产品质量,对产品质量控制产生干扰作用,且GB/T 5836.1—2018《建筑排水用硬聚氯乙烯(PVC-U)管材》现有力学性能指标作为直接性能指标能够满足PVC-U管材的使用性能要求,没有必要增加灰分指标。

悬浮法低聚合度聚氯乙烯树脂的孔隙调控

研究了主分散剂、辅助分散剂、链转移剂的种类和用量对低聚合度聚氯乙烯树脂孔隙率的影响规律,对比了采用恒温聚合和变温聚合工艺制备的低聚合度聚氯乙烯树脂的性能。结果表明,采用较低醇解度的聚氯乙烯醇和羟丙基甲基纤维素作为主分散剂,再加入一定量的辅助分散剂可以提升孔隙结构;变温聚合工艺和链转移剂的加入均能提升孔隙率。

Polymer-Decorated 2D MoS2 Synaptic Transistors for Biological Bipolar Metaplasticities Emulation

Biological bipolar metaplasticities were successfully mimicked in two-dimensional(2D)MoS2 transistors via the implementation of two different MoS2 surface decorations,poly(vinyl alcohol)(PVA)and chitosan bio-polymers.Interestingly,the depressing metaplasticity was successfully mimicked when the PVA bio-polymer was used as the surface decoration layer,whereas the metaplasticity of long-term potentiation was realized when the chitosan bio-polymer was taken as the surface decoration layer.Furthermore,the electronic band structures of the 2D MoS2 devices with different surface decorations were further investigated using first-principles calculations for understanding the underlying mechanisms of such bipolar metaplasticities.These results will deepen our understanding of metaplasticity,and have great potential in neuromorphic computing applications.

MECHANICAL AND THERMAL PROPERTIES OF NANOSIZED TITANIUM DIOXIDE FILLED RIGID POLY(VINYL CHLORIDE)

Nano-sized rod-like titanium dioxide （TiO2） filled rigid poly（vinyl chloride） （PVC） nanocomposites were prepared by using injection-molding method. Vicat, Charpy impact and tensile tests as well as thermogravimetric and dynamic mechanical analyses were used to characterize the structure and properties of the nanocomposites. The results showed that nano-TiO2 could improve Vicat softening temperature and also improve thermal stability of PVC during the stages of dehydrochlorination and formation of carbonaceous conjugated polyene sequences, which can be ascribed to restriction of the nanoparticles on the segmental relaxation as being evidenced by raises in glass transition and β-relaxation temperatures of PVC upon filling TiO2. Addition of TiO2 nanoparticles less than 40 phr （parts per hundreds of resin） could significantly improve impact strength of the composites while the TiO2 agglomeration at high contents leads to a reduction in impact toughness.

聚乙烯蜡对硬质PVC塑化性能的影响

采用转矩流变仪研究了2种聚乙烯蜡(聚合级聚乙烯蜡和副产蜡)用量对硬质聚氯乙烯(PVC)塑化性能的影响,并分析在一定加工温度、转速下,聚乙烯蜡的种类和用量与硬质PVC最小转矩、凝胶化转矩、熔体转矩和塑化时间的关系,为硬质PVC润滑剂配方设计提供试验参数。结果表明:2种聚乙烯蜡在丙烯酸酯类树脂(ACR)增韧硬质PVC和氯化聚乙烯(CPE)增韧硬质PVC 2个配方体系中使用时均具有较好的效果,可以有效降低硬质PVC制品加工过程中的最小转矩、凝胶化转矩和熔体转矩,同时导致塑化时间延长,表现出典型的外润滑剂效果。用户可以根据聚合级聚乙烯蜡和副产蜡的加工温度和用量对硬质PVC塑化性能的影响,设计出最佳的试验配方。

ANTIFOULING PROPERTIES OF POLYVINYL CHLORIDE) MEMBRANES MODIFIED BY AMPHIPHILIC COPOLYMERS P(MMA-A-MAA)

Three well-defined diblock copolymers ofpoly（methyl methacrylate-b-methacrylic acid） （P（MMA-b-MAA）） were synthesized using atom transfer radical polymerization method and varying poly（methacrylic acid） （PMAA） chain lengths. These copolymers were blended with PVC to fabricate porous membranes via phase inversion process. Membrane morphologies were observed by scanning electron microscopy （SEM）, and chemical composition changes of the membrane surfaces were measured by X-ray photoelectron spectroscopy （XPS）. Static and dynamic protein adsorption experiments were used to evaluate antifouling properties of the blend membranes. It was found that, the blend membranes containing longer PMAA arm length showed lower static protein adsorption, higher water permeation flux and better protein solution flux recovery.

环氧大豆油-癸二酸低分子量聚酯对PVC增塑性能的研究

将环氧大豆油(ESO)与癸二酸(SA)进行开环固化反应,通过控制反应时间得到3种不同分子量的环氧大豆油-癸二酸低分子聚酯(ESO-SA_(5)、ESO-SA_(9)和ESO-SA_(13)),并对其化学结构进行了表征;再以ESO-SA_(n)为增塑剂,研究其分子量和添加量对聚氯乙烯(PVC)增塑效果、热性能及力学性能的影响;此外,对比了不同成型方式(溶剂流延膜和熔融压制膜)对PVC增塑膜性能的影响;最后,分析了热稳定剂的加入对熔融压制膜性能的影响。研究表明,不同成型方式制备的PVC增塑膜中,均为添加30份ES0-SA_(9)的增塑膜具有最好的性能,包括增塑效果、力学性能(断裂伸长率269.6%,拉伸强度28.7 MPa)及热性能(初始热分解温度284.3℃)等;熔融压制使PVC与增塑剂分子之间能到达更好的混合效果,可实现分子水平的混合;由于钙锌稳定剂与基体的相容性较差且同时破坏了ESO-SA_(n)在PVC中形成的增塑网络结构,热稳定剂的加入反而导致增塑膜的力学性能及热性能等出现一定程度的降低。

增塑剂对PVC溶胶发泡性能的影响

通过研究6种不同增塑剂制备的聚氯乙烯(PVC)溶胶的发泡性能,分析发泡性能存在差异的原因。结果表明,6种增塑体系中,苯二甲酸酯类增塑剂P4制备的PVC发泡溶胶发泡质量最佳,其次是柠檬酸酯类的P2,己二酸二异壬酯P5的发泡性能较差。T_(f)-T_(ηmax)、T_(f5%)-T_(ηmax)参数对发泡质量的影响显著,T_(f)-T_(ηmax)、T_(f5%)-T_(ηmax)越大,发泡效果越好。增塑剂相对分子质量越小,与糊树脂的相容性越好,均可以使T_(ηmax)减小,T_(f)-T_(ηmax)、T_(f5%)-T_(ηmax)增大,有利于得到综合性能较好的发泡材料。

辐照交联PVC/环氧树脂固化复合发泡材料的制备及性能

采用熔融共混法和辐照交联工艺成功制备了一系列聚氯乙烯(PVC)/环氧树脂(E-12)/马来海松酸酐(MPA)复合发泡材料。通过傅里叶变换红外光谱仪(FTIR)和核磁共振仪(1H-NMR、13C-NMR)表征了MPA的化学结构;通过凝胶含量、力学性能、扫描电子显微镜(SEM)和吸水率等试验,探究了E-12/MPA(EM)固化物含量对PVC/E-12/MPA复合发泡材料性能的影响。结果表明,当EM固化物含量为10%(质量分数,下同)时,PVC/E-12/MPA复合发泡材料的凝胶含量为42.3%,较改性前提高了9.9%,拉伸强度提高了23.4%,压缩强度提高了26.7%,压缩模量提高了32.5%;断裂伸长率从286.11%降至217.68%,吸水率从改性前1.5%增至3.4%,同时具有优异的泡孔结构。