塑化温度和成型温度对增塑PVC及PVC／PNBR弹性体力学性能的影响

当塑化温度分别为135℃和150℃时,通过测定不同成型温度下（145、150、155、160℃）压片制得的增塑PVC和PVC／PNBR共混物的断裂伸长率、拉伸强度、硬度和拉伸永久变形,研究了塑化温度和成型温度对试样力学性能的影响。结果表明：①150℃塑化温度下,物料塑化得更完全,PVC分子链间的作用力增强,试样的拉伸强度、拉伸永久变形、硬度增大;②在成型温度为145-155℃范围内,试样的断裂伸长率、拉伸强度随成型温度的提高都显著增大;③与塑化温度相比,成型温度对试样力学性能的影响更大。     

Hydrothermic aging of plasticized poly(vinyl chloride): Its effect on the dielectric,thermal, and mechanical properties

Accelerated hydrolytic aging (according to the NFT 5166 method) was performed on samples of poly(vinyl chloride) (PVC) plasticized with dioctylphthalate (DOP) and dinonyladipate (DNA) at different concentration ratios. The aging test consisted of immersing the samples in boiling water at 100°C. The samples were removed from water regularly, that is, every 2 h, for mechanical, thermal, and dielectric characterizations. Thermograms of PVC plasticized with DOP revealed no migration of the plasticizer independent of the concentration used. Moreover, the thermal stability of the samples was not affected by the hydrothermal aging. However, for PVC samples plasticized with DNA, a small amount of the plasticizer migrated from the polymer matrix with a considerable effect on the thermal stability. In fact, the data indicated a decrease in the decomposition temperature from 275 to 225°C, particularly for samples containing 50% (w/w) DNA immersed up to 10 h. The mechanical results showed that for a plasticizer content greater than 30% (w/w), the strain at break obtained for samples plasticized with DNA was lower than that for samples plasticized with DOP because the DNA molecules were more likely to be removed by water on account of their polarity and dimension. Finally, the dielectric measurements showed that the permittivity of all the PVC samples plasticized with DOP and immersed in boiling water was higher than that of the virgin samples. On the contrary, the permittivity of the aged unplasticized PVC was less than that of the nonimmersed samples. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3447–3457, 2003     

自制环保稳定剂在增塑PVC制品中应用性能的评价

通过刚果红热稳定性实验、热老化实验、流变、力学性能以及黄色指数测定等实验,对比研究了自制钙/锌稳定剂与国外知名钙/锌稳定剂对增塑PVC热稳定性能、加工性能、热老化性能和力学性能的影响。研究发现:自制钙/锌稳定剂在增塑PVC制品方面各种性能几乎与该国外知名钙/锌稳定剂没有差别,在热老化性能和力学性能方面还优于该国外知名钙/锌稳定剂。     

Polyhedral oligomeric silsesquioxane as a novel plasticizer for poly(vinyl chloride)

This study focuses on investigating the use of polyhedral oligomeric silsesquioxanes (POSS) to plasticize poly(vinyl chloride) (PVC). Conventional organic plasticizers for PVC, such as dioctyl phthalate (DOP), are somewhat volatile, leading to plasticizer loss and unwanted deterioration of the material properties over time. Previous experimental results indicate that methacryl-POSS, which is much less volatile due to its hybrid organic-inorganic structure, has the ability to plasticize PVC. Methacryl-POSS is miscible in the PVC only up to 15 wt%, thereby limiting its suitability as a plasticizer. However, through the use of ternary compositions it is possible to increase the proportion of methacryl-POSS in PVC substantially. The T_g of appropriately formulated ternary PVC/POSS/DOP compounds can be reduced to near room temperature, and these materials exhibit desirable ductile behavior. Binary (PVC/DOP) and ternary (PVC/POSS/DOP) compounds formulated to the same T_g values showed considerably different mechanical properties. Such findings reveal the possibility of using POSS to engineer the mechanical properties of plasticized PVC.     

聚氯乙烯改性丁腈橡胶耐油泡沫鞋底的研究

鉴于丁腈橡腕的优异性能及国产丁腈橡胶的不足，研究了聚氯乙烯（PVC）改性丁腈橡胶耐油泡沫鞋底的性能，探讨了制品发泡工艺条件、主要组分的选择、原料的配比、增塑剂（DOP）、填料（CaCo3）、发泡剂（AC）对其密度、硬度、回弹率、压缩永久变形、断裂伸长率、拉伸强度、耐油性的影响，最终找出了使制品综合性能较好的原料配比。     

低分子量聚四氢呋喃二苯甲酸酯的增塑性能分析

以传统的邻苯二甲酸二辛酯（DOP）和聚醚型二甘醇二苯甲酸酯（DEDB）增塑剂作对比,对聚四氢呋喃二苯甲酸酯（PTMGDB₅₀₀）增塑剂增塑的聚氯乙烯（PVC）材料进行研究。本文对增塑剂增塑的PVC材料进行了FTIR和TG表征,并考察了其力学性能、耐乙醇抽出性及耐迁移性。结果表明,增塑剂PTMGDB₅₀₀增塑的PVC材料在力学性能上介于DOP和DEDB两者之间,而PTMGDB₅₀₀与PVC间的相互作用更强,在耐迁移、耐乙醇抽出、耐热及耐压等性能方面均优于DOP及DEDB,因此PTMGDB₅₀₀可作为部分替代DOP和DEDB的增塑剂。     

粉末丁腈橡胶改性软质PVC的性能研究

以粉末丁腈橡胶作为改性剂,通过正交实验的方法,研究了增塑剂邻苯二甲酸二辛酯(DOP)、粉末丁腈橡胶P83、轻质CaCO3对软质聚氯乙烯(PVC)力学性能和加工性能的影响。结果表明:DOP在常温和热老化的情况下,对伸长率影响最大;P83对常温下拉伸强度、耐油情况下的扯断伸长率影响最大;CaCO3不论是在什么条件下对性能的影响都不是最主要的。综合考虑力学性能和加工性能,3种因素的最佳水平组合应为A2B2C2,即DOP 60份、P83 20份、CaCO320份时最好。     

PVC型材原材料老化性能的评价

通过测试PVC型材原材料、PVC干混料及塑化物的静态热稳定性能、光老化性能，评价了原材料的老化性能，为提高PVC型材的老化性能奠定基础。     

纳迪克酸酐聚酯PVC增塑剂的制备及其性能研究

以纳迪克酸酐(NA)、甲基丙二醇(MPO)为原料、2-乙基己醇为封端剂、环己烷为带水剂、钛酸四正丁酯为催化剂的条件下,经过缩聚、减压蒸馏制备增塑剂聚纳迪克酸甲基丙二醇酯(P-MPO-NA)。通过对醇酸物质的量比、反应时间、封端剂及催化剂用量的考察,得到反应的最佳工艺条件为:纳迪克酸酐、甲基丙二醇、2-乙基己醇物质的量比为1.0 1∶.20 0∶.60,催化剂质量分数为0.15%,反应时间7 h,酯化率达到99.60%。通过红外光谱分析(FT-IR)、热重分析(TG)等对P-MPO-NA的结构和热稳定性进行了表征。将其与邻苯二甲酸二(2-乙基己基)酯(DOP)、邻苯二甲酸二丁酯(DBP)、柠檬酸三丁酯(TBC)分别加入到聚氯乙烯(PVC)树脂中,进行耐抽出、耐迁移、拉伸强度、断裂伸长率和热稳定性能对比研究。结果表明:该聚酯增塑剂较DOP、DBP、TBC有更好的耐迁移、耐抽出性,并且韧性好,同时提高了PVC的热稳定性。     

Oil-resistance studies of dynamically vulcanized poly(vinyl chloride)/epoxidized natural rubber thermoplastic elastomer

Dynamically vulcanized poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) thermoplastic elastomers (TPEs) were prepared with a Brabender plasticorder coupled with a mixing attachment by melt mixing. The blends were prepared at 150°C at a rotor speed of 50 rpm. Curatives concentration was steadily increased from 0 to 1 phr in order to study the vulcanization effect on the plasticized blend. The effectiveness of the dynamic vulcanization was indicated by the Brabender plastograms. The properties investigated include mass swell, tensile strength, elongation at break, modulus at 100% elongation (M100), tear strength, and hardness. The PVC/ENR samples were exposed to two types of environments, namely, air and oil under otherwise identical conditions. The effect of oil and thermooxidative aging on the mechanical properties were characterized at room temperature and 100°C. It was found that at ambient temperature the samples immersed in oil possessed similar properties to those that were exposed to air. Significant enhancement in mechanical properties were observed for both environments at 100°C. This has been attributed to the increase in crosslink density which was manifested by a steady reduction in percent mass swell with increased sulfur loading. The excellent mechanical behavior of the PVC/ENR TPEs even after immersing the samples in oil at 100°C has provided a good indication of the oil resistance of the materials. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1357–1366, 1998     

Evaluation of the effects of biobased plasticizers on the thermal and mechanical properties of poly(vinyl chloride)

Blends were prepared of poly(vinyl chloride) (PVC) with four different plasticizers; esters of aconitic, citric, and phthalic acids; and other ingredients used in commercial flexible PVC products. The thermal and mechanical properties of the fresh products and of the products after 6 months of aging were measured. Young's modulus of the PVC blends was reduced about 10‐fold by an increase in the plasticizer level from 15 to 30 phr from the semirigid to the flexible range according to the ASTM classification, but a 40‐phr level was required for PVC to retain its flexibility beyond 6 months. At the 40‐phr level, tributyl aconitate performed better than diisononyl phthalate (DINP) or tributyl citrate, in terms of lowering Young's modulus, both in the fresh materials and those aged for 6 months. The effects of the four plasticizers on the glass‐transition temperature (T_g) were similar, with T_g close to ambient temperature at the 30‐ and 40‐phr levels in freshly prepared samples and at 40–60°C in those aged for 6 months. The thermal stability of the PVC plasticized with DINP was superior among the group. Overall, tributyl aconitate appeared to be a good candidate for use in consumer products where the alleged toxicity of DINP may be an issue. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1366–1373, 2006     

Evaluation effects of biobased plasticizer on the thermal,mechanical, dynamical mechanical properties,and permanence of plasticized PVC

Sunflower oil (SO) is a renewable resource that can be epoxidized, and the epoxidized SO has potential uses as an environmentally friendly in polymeric formulations, especially for poly (vinyl chloride) (PVC). Epoxidized sunflower oil (ESO) was prepared by treating the oil with peracetic acid generated in situ by reacting glacial acetic acid with hydrogen peroxide. Epoxidation was confirmed using spectroscopic and titration methods. ESO was used as a coplasticizer in PVC for the partial replacement of di‐(2‐ethyl hexyl) phthalate (DEHP). The effect of ESO on the thermal stability of plasticized PVC was evaluated by using synmero scale for the sheets. In presence of ESO plasticized PVC samples showed a reduction in discoloration and the number of conjugated double bonds. By using thermogravimetry, the incorporation of 15/45 of ESO/DEHP in PVC presents the lowest weight loss. The results of the shore hardness and mechanical properties showed that a proportion of DEHP could be substituted by ESO. By use of DMA, the formulation which contains 25 % wt of ESO in plasticizer system shifts the glass transition temperature (T_g) to ambient temperature. The migration phenomenon was studied on PVC based samples plasticized with DEHP and ESO in varying amounts. The migration was monitored by the weight loss percentage of the samples immersed into n‐hexane or heated in an oven. The amount of extracted or volatilized DEHP is proportional to the added ratio of ESO in plasticizer system. All of this favored the partial replacement of DEHP by ESO as biobased plasticizer for flexible PVC. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

氙灯加速老化对聚酯纤维/PVC柔性复合材料力学性能影响的研究

聚酯纤维/PVC柔性复合材料由于多用于户外,易受阳光照射而老化,从而影响材料的力学性能。通过模拟大气环境较好的氙灯耐气候试验箱,考察了氙灯加速老化对聚酯纤维/PVC柔性复合材料顶破性能和撕裂性能的影响。采用CRT材料试验机,研究了聚酯纤维/PVC柔性复合材料的顶破性能和撕裂性能的变化,并比较了两种不同撕裂模式的破坏机理;采用FTIR研究了PVC涂层吸收峰和峰强的变化;采用SEM研究老化前后涂层表面的微观形貌。研究表明:氙灯人工气候老化下,聚酯纤维/PVC柔性复合材料的老化机理主要是羰基化合物和共轭双键的形成;柔性复合材料撕裂性能下降明显;不同撕裂模式对评价柔性复合材料差异较大。     

国内外聚氯乙烯塑料门窗的现状及展望

介绍了未增塑聚氯乙烯塑料门窗的导热系数低、防水、防潮等特点,利用PVC型材作门窗是节约建筑材料的一条重要途径.重点阐述了国内外聚氯乙烯塑料门窗的生产、使用情况及国内产品存在的缺陷,另外还论述了国内塑料门窗的发展趋势,对PVC塑料门窗在国内的发展应用有促进作用.     

Poly(vinyl chloride) and its fire properties

This work provides an up‐to‐date review of the fire properties of poly(vinyl chloride) (PVC) materials, both rigid (unplasticized) and flexible (plasticized). The fire properties addressed include ignitability, ease of extinction (oxygen index), flame spread (small scale and intermediate scale), heat release, smoke obscuration, smoke toxicity, hydrogen chloride emission and decay, and performance in real‐scale fires. This comprehensive review includes a wide selection of references and tables illustrating the properties of PVC materials in comparison with those of other polymeric materials, including, in many instances, wood materials. The work puts these fire properties in perspective, showing that the heat release rate (the key fire property) of rigid PVC (and that of properly flame‐retarded flexible PVC) are among the lower values found for combustible materials. This work also shows that the smoke toxicity and smoke obscuration resulting from burning PVC materials in real‐scale fires is in the same range as those of other materials.     

Dielectric Properties of PVC Plasticized with Dioctyl Sebacate (DOS)

Abstract

The dielectric properties of PVC plasticized with dioctyl sebacate (DOS) was studied. The dielectric loss tangent was found to decrease for the plasticized samples which interpreted according to the increase in the intermolecular interactions upon plasticization. The plasticizer contribute to the dielectric strength not only via its own polarity but also by markedly changing the nature of the relaxation process. The calculated Frohlich-Kirwood “g” factor indicates that there is a strong interaction between the C-Cl group (of the polymer) and the C = O group (of the plasticizer).     

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。     

PP-g-（DMC-co-St）增容PP／PVC共混体系的研究

利用合成的多单体接枝物[PP-g-（DMC-co-St）]增容PP／PVC共混体系,研究了其用量对共混物力学性能以及流变性能的影响,并通过扫描电镜（SEM）分析了共混物的亚微观相结构。结果表明：①在试验条件下,共混物熔体具有典型的假塑性流体特征,在PP-g-（DMC-co-St）用量为6份时,熔体的表观黏流活化能和非牛顿指数最大;②PP-g-（DMC-co-St）对PP／PVC共混体系有较好的增容效果,增容后在PP-g-（DMC-co-St）用量为6份时,试样的拉伸强度、缺口冲击强度出现最大值,与扫描电镜照片的分析结果一致。     

糊树脂标准糊粘度测定方法的改进

重点利用标准糊的配比、搅拌转速和时间、恒温温度、恒温时间等几个方面,作为采用正交设计实验条件,研究各实验条件下PVC增塑糊粘度及稳定性,以确定最佳实验条件。     

The Effect of Epoxidized Sunflower Oil on the Miscibility of Plasticized PVC/NBR Blends

Blends of plasticized poly(vinyl chloride) (PVC) with several ratios of nitrile rubber (NBR) were studied. The effects of epoxidized sunflower oil (ESO) in combination with di-(2-ethylhexyl)phthalate (DEHP) in the PVC blends on the tensile strength, elongation, hardness, and dynamical mechanical analysis (DMA) were studied. The modulus and hardness results revealed that the addition of ESO to the blend favors the miscibility of PVC and NBR. The PVC/NBR/(DEHP-ESO) blends behave as a compatible system as is evident from the single T _g observed in DMA. The moderate level broadening of the T _g zone in blends is due to the presence of ESO in the plasticizer system. Blends of plasticized PVC and nitrile rubber showed promising properties. The ESO is suitable to partially replace DEHP in PVC/NBR blends.