PVC五金件专用料的热稳定性研究

研究了多种稳定剂以及它们之间的相互协同作用对PVC五金件专用料的热稳定性的影响 ,结果表明 :选用三盐基硫酸铅作为主稳定剂 ,二盐基亚磷酸铅、硬脂酸钡和硬脂酸作为助稳定剂 ,在适当的配比下 ,再配合使用环氧大豆油和亚磷酸三苯酯将可使PVC的动态热稳定时间提高到 36min     

有机锡热稳定剂对CPE脱氯化氢热降解性的影响

采用刚果红法研究有机锡热稳定剂对氯化聚乙烯(CPE)脱氯化氢热降解性的影响。结果表明，硫醇锡复合热稳定剂T-137和T-395A抑制CPE脱氯化氢的效果优于非硫醇锡热稳定剂二月桂酸二丁基锡；环氧大豆油能协同二月桂酸二丁基锡减慢CPE脱氯化氢速度；热稳定剂用量小于3份时，二月桂酸二丁基锡／二盐基亚磷酸铅和二月桂酸二丁基锡／硬脂酸钡并用体系(并用比1：1)抑制CPE脱氯化氢的效果较二月桂酸二丁基锡差，热稳定剂用量为3份时则较好。     

Effects of epoxidized sunflower oil on the mechanical and dynamical analysis of the plasticized poly(vinyl chloride)

Epoxidized soybean oil (ESBO), is one of the most commonly used epoxides because of its typical combined roles as a plasticizer and heat stabilizer. In this study, a novel plasticizer of poly(vinyl chloride) (PVC) resins, epoxidized sunflower oil (ESO), was synthesized, and its performance was evaluated. ESO was designed to act as a coplasticizer and a heat stabilizer like ESBO. ESO is used as organic coplasticizer for plasticized PVC containing Ca and Zn stearates as primary stabilizers and stearic acid as lubricant. Di‐(2‐ethylhexyl) phthalate (DEHP), a conventional plasticizer for PVC, was partially replaced by ESO. Mechanical properties (tensile and shore D hardness) were investigated. The performance of ESO to ESB0 (20 g) for comparison, indicated that ESO could be used as secondary plasticizer for PVC in combination with DEHP. All mechanical and dynamical properties of plasticized PVC sheets varied with the oxirane oxygen of the ESO. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

注射交联发泡成型超轻材料的研究

通过共混乙烯一乙酸乙烯酯共聚物(EVA)与马来酸酐接枝乙烯一丙烯酸酯的共聚物(Fusabond)，得到注射超轻发泡材料；考察了过氧化二异丙苯(DCP)、发泡剂(ACH)、氧化锌(ZnO)、硬脂酸(St)、硬脂酸锌(ZnSt)和填充剂(TA)对材料力学性能的影响。结果表明，当EVA用量为92份、Fusabond 8份、DCP 0．75份、ACH2．50份、St 0．40份、ZnSt 0．50份、ZnO 1．80份，且硫化温度为448K、交联发泡时间为320s时，材料的力学性能符合Adidas的标准，可用于生产Adidas运动鞋的中底。’     

绿色环保硬质PVC基料的开发及应用

通过正交试验优化了硬质PVC的配方，研究了钙锌稳定剂、DOP、ACR、硬脂酸钙4种组分对PVC共混体系流变性能及试样力学性能的影响，结果表明：①绿色环保硬质PVC基料的最佳配方为：PVC100份、钙锌稳定剂5份、DOP4份、硬脂酸钙0．5份、ACR2份、PE蜡0．7份、硬脂酸0．3份；②影响PVC共混体系流变性能的最主要因素是钙锌稳定剂，其次为DOP，影响最小的是ACR；影响试样力学性能的最主要因素是DOP，其次是钙锌稳定剂，影响最小的是ACR。     

环氧大豆油对软PVC性能影响的研究

研究了环氧大豆油对软聚氯乙烯(PVC)性能的影响。实验表明,铅盐和有机锡的热稳定性较好,单独使用硬脂酸钙、硬脂酸锌、环氧大豆油或不足量的有机锡热稳定剂时,PVC样品很快变色。环氧大豆油与硬脂酸钙、硬脂酸锌、有机锡热稳定剂并用时,环氧大豆油具有很好的协同效应;但环氧大豆油和硬脂酸钙、硬脂酸锌不能简单替代有机锡稳定剂。热重分析证明了不同热稳定剂的效果。作为辅助增塑剂,环氧大豆油用量应低于5份。     

Ionic thermoplastic elastomer based on maleated epdm rubber. I. Effect of zinc stearate

Neutralization of maleated EPDM rubber by zinc oxide results in an ionic elastomer. The rate and extent of the neutralization reaction increase by addition of stearic acid. Although the rubber is not easy processable as such, incorporation of zinc stearate at a loading of 30 phr makes the rubber behave the rubber behave like a thermoplastic during high temperature (≥ 150°C) processing. Furthermore, zinc stearate causes improvement in the physical properties of the rubber under ambient conditions. It is believed that zinc stearate acts as a reinforcing filler under ambient conditions and as a plasticizer for the ionic domains at higher temperature (that is, above its melting point, 128°C). The conclusions are based on the results of dynamic mechanical, rheological, and infrared spectroscopic studies. © 1996 John Wiley & Sons, Inc.     

稀土稳定剂的制备与应用

用皂化法制备硬脂酸稀土,以硬脂酸稀土为稳定剂,CPE为改性剂,轻质碳酸钙为填料,同时加入硬脂酸钡、硬脂酸、石蜡、钛白粉等助剂,对PVC进行共混改性。研究了硬脂酸稀土在PVC加工中的应用特点。结果表明,硬脂酸稀土具有优异的热稳定性和耐候性,对PVC的力学性能、加工性能都有不同程度的提高。与其他稳定剂共用时,表现出良好的协同效应,可部分取代铅、镉、钡等金属盐类稳定剂。     

Kinetics of degradation of PVC‐containing novel neem oil as stabilizer

The effectiveness of adding epoxidized neem oil (ENO) in poly(vinyl chloride) (PVC) to enhance heat stability was investigated. Neem oil, of vegetable extract, was characterized for its fatty acid profile and other properties. The virgin oil was epoxidized at 60°C with peroxymethanoic acid (performic acid) generated in situ in the reaction mixture by reacting hydrogen peroxide and methanoic acid. ENO was characterized by FTIR and NMR studies, and the degree of epoxidation was measured with iodine value and oxirane oxygen content. Solubility parameters of neem oil and ENO were estimated. Thermal degradation of PVC‐containing ENO was studied using the static heat stability test and artificial aging at temperatures of 100, 110, 120, and 130°C. Results were compared with the samples prepared with conventional heat stabilizers systems used in PVC, such as Ca/Zn stearates and mixtures of both Ca/Zn stearates and ENO. The changes in elastic modulus of the ENO/PVC combination and the conventionally stabilized Ca/Zn system during aging were kinetically modeled, and the rate constants for the degradative influence of modulus were determined. The activation energies and preexponential factors for the degradative process were obtained from Arrhenius plots and their relationship through a compensation effect was found. In general, ENO was found to be an effective retarder of the degradation of PVC; use of 10 phr level of ENO showed the least degradation with the highest activation energy. A synergistic effect of ENO and Ca/Zn stearate system was also observed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Stabilization of poly(vinyl chloride). II. Stabilization mechanism through metal soaps by complementary color action

In a previous paper, it was pointed out that the stabilization mechanism through metal soaps might be affected by an effect of complementary color. In this work, the colors of heated poly(vinyl chloride) (PVC) films mixed with various metal soaps were investigated by using a differential colorimeter and a spectrophotometer. Monochromatic coloration was observed with PVC, PVC–Ca stearate, and PVC–Ba stearate systems. On the other hand, the phenomenon of color mixing was observed with PVC–Zn stearate, PVC–Cd stearate, PVC–Zn/Ca stearate, and PVC–Cd/Ba stearate systems. In particular, achromatic color remained with PVC–Zn/Ca stearate and Cd/Ba stearate systems for longer heating periods. This means that the stabilization mechanism for PVC compounded with metal soaps should be effected finally by subtractive complementary colors situated between polyene color and the color effected with the metal complex, in addition to being subject to the usual chemical stabilization mechanisms.     

发泡剂AC的热分解活化机理及影响因素*

采用动力学和热力学相结合的方法,用自行设计的发泡剂发气量测量装置研究了重金属盐、金属氧化物、有机酸及其盐等对发泡剂ＡＣ热分解特性的影响;用ＤＳＣ差示扫描量热仪测定了各体系的动态分解温度和热效应。结果表明,三盐基硫酸铅、二盐基亚磷酸铅、硬脂酸铅和柠檬酸对发泡剂ＡＣ都有较强的活化作用,属于加速型发泡助剂;氧化锌是发泡剂ＡＣ较理想的活化引发剂,当其用量为０１份时,活化作用较好;而硬脂酸、硬脂酸钡和柠檬酸钠的活化作用较小,属于延缓型发泡助剂     

90℃环保PVC护套料的研制

通过研究基础树脂、复合稳定剂、增塑剂、填充剂等对电线电缆用环保聚氯乙烯(PVC)护套料性能的影响,确定了电线电缆用环保PVC护套料配方:PVC为100.0 phr,Ca/Zn复合稳定剂为8.0 phr,邻苯二甲酸二异癸酯为40.0 phr,对苯二甲酸二辛酯为10.0 phr,重质CaCO3为35.0 phr.对产物性能的表征表明,整个配方体系不含对人和环境有害的Pb、Cd、Hg、Cr6 等重金属及多溴联苯及其醚类,护套料性能完全满足90℃环保PVC护套料的标准性能要求,挤出工艺性能优良.     

Migration resistant polymeric plasticizer for poly(vinyl chloride)

Flexible films of poly(vinyl chloride) (PVC) and linear or branched poly(butylene adipate) (PBA), synthesized from 1,4‐butanediol and adipic acid or dimethyl ester of adipic acid, were aged in an aqueous environment for 10 weeks to study how branching, molar mass, and end‐group functionality affect the leaching of polyester plasticizer from thin films. Principal component analysis was applied to reveal patterns and correlations between mechanical properties, material characteristics, and aging behavior. Introduction of branches in the polyester structure increased the miscibility between PVC and the polyester, resulting in improved mechanical properties and lower water absorption. Methyl ester end‐group in PBA polyester stabilized the polymeric plasticizer toward hydrolysis, and reduced the formation and migration of monomeric degradation products from the blends during aging in water. The combination of branched structure with methyl ester end‐groups resulted in a migration resistant polymeric plasticizer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2458–2467, 2007     

碳酸钙晶须改性对其与天然橡胶复合材料性能的影响

采用Si-69、硬脂酸钠、NDZ101、硬脂酸和十八酸锌5种表面改性剂对碳酸钙晶须进行表面处理,研究了改性碳酸钙晶须对NR性能的影响。结果表明,选用Si-69改性碳酸钙晶须,且用量为5份时,复合材料的力学性能最好,300%定伸应力、拉伸强度、撕裂强度比未改性时分别提高了26.0%,21.1%和22.5%;复合材料的损耗因子(tanδ)最小,比纯胶降低了0.20,玻璃化转变温度(Tg)为-82.8℃,耐寒性最好。     

Accelerated degradation of highly loaded polypropylene

The accelerated aging of six formulations of polypropylene highly loaded with calcium carbonate and containing a surfactant additive (stearic acid) as well as an ultraviolet (UV) stabilizer was studied. Degradation was followed by measuring mechanical properties (elongation percentage and impact resistance), the dynamic mechanical behavior and some chemical changes such as molecular weight and carbonyl group formation along with oxidation temperatures, found by chemiluminescence. The addition of 30 phr of filler to the polymer reduced the stability of the mixture, and the stearic acid used to treat the filler enhanced this effect considerably. On the other hand, the addition of the photostabilizer controlled to some extent such negative effects, though not completely. The most stable formulation was the polypropylene containing only the UV stabilizer.     

Study of additive compatibility with poly(vinyl chloride) (PVC). 2: Dynamic mechanical analysis of PVC lubrication by stearic acid and its derivatives

The glass transition temperatures of PVC containing stearic acid derivatives as lubricants have been used to define two new parameters of lubrication: the saturation concentration and the efficiency constant. The saturation concentration represents the maximum amount of lubricant compatible with PVC in a specific formulation. The lubricant molecules are associated with the surface molecules of the PVC primary particles or are in the interstitial space between them. The use of lubricants at significantly lower concentration than the saturation concentration ensures their permanence in the polymer. They then act as internal lubricants reducing the viscosity of the melt. The use of lubricants at much higher concentrations than saturation concentration leads to formation of lubricant pools between PVC primary particles. Increased temperature or longer time ensures the release of lubricants from these pools at the surface of the polymer giving the lubricants an external character. At a normal usage of 0.5 to 1.5 phr (approximately 1.6–5 meq stearate) to 100 g PVC, methyl, barium and calcium stearates may be considered internal, aluminum and sodium internal/external, zinc, lithium, magnesium stearates and stearic acid itself external lubricants.     

Effect of stearic acid concentration on the reversion behavior of epoxidized natural rubber

The effect of stearic acid concentration on the reversion behavior of epoxidized natural rubber (ENR 25 and ENR 50) was carried out in the temperature range of 150–180°C and 0.5–14.5 phr of stearic acid loading. Three common accelerators; namely, zinc dimethyldithiocarbamate (ZDMC), tetramethylthiuram disulfide (TMTD), and N-morpholinylbenzothiazole-2-sulfenamide (MBS) and conventional sulfur vulcanization system was used throughout the study. A Monsanto oscillating-disk rheometer was used to determine the reversion behavior of the rubber. Results indicate that for all the accelerators used, reversion decreases with increasing stearic acid concentration. The rate of decrease is more gradual up to about 6.5 phr of stearic acid, after which a rapid drop of reversion is observed for both ENR 25 and ENR 50. This observation is attributed to the increasing amount of mono- and disulfidic crosslinks as a result of desulfuration of polysulfidic crosslinks. The higher the stearic acid loading, the greater is the retardation effect on vulcanization; that is, more time is available for desulfuration. Increasing temperature would increase the reversion of the rubber vulcanizate because of the increase in thermal energy to decompose more crosslinks, including mono- and ether crosslinks for temperature higher than 160°C. ZDMC (an ultrafast accelerator) gives a higher reversion than MBS (a delay-action accelerator), because desulfuration occurs more slowly in the former system. The observed decrease in reversion as stearic acid concentration increases is technologically importance, because the aging property of the rubber vulcanizate is significantly improved. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1165–1169, 1999     

绿色增塑剂环氧大豆油的合成与表征

用自制的催化剂合成了一种环氧大豆油。通过L16(45)正交试验考察了双氧水用量、催化剂用量、反应时间和反应温度对环氧大豆油环氧值的影响。结果表明:在双氧水用量100份、催化剂用量0.5份(大豆油用量定为100份)、反应温度50℃、反应时间12.5 h的最佳工艺条件下,产品的环氧值为6.58%,碘值为0.83 gI/100g。产品通过红外和核磁共振表征,确定大豆油被环氧化生成环氧大豆油。     

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.     

一种新型蓖麻油酸季戊四醇酯的制备及应用

用季戊四醇和蓖麻油酸通过酯化反应反应制备了蓖麻油季戊四醇酯。采用红外光谱仪和核磁共振仪对制备的产品的化学结构进行表征。并将其作为增塑剂与聚氯乙烯（PVC）共混,研究了塑化PVC的平衡扭矩、热性能和力学性能,对该增塑剂在不同溶媒中的耐迁移性进行了研究,并与邻苯二甲酸二辛酯和环氧大豆油的塑化性能进行了对比。结果表明,蓖麻油季戊四醇酯塑化PVC的加工平衡扭矩为14.9 N·m,改善了PVC的加工稳定性;塑化PVC的拉伸强度为23.28 MPa,断裂伸长率为263.13 %,耐迁移性能较邻苯二甲酸酯和环氧豆油较好,可以作为PVC增塑剂使用。