成核剂对阻燃PP结晶和力学性能影响

研究了成核剂有机山梨醇类、取代芳基磷酸酯盐和有机羟基铝盐三种不同成核剂对阻燃聚丙烯(PP)改性塑料力学性能影响,并通过差示扫描量热仪(DSC)表征成核剂对阻燃改性PP结晶的影响.结果表明成核剂有利于改善阻燃PP力学性能,提高PP的结晶峰温度和晶粒均匀度,其中取代芳基磷酸酯盐类成核剂的效果最好.     

聚丙烯成核剂的应用与研究进展

介绍了无机类成核剂、有机类成核剂（芳基磷酸盐类、山梨醇类、磷酸金属盐类、松香类成核剂、脱氢枞酸及其盐类和羧酸金属盐类）和聚合物型成核剂的主要类型和特性,阐述了成核剂在聚丙烯中的成核机理及其对聚丙烯性能的影响。     

取代芳基杂环磷酸金属盐类成核剂在等规聚丙烯中的成核效应

采用DSC考察了2,2′-亚甲基双（4,6-二叔丁基苯基）磷酸的不同金属盐在等规聚丙烯中的成核效应,并研究了这些成核剂对等规聚丙烯力学性能和光学性能的影响.结果表明,一价的取代芳基杂环磷酸金属盐如钠盐、锂盐、钾盐具有很好的成核效果,添加0.2%（质量）的钠盐、锂盐或钾盐,可使聚丙烯的结晶峰温度分别提高13.5、13.6℃和15.0℃,结晶度提高5％左右,结晶速率显著提高;同时可使聚丙烯的拉伸强度提高10％左右,弯曲模量提高30％左右,雾度降低40％左右.而二价的钙盐、镁盐、锌盐和三价的铝盐的成核效果不明显.同时非等温结晶动力学研究表明一价的钠盐、锂盐和钾盐的加入可使聚丙烯的结晶方式发生明显的改变.     

透明聚丙烯成核剂的种类及其应用

介绍了无机类透明成核剂、有机类透明成核剂（芳基磷酸盐、山梨醇类、羧酸金属盐、脱氢枞酸及其盐类、支化酰胺类化合物）和聚合物型透明成核剂的主要品种、特点、在聚丙烯中的成核机理及其对聚丙烯性能的影响。     

六氢化邻苯二甲酸金属盐类成核剂的制备及应用研究

以六氢化邻苯二甲酸酐和不同金属盐为原料,合成了新型、高效的六氢化邻苯二甲酸(HHPA)金属盐类聚丙烯(PP)成核剂。采用傅里叶变换红外光谱仪、差示扫描量热仪分别测试了HHPA金属盐的结构和HHPA金属盐类成核剂改性PP的结晶和熔融行为,并对其进行吸湿性测试。结果表明,HHPA金属盐类成核剂是一类高效的PPα-晶型成核剂,当其添加量为0.3%(质量分数,下同)时,PP的结晶温度有不同程度的提高,其中六氢化邻苯二甲酸钠(HHPA-Na)的效果最好,可使PP的结晶温度提高12.1℃;与传统的成核剂苯甲酸钠相比,HHPA金属盐类成核剂具有较低的吸湿性,有利于成核剂及成核改性PP制品的保存。     

磷酸双酚酯盐成核剂的合成及在PP中的应用

通过新技术路线合成磷酸双酚酯盐成核剂,并将其应用于聚丙烯(PP)。结果表明,新方法合成的磷酸双酚酯盐成核剂的产率明显提高,达到98%。通过亚磷酸双酚酯和羧酸盐复配助剂就地形成的芳基磷酸脂盐具有明显的成核效应,促使PP的结晶温度由111.0℃提高到126.3℃。成核剂的加入使复合材料拉伸和弯曲强度得到不同程度提高,其中拉伸强度提高了9%,弯曲强度提高了20%,但冲击强度下降了20%左右,维卡软化点比纯PP的提高8.5℃。     

成核剂TMC-300对聚乳酸等温结晶的影响

通过DSC考察了成核剂TMC-300对聚乳酸（PIA）成核结晶过程的影响,发现成核剂TMC-300可以有效地促进聚乳酸的成核结晶。在使用Avrami方程对该体系进行评价时发现,该方程只适应于聚乳酸结晶初期的评价,而在后期则出现严重偏离现象。     

TMP系列成核剂通过中试鉴定

由山西省化工研究所完成的TMP系列芳基磷酸酯盐类成核剂中试项目目前通过山西省科技厅组织的技术鉴定。TMP系列成核剂包括TMP-1。TMP-3、TMP-5和TMP-6等四个品种，首次提出聚丙烯“点-线”结晶理论，而以此为基础开发的复合型芳基磷酸酯盐类成核剂品种的应用性能明显优于单一结构的芳基酸酯盐成核剂，中试项目投产以来，产品先后通过中科院化学所，中国石化燕山分公司树脂应用研究所、上海石化塑料事业部、中国石化广州分公司、广州金发科技股份有限公司等科研和应用单位的评价测试和工业应用，取得了良好的经济和社会效益。     

TMP系列成核剂通过中试鉴定

由山西省化工研究所完成的TMP系列芳基磷酸酯盐类成核剂中试项目日前通过山西省科技厅组织的技术鉴定。TMP系列成核剂包括TMP-1、TMP-3、TMP-5和TMP-6等4个品种，首次提出聚丙烯“点-线”结晶理论，而以此为基础开发的复合型芳基磷酸酯盐类成核剂品种的应用性能明显优于单一结构的芳基磷酸酯盐成核剂。中试项目投产以来，产品先后通过中科院化学所、中国石化燕山分公司树脂应用研究所、上海石化塑料事业部、中国石化广州分公司、广州金发科技股份有限公司等科研和应用单位的评价测试和工业应用，取得了良好的经济和社会效益。     

苯基磷酸锌对聚乳酸结晶行为影响的研究

采用DSC,POM研究了成核剂苯基磷酸锌（PPZn）对聚乳酸结晶行为的影响。结果表明：PPZn可以作为聚乳酸的高效成核剂,PPZn的加入显著提高了聚乳酸的结晶速率和结晶度。当PPZn的质量分数为5％0时TCs（起始结晶温度）降低了约24℃,TCe（终止结晶温度）降低了约29℃。PPZn的加入使聚乳酸的半结晶时间大大缩短。当PPZn的质量分数为2％时,结晶速率常数增大约5个数量级。     

Effects of substituted aromatic heterocyclic phosphate salts on properties,crystallization, and melting behaviors of isotactic polypropylene

Nucleation effects of 2,2′‐methylene‐bis (4,6‐di‐tert‐butylphenyl) phosphate metal salts as a nucleating agent for isotactic polypropylene (iPP) were investigated with differential scanning calorimeter and polarized optical microscope, and their effects on mechanical, optical, and heat resistance properties of iPP were also studied. The results showed that monovalent metal salts of substituted aromatic heterocyclic phosphate such as sodium salt, lithium salt, and potassium salt had a good performance. With 0.2 wt % of sodium salt, lithium salt, or potassium salt incorporated into iPP, the crystallization peak temperature of iPP could be increased by 13.5, 13.6, and 15.0°C, respectively; the mass fraction of crystallinity of iPP could be increased by about 5%; and crystallization rate was enhanced increasingly. Meanwhile the tensile strength and flexural modulus of iPP could be increased by about 10 and 30%, respectively, and the clarity and heat distortion temperature of iPP could also be improved significantly. But bivalent and trivalent metal salts of substituted aromatic heterocyclic phosphate had little effect on properties of iPP. Meanwhile the morphology study showed that the addition of monovalent sodium salt could decrease the spherulite size of iPP significantly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4868–4874, 2006     

Isothermal and nonisothermal crystallization kinetics of isotactic polypropylene nucleated with substituted aromatic heterocyclic phosphate salts

The crystallization kinetics of isotactic polypropylene (iPP) and nucleated iPP with substituted aromatic heterocyclic phosphate salts were investigated by means of a differential scanning calorimeter under isothermal and nonisothermal conditions. During isothermal crystallization, Avrami equation was used to describe the crystallization kinetics. Moreover, kinetics parameters such as the Avrami exponent n, crystallization rate constant Z_t, and crystallization half‐time t_1/2 were compared. The results showed that a remarkable decrease in t_1/2 as well as a significant increase in overall crystallization rate was observed in the presence of monovalent salts of substituted aromatic heterocyclic phosphate, while bivalent and trivalent salts have little effect on crystallization rate of iPP. The addition of monovalent metal salts could decrease the interfacial free energy per unit area perpendicular to PP chains σ_e value of iPP so that the nucleation rate of iPP was increased. During nonisothermal crystallization, Caze method was used to analyze the crystallization kinetics. It also showed that monovalent metal salts had better nucleation effects than bivalent and trivalent metal salts. From the obtained Avrami exponents of iPP and nucleated iPP it could be concluded that the addition of different nucleating agents changed the crystal growth pattern of iPP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3307–3316, 2006     

Nonisothermal crystallization kinetics and morphology of poly(ethylene terephthalate) modified with poly(lactic acid)

The nonisothermal crystallization kinetics of poly(ethylene terephthalate) (PET) copolymers modified with poly(lactic acid) (PLA) were investigated with differential scanning calorimetry, and a crystal morphology of the samples was observed with scanning electron microscopy. Waste PET (P100) obtained from postconsumer water bottles was modified with a low‐molecular‐weight PLA. The PET/PLA weight ratio was 90/10 (P90) or 50/50 (P50) in the modified samples. The nonisothermal melt‐crystallization kinetics of the modified samples were compared with those of P100. The segmented block copolymer structure (PET‐b‐PLA‐b‐PET) of the modified samples formed by a transesterification reaction between the PLA and PET units in solution and the length of the aliphatic and aromatic blocks were found to have a great effect on the nucleation mechanism and overall crystallization rate. On the basis of the results of the crystallization kinetics determined by several models (Ozawa, Avrami, Jeziorny, and Liu–Mo) and morphological observations, the crystallization rate of the samples decreased in the order of P50 > P90 > P100, depending on the amount of PLA in the copolymer structure. However, the apparent crystallization activation energies of the samples decreased in the order of P90 > P100 > P50. It was concluded that the nucleation rate and mechanism were affected significantly by the incorporation of PLA into the copolymer structure and that these also had an effect on the overall crystallization energy barrier. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Modifying the thermal and mechanical properties of poly(lactic acid) by adding lithium trifluoromethanesulfonate

The effect of the addition of lithium trifluoromethanesulfonate (LiCF₃SO₃) on the linear viscoelastic properties, crystallization behavior, and mechanical properties of poly(lactic acid) (PLA) was studied. The glass transition temperature (T_g) was enhanced by adding LiCF₃SO₃, without any loss of transparency of the PLA. This was attributed to the ion-dipole interaction between the lithium cation and oxygen atom in the PLA carbonyl group. The interaction weakened at higher temperature. Consequently, the rheological terminal region was clearly detected, which suggested that the system possessed good melt-processability. The Young’s modulus and yield stress at room temperature were also enhanced by the addition of LiCF₃SO₃, although the toughness was reduced due to the brittle failure. Finally, the presence of LiCF₃SO₃ retarded the crystallization of PLA, because the segmental motion of the PLA chains was reduced.     

聚乳酸/环氧化聚丁二烯抗冲树脂结晶性能的研究

采用差示扫描量热仪(DSC)对聚乳酸/环氧化聚丁二烯抗冲聚乳酸树脂(PLA/PB(EPB))的结晶性能进行了考察,并与纯聚乳酸(PLA)的结晶行为进行了对比,研究了环氧化聚丁二烯(EPB)对PLA等温/非等温条件下结晶行为的影响规律。结果表明:聚丁二烯橡胶(PB)对PLA的结晶行为影响较小,而EPB对PLA的晶体完善程度影响较为明显。PLA和PLA/PB更倾向于在低温条件下结晶,而PLA/EPB20.9%和PLA/EPB46.5%更倾向于在高温条件下结晶。抗冲聚乳酸树脂的结晶速率高于纯PLA,并且随着EPB环氧化度的增大,抗冲聚乳酸树脂的结晶速率呈逐渐增大的趋势。     

Crystallization behavior and morphology of polylactic acid (PLA) with aromatic sulfonate derivative

This article provides a detailed investigation of crystallization behavior and morphology of polylactic acid (PLA) in the presence of a nucleating agent: potassium salt of 5‐dimethyl sulfoisothalate, an aromatic sulfonate derivative (Lak‐301). Isothermal crystallization kinetics of PLA melt mixed with Lak at concentrations of 0.25–1 wt % was investigated at a range of crystallization temperature, 140–150 °C. To gain further insight on the effect of Lak, nonisothermal differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD), polarized optical microscope (POM), heat deflection temperature (HDT), and rheology were also performed. At 0.25 wt % Lak, crystallinity of PLA increased from 10% to 45%, and in 1 wt % Lak, maximum crystallinity of 50% was achieved. With 1 wt % Lak, crystallization half time reduced to 1.8 min from 61 min for neat PLA at 140 °C. The isothermal crystallization kinetics was analyzed using Avrami model. Values of the Avrami exponent for PLA with Lak were mainly in the range of 3 indicating a three dimensional crystal growth is favored. Crystallization rate was found to increase with increase in Lak content. Observation from POM confirmed that the presence of Lak in the PLA matrix significantly increased the nucleation density. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43673.     

Crystallization morphology and crystallization kinetics of poly(lactic acid): effect of <Emphasis Type="Italic">N</Emphasis>-Aminophthalimide as nucleating agent

The effect of N-Aminophthalimide compound (NA-S) as nucleating agent on crystallization behavior and morphology of poly(lactic acid) was studied. With polarized optical microscope (POM), the unique phenomena of nucleation and epitaxial crystallization of PLA/NA-S system were observed. Dynamic morphology of crystallization was also studied by POM to investigate the relationship between growth behavior of PLA and nucleating agent. Isothermal and non-isothermal crystallization behavior of PLA were studied by differential scan calorimeter (DSC). When nucleating agent was added, a new peak appeared in wide angle X-ray diffraction (WAXD) compared with pure PLA, indicating the nucleating effect of NA-S on crystallization of PLA. All the results indicate that the nucleating agent of NA-S shows obvious nucleating effect on isothermal crystallization above 120 °C and in non-isothermal crystallization after it is added in PLA, that is, the induction crystallization time is reduced, the crystallization rate and nucleation density of PLA are increased.     

Effect of biobased and biodegradable nucleating agent on the isothermal crystallization of poly(lactic acid)

The effect of chemically modified thermoplastic starch (CMPS) on the thermal properties and isothermal crystallization kinetics of poly(lactic acid) (PLA) was studied by differential scanning calorimetry (DSC) and compared to that of granular starch and an inorganic nucleating agent, talc. Nucleated PLA showed an additional crystallization of PLA, which affected the melting temperature. The crystallinity and crystallization rate of PLA were considerably enhanced by addition of CMPS, even at 0.1% content, and the amount of the CMPS had little effect on the thermal properties and isothermal crystallization kinetics of PLA. The effect of CMPS as a nucleating agent was comparable to that of granular starch but slightly less than that of talc. However, CMPS can offer a fully biodegradable nucleating agent with no residues remaining for the biobased and biodegradable polymers.     

Effect of plasticizer on the crystallization behavior of poly(lactic acid)

In this article, the spherulitic morphology and growth rate of the neat and plasticized poly(lactic acid) (PLA) with triphenyl phosphate (TPP) were compared and analyzed by polarizing optical microscopy with hot stage at a temperature range of 100?142°C. The spherulitic morphology of the neat PLA underwent a series of changes such as the typical Maltese Cross at less than 132°C, the disappearance of the Maltese Cross at 133°C, the irregular and distorted spherulites at higher than 134 and 142°C, respectively. For plasticized PLA, the spherulitic morphology exhibited the same changes as neat PLA, but these changes were shifted to lower temperature when compared with neat PLA. In the case of the spherulitic growth, neat PLA had the maximum value of 0.28 μm/s at 132°C, and plasticized PLA had higher values than that of neat PLA. Further analysis based on the Lauritzen–Hoffman theory was presented and results showed that the values of nucleation parameter K_g increased with TPP content. The crystallization behavior of PLA was analyzed by differential scanning calorimetry and wide‐angle X‐ray diffraction. The results showed that the degree of crystallinity of plasticized PLA markedly increased when compared with neat PLA sharply with the incorporation of plasticizer. The crystallization kinetics for the neat and plasticized PLA under isothermal crystallization at 114°C was described by the Avrami equation and the Avrami exponent is close to 2, implying that the crystallization mechanism did not change. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009