成核剂二(3,4-二甲基二苄叉)山梨醇对聚丙烯结晶性能的影响

以二(3,4-二甲基二苄叉)山梨醇(DMDBS)为成核剂,使用溶液沉淀法制备 DMDBS 质量分数分别为0.1%、0.3%、0.5%、0.7%、0.9%的粉末聚丙烯(PP)样品,采用红外光谱仪、差示扫描量热仪,X 衍射仪和偏光显微镜等技术进行结晶性能的研究。结果表明,透明成核剂 DMDBS 是 PP 的有效α诱导剂,DMDBS 的加入能诱导大量球晶生成,使结晶峰尖锐,结晶温度区间变窄,提高 PP 的结晶速率和结晶度,其中熔融吸收峰温度提高1.7～3.1℃,结晶度提高16%左右。在 PP 中添加0.3%DMDBS 时,PP 的改性效果最好,结晶度达到最大值。     

DMDBS成核改性聚丙烯抗菌薄膜的研究

以二(3,4-二甲基二苄叉)山梨糖醇(DMDBS)为成核剂,油酸酰胺改性载银磷酸锆为抗菌剂,聚丙烯(PP)为基体树脂,制备了成核剂母粒、抗菌剂母粒和PP抗菌薄膜,并对PP抗菌薄膜的抗菌性能、光学性能及力学性能等进行了研究。结果表明:经DMDBS改性的PP抗菌薄膜,球晶尺寸减小,结晶密度增大,结晶温度提高;含0.2%DMDBS和0.8%改性载银磷酸锆的PP薄膜的纵、横向拉伸强度分别为49.92、33.42MPa,透光率为88.5%,雾度为3.0%,对大肠杆菌和金黄色葡萄球菌抗菌率分别为99.33%和98.35%。     

1,3,5-苯三甲酸衍生物类新型成核剂的合成及应用研究

合成了新型成核剂1,3,5-苯三甲酸三（环己胺）（BTCA-TCHA）,研究了该成核剂对等规聚丙烯力学性能、结晶行为和熔融行为的影响。结果表明,成核剂BTCA-TCHA可明显改善等规聚丙烯的力学性能和光学性能,并可以大幅度提高结晶峰温度。当BTCA-TCHA添加量为0.2 %时,等规聚丙烯的拉伸强度和弯曲模量可分别提高9.72 %和12.4 %,雾度降低53.5 %。当降温速率为20 ℃/min时,添加BTCA-TCHA的等规聚丙烯的结晶峰温度可从空白样的114.6 ℃提高到126.8 ℃。BTCA-TCHA的性能与传统的山梨醇类成核剂Millad 3988基本接近。     

成核剂DMDBS改性聚丙烯的等温结晶研究

采用差示扫描量热法(DSC)对成核剂二-(3,4-二甲基苄叉)山梨醇(DMDBS)改性聚丙烯的等温结晶动力学进行了研究。结果表明DMDBS的加入可大幅度缩短聚丙烯的半结晶时间t1/2,加快聚丙烯的结晶速度。在等温条件下DMDBS的加入对聚丙烯的结晶方式影响不大,但可显著降低聚丙烯球晶生长的单位面积折叠表面自由能σe,从而明显加快成核速率。     

二环[2.2.1]庚烷二羧酸盐成核剂对聚丙烯结晶行为和力学性能的影响

研究了二环[2.2.1]庚烷二羧酸盐成核剂(商品名:HPN-68)对聚丙烯(PP)结晶行为和力学性能的影响。结果表明:HPN-68是一种典型的聚丙烯α晶型成核剂,在PP中具有很高的成核效率。在较低的添加浓度下可明显提高PP的结晶峰温度和力学性能。然而,其添加量存在一个饱和值。当成核剂含量达到该饱和值以后,PP的结晶峰温度和力学性能就趋于稳定。当成核剂HPN-68的添加量为0.2 phr时,PP的结晶峰温度可升高15℃左右,拉伸强度和弯曲模量分别可提高12.7%和18.2%。     

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.     

α-成核剂对均聚聚丙烯性能的影响

考察了几种α-成核剂对聚丙烯性能的影响,选取改性性能较好的成核剂,分析了该成核剂对聚丙烯力学性能和结晶性能的影响。结果表明:随着成核剂用量的增加,聚丙烯的力学性能先升高再降低;加入成核剂可明显提高聚丙烯的结晶温度,加快结晶速率,晶粒尺寸明显变小。     

1,3,5-苯三甲酸三(环己胺)在PP中的成核效应

研究了1,3,5–苯三甲酸三(环己胺)(BTCA–TCHA)成核剂的添加量对聚丙烯(PP)拉伸性能、弯曲性能、雾度以及结晶峰温度的影响,并与高效的商用二苄叉山梨醇类成核剂Millad 3988进行了比较。结果表明,成核剂BTCA–TCHA在较低的添加量(质量分数为0.20%左右)就具有非常优异的成核效果。当BTCA–TCHA质量分数为0.2%时,PP的拉伸强度和弯曲弹性模量可分别从纯PP的30.85 MPa和1 530 MPa提高到33.85 MPa和1 720 MPa(分别提高9.73%和12.42%),雾度可从空白PP的80.12%降低到37.25%,降低幅度为53.51%,而冷却速率为20℃/min时其结晶峰温度可比纯PP提高12℃左右,其成核效果与Millad 3988类似。此外,BTCA–TCHA在PP中的添加量存在一饱和值(质量分数为0.2%),当添加量超过该值以后,继续添加成核剂对PP性能的改善效果不明显。     

新一代聚丙烯成核剂的合成及应用

介绍了二(3,4-二甲基二苄叉)山梨糖醇(DMDBS)的合成路线和作用机理,并以山梨糖醇和3,4-甲基苯甲醛为原料,在固体酸的作用下,不用分离水就能直接合成出新一代聚丙烯透明成核剂DMDBS.结果表明,在醇醛物质的量比2.1、催化剂加量4.5％(质量分数,以醇醛质量总和为基准,下同)、反应温度25℃、反应时间5h、溶剂...     

成核剂1,3-2,4-二（3,4-二甲基）亚苄基木糖醇的合成及其对聚丙烯的改性

以3,4-二甲基苯甲醛和木糖醇为原料合成1,3-2,4-二（3,4-二甲基)亚苄基木糖醇（DMDBX）,将DMDBX作为成核剂使用溶液沉淀法制备DMDBX质量分数分别为0、0.1%、0.3%、0.5%、0.7%、0.9%的聚丙烯（PP）样品,采用红外光谱仪、差示扫描量热仪、X射线衍射仪和偏光显微镜等方法,研究了DMDBX对PP结晶结构和结晶性能的影响。结果表明,DMDBX是PP的有效α晶型诱导剂,DMDBX的加入能诱导大量球晶生成,导致结晶峰尖锐,结晶温度区间变窄,结晶度提高15％左右,FT-IR、X射线衍射和DSC等分析结果一致。在PP中添加0.3%～0.5％DMDBX时,聚丙烯的改性效果最好,结晶度达到最大值。采用修正Avrami方程Jeziorny法处理非等温结晶动力学结果表明,添加DMDBX的PP Avrami指数约为3,说明DMDBX起到了异相成核的作用,使PP结晶过程的成核和生长方式发生了改变。     

Improving crystallization behaviors of isotactic polypropylene via a new POSS‐sorbitol compound

A new compound was synthesized by chemical combination of (3‐mercapto)propyl‐heptaisobutyl polyhedral oligomeric silsesquioxane (POSS‐SH) and 1,3:2,4‐bis(3,4‐dimethylbenzylidene) sorbitol (DMDBS) via epichlorohydrin while hydroxyl groups were still retained in the product POSS‐DMDBS. The prepared POSS‐DMDBS was introduced into isotactic polypropylene (iPP) to improve crystallization behaviors of iPP and obtain nanocomposites with suitable mechanical properties. Crystallization and mechanical properties of iPP/POSS‐DMDBS were systematically investigated by wide‐angle X‐ray diffraction, polarization microscopy, atomic force microscopy, differential scanning calorimetry, and tensile tests. The spherulite size of the modified iPP was obviously decreased with the addition of POSS‐DMDBS, while the crystallization temperature was increased by 5°C to 9°C depending on the content of POSS‐DMDBS incorporated. POSS‐DMDBS exhibited relatively higher nucleating efficiency on iPP which is similar to that of DMDBS, confirmed by the increased crystallization temperature. It was also found that the tensile modulus of iPP after adding POSS‐DMDBS increased significantly with respect to pristine iPP, but the elongation values decreased. Introduction of POSS‐DMDBS in content less than 1 wt% could bring about effective influence on the crystallization behaviors of iPP, demonstrating its potential applications . POLYM. ENG. SCI., 57:357–364, 2017. © 2016 Society of Plastics Engineers     

Structural characterization of α‐ and β‐nucleated isotactic polypropylene

Modification of isotactic polypropylene (iPP) with two nucleation agents, namely 1,3:24‐bis(3,4‐dimethylobenzylideno) sorbitol (DMDBS) (α‐nucleator) and N, N′‐dicyclohexylo‐2,6‐naphthaleno dicarboxy amide (NJ) (β‐nucleator), leads to significant changes of the structure, morphology and properties. Both nucleating agents cause an increase in the crystallization temperature. The efficiency determined in a self‐nucleation test is 73.4 % for DMDBS and 55.9 % for NJ. The modification with NJ induces the creation of the hexagonal β‐form of iPP. The addition of DMDBS lowers the haze of iPP while the presence of NJ increases the haze. Copyright © 2004 Society of Chemical Industry     

The effect of bicyclo[2.2.1]hept‐5‐ene‐2,3‐dicarboxylate on the mechanical properties and crystallization behaviors of isotactic polypropylene

The mechanical and optical properties of iPP nucleated with bicyclo[2.2.1]heptenedicarboxylate salts (BCHED) have been investigated. The results showed that aluminum bicyclo[2.2.1]heptenedicarboxylate (BCHE13) is the most effective nucleating agent to improve the mechanical and optical properties. Then the effects of the BCHE13 concentration on mechanical and optical properties and crystallization behaviors were studied. The results indicated that the saturated concentration of BCHE13 is about 0.2 wt %, at which nucleated iPP showed the better comprehensive mechanical and optical properties and high crystallization peak temperature. Nonisothermal crystallization kinetics of iPP nucleated with different BCHE13 contents have been investigated by Caze method. The results indicated Avrami exponents of nucleated iPP gradually increased with the increasing of BCHE13 concentration. The results can be explained that crystallization and growth model of nucleated iPP is heterogeneous nuclei followed by more than three‐dimension spherical growth during nonisothermal crystallization, which can be proved by agglomeration of BCHE13 in melt iPP. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

β成核剂对抗冲聚丙烯共聚物的结晶和力学性能研究

分别用α晶型成核剂和β晶型成核剂对抗冲聚丙烯共聚物（iPP）的结晶和力学性能进行研究,并用偏光显微镜（POM）、广角X射线衍射仪（WAXD）和差示扫描量热仪（DSC）对其进行了详细的表征。结果表明,α和β成核剂使iPP的起始结晶温度（ton）提高15.3℃和12.7℃,结晶峰温度（tp）提高17℃和13.7℃,结晶速率加快。两种成核剂都能使球晶细化,使结晶更加均匀化、规整化,从而使结晶度增加。α成核剂（TMA-3）使iPP的拉伸强度、冲击强度和断裂伸长率分别提高到23.43MPa、22.27kJ/m2和788%;β成核剂因主要是改变球晶的形态,形成与α球晶完全不同的β晶型,使iPP的拉伸强度、冲击强度和断裂伸长率的提高比α成核剂显著,分别达到24MPa、32.81kJ/m2和861%。     

α/β复合成核剂对等规聚丙烯结晶形态的影响及非等温结晶动力学

采用偏光显微镜(POM)及示差扫描量热(DSC)法考察了3种α/β复合成核剂NA40/NABW、NA40/HHPA-Ba、NA40/PA-03对成核等规聚丙烯(iPP)的结晶形态及非等温结晶动力学的影响。对成核iPP结晶形态的研究结果表明：α/β复合成核剂的加入能够减小iPP的球晶尺寸。影响α/β复合成核剂成核iPP结晶形态的主要因素是ΔT_Cp（ΔT_Cp为成核iPP结晶峰值温度与iPP结晶峰值温度的差值）,即复合体系中ΔT_Cp较大的成核剂在iPP结晶过程中起主导作用,最终的结晶形态与单独添加这一成核剂时iPP的结晶形态相类似;当两种成核剂的ΔT_Cp接近相同时,两者竞争成核,成核iPP的结晶形态表现为两种成核剂共同作用的结果。因此,通过改变α/β复合成核剂的复合比例即改变两种成核剂的添加浓度,进而改变其ΔT_Cp,可以得到结晶形态完全不同的iPP。采用Caze法对非等温动力学进行了研究,结果表明：添加α/β复合成核剂能够提高iPP的结晶温度,缩短半结晶时间。复合成核剂成核iPP的结晶行为也同样受成核剂ΔT_Cp的影响,复合成核iPP的Avrami指数接近于复合体系中ΔT_Cp较大的成核剂单独添加时iPP的Avrami指数。     

A highly active novel β-nucleating agent for isotactic polypropylene

A highly active novel β-nucleating agent for isotactic polypropylene (iPP), cadmium bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate (BCHE30), was found and its effects on the mechanical properties, the content of β-crystal, and crystallization behavior of iPP were investigated, respectively. The results show that the impact strength and crystallization peak temperature of nucleated iPP are greatly increased, while the spherulite size of nucleated iPP is dramatically decreased than that of pure iPP. The content of β-form of nucleated iPP (k_β value) can reach 87% with 0.1 wt% BCHE30. The Caze method was used to study the non-isothermal crystallization kinetics of nucleated iPP and the crystallization active energy was achieved by Kissinger method.     

A novel highly efficient β‐nucleating agent for isotactic polypropylene

A novel highly efficient β‐nucleating agent for isotactic polypropylene (iPP), hexahydrophthalic barium (HHPA‐Ba), was found and its effects on the mechanical properties, the β‐phase content, and crystallization behavior of iPP were investigated, respectively. The results show that the β‐phase content of nucleated iPP (k_β value) can reach 80.2% with 0.4 wt % HHPA‐Ba. The impact strength and crystallization peak temperature of nucleated iPP are greatly increased. Compared with pure iPP, the impact strength of nucleated iPP can increase 2.4 times. Meanwhile, the spherulite size of nucleated iPP is dramatically decreased than that of pure iPP. The Caze method was used to investigate the nonisothermal crystallization kinetics of nucleated iPP and the crystallization active energy was achieved by Kissinger method. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

长支链聚丙烯诱导β晶成核效应

利用乙烯基聚二甲基硅氧烷/苯乙烯接枝型长支链聚丙烯(PP-g-VS/St)在剪切和快速降温过程中可以诱导形成β晶聚丙烯这一优势,研究了PP-g-VS/St在注塑加工过程中作为高分子β晶成核剂对等规聚丙烯(iPP)结晶温度、晶体结构及力学性能的影响。结果表明改性聚丙烯的结晶温度、β晶相对含量和力学性能随着PP-g-VS/St添加量的增加而增加。当PP-g-VS/St的添加量为50%(质量分数)时,改性聚丙烯的结晶温度相对于纯iPP提高约10℃,β晶相对含量达32.8%,冲击强度、弯曲模量和拉伸强度分别相对于纯iPP提高了355.3%、53.8%和15.9%。这些结果为聚丙烯高分子β晶型成核剂的设计提供了新思路。