原材料对硅烷接枝交联高熔体强度聚丙烯流动性能影响的研究

采用不饱和硅烷为接枝单体,不饱和烯烃为共单体,在双螺杆挤出机上实现均聚型聚丙烯的接枝交联,制得了高熔体强度聚丙烯。实验通过熔体指数(MFR)和凝胶含量的变化研究原材料对改性PP的影响。结果显示,体系中的试剂均严重影响材料的熔体流动性能。在硅烷和共单体共存的条件下,材料的熔体流动性能随引发剂A含量的增加而下降。共单体起到稳定大分子自由基的作用,增加了硅烷的接枝效率和接枝速率,共单体与硅烷最佳摩尔比为1∶1。改性后材料的耐热性、力学性能等均有较大提高。     

硅烷接枝交联法制备发泡用高熔体粘度聚丙烯

以过氧化物为引发剂,不饱和硅烷为接枝单体,不饱和烃类为接枝助剂,并加入交联催化剂,通过反应型双螺杆挤出机一步实现共聚型聚丙烯的接枝和交联;制备出了可用于发泡的高熔体粘度聚丙烯。通过熔体质量流动速率(MFR)和凝胶含量的变化,研究试剂体系对接枝交联改性的作用。结果显示,改性后PP的MFR可降低至0．1 g／ 10min以下,凝胶含量可高达48％以上,体系中各组分都显著影响改性材料熔体的流动性和凝胶含量,缺一不可。随引发剂和硅烷单体含量的增加,体系熔体流动性逐渐降低,凝胶含量增加。而硅烷单体与接枝助剂的最佳量之比为1 :1。通过PP改性前后的力学性能和发泡性能对比研究表明,接枝和交联使改性后PP的耐热性、抗冲击性、拉伸性能均有所改善;而且用改性PP发泡可以获得泡孔均匀、细密,且具有独立泡孔的高质量泡沫塑料。     

一步法硅烷接枝交联改性均聚型聚丙烯的研究

通过反应挤出法一步实现均聚型聚丙烯的硅烷接枝和交联,制备出具有部分交联结构的高熔体强度聚丙烯。通过熔体强度、熔体黏度测试和熔体流动速率(MFR)、凝胶含量的变化研究了试剂体系对接枝交联改性的作用。结果显示,改性PP的MFR可降低至0.5g/10m in以下,熔体强度提高4.1倍,熔体剪切黏度提高1.707倍;加入的助剂体系中的各个组分都是有效和必要的,而且体系各个组分之间有相互协同作用;改性配方中各个组分的用量比显著影响改性PP的熔体流动速率和凝胶含量,当引发剂、接枝单体、接枝助剂的用量比为(0.36~0.54)∶1∶0.38时,可以获得最佳的改性效果。     

反应挤出共混法制备发泡用聚丙烯的研究

采用反应型双螺杆挤出机,以过氧化苯甲酰(BPO)做引发剂,不饱和烯烃为交联助剂,一步实现聚丙烯(PP)与少量低密度聚乙烯(LDPE)的共混、接枝与交联,制备出了具有高熔体黏度的发泡用聚丙烯.研究结果表明,改性后PP的熔体流动速率(MFR)可降至0.1 g/10min以下,体系中有质量含量高达48%以上的凝胶产生,当交联助剂含量与引发剂含量的质量比例约为1.31时,可以获得最佳的改性效果.体系中的引发剂和交联助剂均显著影响改性材料的熔体流动性和凝胶含量,在引发剂质量含量达到0.8%以上时,MFR和凝胶含量变化趋势减缓;差示扫描量热分析(DSC)研究表明,交联使体系中PP相和PE相的结晶速率都下降.对改性后的样品进行发泡实验,结果表明采用反应共混改性PP可获得泡孔细密均匀、穿孔很少的高质量泡沫塑料.     

乙烯基不饱和硅烷交联改性PP制备HMSPP

采用乙烯基不饱和硅烷接枝交联复合改性聚丙烯(PP)制备高熔体强度聚丙烯(HMSPP)。由正交试验可知,过氧化二苯甲酰对乙烯基长链不饱和硅烷交联改性PP制备的HMSPP熔体强度的影响最显著。通过优化实验得到的HMSPP熔体强度为19.9cN。二乙烯基苯(DVB)作为助交联剂可有效提高HMSPP的熔体强度,w(DVB)不宜超过1.0%。苯乙烯质量分数为1.0%时,对HMSPP链断裂抑制较明显。采用复合改性PP制备的HMSPP的断裂拉伸应变略有下降,熔体强度相比PP提高4.7倍,悬臂梁缺口冲击强度提高0.82倍。     

发泡用高熔体强度聚丙烯的研究

以过氧化苯甲酰(BPO)为引发剂,在同向双螺杆挤出机上对聚丙烯(PP)进行硅烷交联,制备了高熔体强度聚丙烯(HMSPP),然后制得高发泡倍率的PP制品.实验对改性PP的熔体强度、力学性能、热性能和发泡性能进行了表征.结果表明:自制HMSPP的熔体强度是纯PP的5.01倍,力学性能和耐热性与纯PP相比均有较大提高,可用于成型高发泡倍率制品.     

高熔体强度聚丙烯结晶行为及其发泡性能

在双螺杆挤出机上采用一步硅烷接枝交联法制得了高熔体强度聚丙烯,采用DSC、偏光显微镜研究高熔体强度聚丙烯的结晶行为、结晶结构和结晶形态.研究结果表明:高熔体强度聚丙烯的结晶温度明显增加,硅烷接枝交联促进了聚丙烯的异相成核,使晶粒细化,高熔体强度聚丙烯的发泡效果明显优于普通PP.     

一步法硅烷接枝交联改性聚丙烯的研究

采用反应挤出法一步实现聚丙烯（PP）的硅烷接枝和交联改性，制备出了具有部分交联结构的高熔体强度PP。通过改性前后红外光谱、熔体流动性能、凝胶含量、结晶行为、力学性能和发泡性能的变化考察了改性对材料性能的影响。结果表明，一步法改性后PP大分子中引入了硅烷接枝交联结构，使熔体强度、熔体黏度提高，熔体流动速率显著降低，并且体系中出现了高达48％的凝胶；交联结构的引入使PP的结晶速率减缓；改性后材料的力学性能有所提高，而发泡性能大大改善，可以获得高质量的泡沫塑料。     

硅烷固相接枝熔融法制备交联聚丙烯

以硅烷为接枝单体，采用固相接枝法得到硅烷接枝聚丙烯，将接枝产物水解熔融得到交联聚丙烯（MPP），研究了接枝单体和引发剂种类对聚丙烯（PP）固相接枝率的影响，选择相同条件下接枝率最大时所用单体3-（甲基丙烯酰氧）丙基三甲氧基硅烷（MAPTMS）和引发剂过氧化苯甲酸叔丁酯（TBPB）考察后续交联产物性能，进一步研究了MAPTMS和TBPB加入量对MPP熔体流动速率（MFR）、凝胶含量、结晶温度、熔融温度、弹性模量和复数黏度的影响。结果表明：与纯PP相比，MPP的MFR降低，凝胶含量、弹性模量、复数黏度均升高，当MAPTMS与TBPB加入量分别为0.06,4.00 mL时，MPP的MFR降至2.4 g/10 min，凝胶含量高达54%，弹性模量和复数黏度均达到最大；与纯PP相比，MPP显示出更高的结晶温度，更低的结晶温度，产物不发生相分离。     

双单体固相接枝制备高熔体强度聚丙烯

采用一种有机溶胀剂作为聚丙烯(PP)基体的溶胀剂及接枝单体的溶剂,协助1,6-己二醇二丙烯酸酯(HDDA)及苯乙烯(St)固相接枝PP。考察了单体用量、引发剂用量、反应条件和溶胀条件对接枝反应的影响。用红外光谱和热重分析法对接枝产物的结构及性能进行分析。结果表明:接枝产物的接枝率、熔体强度相对于未溶胀时均有所提高。在优化反应条件下,即按照PP,HDDA,St与偶氮二异丁腈的质量比为100.00∶4.00∶1.82∶0.30投料,用6.6 g溶胀剂在40℃溶胀3 h,85℃反应2.0 h,接枝产物的熔体强度增加到2.51 kPa.s(为原料的4.48倍)。热稳定性与原料相比明显增强。     

Preparation of Silane-Grafted and Moisture Cross-Linked Low Density Polyethylene: Part I: Factors Affecting Performance of Grafting and Cross-Linking

In the present work, the silane grafting and water cross-linking of low density polyethylene (LDPE) were investigated. The grafting reaction was carried out in an internal mixer and polyethylene cross-linking was done in hot water. The effect of silane, peroxide, catalyst, carbon black, cross-linking time, and cross-linking temperature on the grafting and cross-linking processes are reported. Vinyl trimethoxy silane (VTMO) and di-cumyl peroxide (DCP) were selected as grafting agent and initiator respectively. Silane grafting on polyethylene was determined using Fourier transform infrared (FTIR) spectroscopy and torque monitoring of the mixer. Absorption peak due to –Si–OCH₃ groups in FTIR and torque increasing due to silane grafting in the mixer illustrated that silane-grafting reactions occurred. The FTIR data demonstrated that the extent of silane grafting was increased as the concentration of silane and peroxide was increased. Thermogravimetry analysis (TGA) determined that the thermal stability of LDPE increased by increasing the amount of silane grafting. Gel fraction increased with silane and peroxide concentration. As the percent of of catalyst increase the time scale for specified gel content shifted to shorter times. Incorporation of carbon black into LDPE decreased the extent of silane grafting and gel fraction. Water temperature increasing in cross-linking stage reduced the time to maximum degree of cross-linking.     

Mechanism of a one-step method for preparing silane grafting and cross-linking polypropylene

A high-melt-strength polypropylene (HMSPP) with partially cross-linking, modified from a normal isotactic polypropylene (IPP), is prepared by a one-step silane grafting and cross-linking method in a twin-screw reactive extruder. The melt grafting and cross-linking of IPP is achieved by using vinyl unsaturated silane with long chain as a grafting monomer, benzoyl peroxide (BPO) as an initiator, styrene as a coagent, and a little water as a catalyst for cross-linking. By analyzing the difference of the Fourier transformed infrared spectra between raw and modified PP, comparing the variety of the melt flow rate (MFR) and gel percentage between cured and uncured PP samples, and investigating the effect of catalyst on the MFR and gel percentage of modified PP, the partially cross-linked polypropylene in the way of one-step reactive extrusion has been verified. We put forward the reactive mechanism of one-step method based on our experimental results. In this mechanism, the hydrolysis and condensation of silane occur first through the catalysis of water and a compound with two or more double-bond is formed, which then the compound reacts with PP macroradicals to form the partially cross-linked PP. POLYM. ENG. SCI., 47:1004–1008, 2007. © 2007 Society of Plastics Engineers     

发泡高熔体强度聚丙烯研究进展

高熔体强度聚丙烯具有优异的物理机械性能,其发泡制品拥有广泛的用途。文章综述了制备高熔体强度聚丙烯的制备方法,主要有直接聚合法、辐射接枝交联法、硅烷接枝交联法等。硅烷接枝交联法成本适中、产品质量优异,是目前最有希望的改性技术。综述了发泡高熔体强度聚丙烯材料的应用。     

A reactive extrusion process for the free radical grafting of silanes onto polypropylene: Effects of processing conditions and properties of water cross‐linked silane‐grafted polypropylene

Silane grafting and water cross‐linking of polypropylene (PP) are a recent method to modify its properties, such as melt strength, heat, and chemical resistance. This work aims at grafting silanes onto PP by reactive extrusion. The occurrence of the grafting of silane onto PP was confirmed by Fourier transform infrared (FTIR) and a method based on FTIR was developed to quantify the amount of polymerized silane and that of silane grafted onto PP. The molar mass of the silane‐grafted PP and its melt viscosity were also measured. A multiobjective optimization strategy was used to study the effects of processing conditions on the quality of the silane‐modified PP. It was concluded that to maximize the amount of silane grafted on PP and minimize the amount of polymerized silane and the decrease in PP chain scission, screw speed and barrel temperature should be low and feed rate high. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Thermal and crystallization behavior of silane‐crosslinked polypropylene

Silane‐crosslinked polypropylene (PP) has been prepared first by the grafting of silane onto the backbone of PP in a melt process and then by crosslinking in warm water. The effects of type and concentration of silane and peroxide on the silane grafting on PP were investigated. The thermal behavior of the silane‐crosslinked PP was studied by thermogravimetric (TG) and differential scanning calorimetry (DSC) methods. TG results show that PP prepared via silane crosslinking increases its thermal stability greatly. It has been found from DSC measurements that the crystallization temperatures, ie the onset temperature and peak temperature of the exotherm of the silane‐crosslinked PP, increase compared with those of the pure PP. The silane crosslinking hardly changes the crystallinity degree of PP. The crystallization behavior of the silane‐crosslinked PP was also studied by wide‐angle X‐ray diffraction analysis. Copyright © 2004 Society of Chemical Industry     

Properties and Characterization of Filled Poly(Propylene) Composites Crosslinked Through Siloxane Linkage

Summary: The silane‐grafting and water‐crosslinking of poly(propylene) (PP) and its composites with calcium carbonate are described. Particular consideration is made on the properties and characterization of the grafted‐ and crosslinked‐products. Silane‐grafting of the polymers was performed in the melt by the use of vinyltrimethoxysilane and dicumyl peroxide. The results show that during the grafting process, PP chain‐scission was accompanied as a side reaction. Peroxide concentration was found to be a major factor in determining the extents of grafting and PP degradation. After conducting a crosslinking reaction, the degree of crosslink determined from the direct measurement of gel content and indirect method by evaluating FTIR data was compared. The effects of silane crosslink on the thermal and mechanical properties of the PP composites were discussed. A combined effect of filler and silane crosslink network in enhancing composite modulus, tensile stress, heat distortion, and decomposition temperatures is evident.

Formation of stable siloxane linkages.     

PP-g-Si对PP／GF的增容作用

制备了硅烷接枝聚丙烯(PP-g-Si)，研究了PP-g-Si作为聚丙烯／玻纤(PP／GF)复合体系的界面相容剂对界面结合和力学性能的影响，并与马来酸酐接枝聚丙烯(PP-g-MAH)的增容效果进行了比较。结果表明，PP-g-Si对PP／GF体系有增容作用，不仅可以改善PP／GF复合体系的拉伸强度，而且可以改善其韧性。硅烷接枝聚丙烯可以降低PP／GF复合体系的最大扭矩。玻纤的加入可以提高聚丙烯的热变形温度，硅烷接枝聚丙烯对PP／GF复合体系的热变形温度有稍微改善。扫描电镜观察表明，玻纤与基体间具有强有力的界面结合，硅烷接枝聚丙烯的增容效果优于马来酸酐接枝聚丙烯。     

高熔体强度聚丙烯的研究进展

综述了国内外采用接枝与交联改性法制备高熔体强度聚丙烯(HMSPP)的研究进展。分析了目前采用接枝与交联改性PP所存在的问题,指出硅烷接枝交联改性技术的成本适中,产品质量好,是获得HMSPP的最有希望的改性技术。     

聚苯乙烯-铂络合物对不饱和化合物硅氢加成反应的催化活性

合成了聚苯乙烯－铂络合物,研究了它对不同类型不饱和化合物与甲基一氯硅烷及甲基氢二乙氧基硅烷硅氢加成反应的催化特性。结果表明,其催化活性和选择性受不饱和化合物的电子效应和空间位阻效应以及硅氯化试剂结构等多种因素的影响。聚苯乙烯－铂络合物对连有一个取代基的苯乙烯、丙烯酸甲酯与 氯硅烷及甲基氢二乙氧基硅 硅氢加成反应具有很高的催化活性,对连有两个取代基的甲基丙烯酸甲酯无催化活性;该催化剂可选择性催化烯丙