硅烷接枝交联聚乙烯的研究

用不同结构的乙烯基硅烷与聚乙烯进行熔融接枝及水解缩合交联反应，通过对 支物的结构表征，交联行为以及交联前后结晶性质，高温应力－应变曲线的测定，研究了不同结构的乙烯基硅烷对硅与聚乙烯的接枝反应和交联反应的影响。     

LLDPE硅烷接枝交联反应的研究

选用线性低密度聚乙烯(LLDPE),接枝单体乙烯基三甲氧基硅烷(VTMOS),以过氧化二异丙苯(DCP)为引发剂,采用熔融挤出法对LLDPE进行硅烷接枝,然后在催化剂二月桂酸二丁基锡(DBTDL)存在下进行水解交联反应.研究了凝胶含量随水解时间的变化关系.通过改变VTMOS、EGP用量,系统地考察了对交联LLDPE的凝胶含量、力学性能以及结晶性能的影响.结果表明:凝胶含量在水解初期随时间的增长而快速增加,10h后凝胶含量趋于平缓.硅烷接枝交联LLDPE,由于其三维网络结构的存在,使得力学性能显著提高,其熔点和结晶度则都有不同程度的降低.     

不饱和硅烷熔融挤出接枝聚乙烯的研究

采用熔融挤出法对低密度聚乙烯进行硅烷接枝,然后在催化剂二月桂酸二丁基锡存在进行水解交联,对接枝产物的熔体流动速率和交联样品的凝胶率的影响因素进行了系统的研究,接枝单体为乙烯基三乙氧基硅烷,主要引发剂为过氧化二异丙苯。     

硅烷接枝交联对MgO/高密度聚乙烯复合材料性能的影响

采用两步法反应挤出工艺制备硅烷接枝交联MgO/高密度聚乙烯(MgO/HDPE)导热复合材料,研究了硅烷接枝、交联对MgO/HDPE复合材料的结晶性能、力学性能、耐热性、导热性能的影响,并利用FTIR和DSC对其接枝交联、结晶情况进行表征。结果表明,交联MgO/HDPE复合材料的拉伸强度、缺口冲击强度、热变形温度(HDT)分别由未交联时的20.41 MPa、1.875kJ/m~2和74.6℃提升到27.24 MPa、7.875kJ/m~2和83.5℃,并且热导率保持基本不变0.447 W/(m·K)。     

硅烷交联聚乙烯/纳米蒙脱土复合材料的研究

以聚乙烯接枝马来酸酐为载体树脂制备纳米蒙脱土母料，在双螺杆挤出机中制备了硅烷交联聚乙烯／有机蒙脱土复合材料，研究了有机蒙脱土含量对硅烷交联聚乙烯接枝料力学性能、热性能以及交联料交联度的影响，并使用X射线衍射(XRD)、透射电子显微镜(TEM)研究了复合材料的微观结构。结果表明：硅烷交联聚乙烯接枝料的力学性能得到了提高，拉伸强度最大提高了近30％，断裂延伸率基本不变；维卡软化温度及热稳定性有一定提高；交联料的交联度有所下降，但可以通过延长交联时间弥补。XRD和TEM表明硅烷接枝聚乙烯大分子能够实现对有机蒙脱土的插层。     

Study on Crosslinking Kinetics of PVBC! by Real-time FTIR

利用傅里叶变换红外光谱仪(FTIR)在线追踪聚乙烯基苄基氯(PVBCl)与N,N,N′,N′-四甲基-1,6-己二胺(TMHDA)的交联反应历程,考察了反应时间与温度对交联程度的影响.实验结果表明,随着反应时间的延长,交联程度先迅速增大,而后趋于平缓直至不变；反应温度越高,交联程度越大.对反应进行动力学的研究计算结果显示,该交联反应的反应级数n=4,表观活化能Ea=97.2kJ/mol.     

LDPE固相接枝MAH及其产物在PA66/LDPE共混物中的应用

采用固相接枝法制备低密度聚乙烯(LDPE)接枝马来酸酐(MAH),并利用FT-IR表征了接枝产物的化学结构.研究了反应温度、引发剂用量、单体用量、界面剂用量以及反应时间对产物接枝率和交联度的影响.同时考察了接枝产物(LDPE-g-MAH)对聚酰胺66/低密度聚乙烯(PA66/LDPE)共混物的力学性能和形态的影响.结果...     

消息报道

硅烷交联聚乙烯电缆料通过技术鉴定由江苏石油化工学院研制开发的硅烷交联聚乙烯电缆料，最近在常州通过了江苏省科委组织的技术鉴定。硅烷交联聚乙烯电缆料由聚乙烯、乙烯基硅烷及特殊催化剂、早期交联抑制剂等经过熔融接枝工艺生产而成。较之传统的Sioplas工艺，该技术在乙烯基硅烷的复配、使用及防止产物的早期交联方面有了重要的突破。在熔融接校设备和接枝工艺条件的设定方面也有独到之处。产品质量经国家电线电缆质量检验中心检测，各项技术性能指标达到GB12706．91，10KV以下电缆要求，挤出加工性能及热延伸性能优于韩国LG公司同…     

在线红外光谱法研究聚乙烯基苄基氯的交联反应动力学

利用傅里叶变换红外光谱仪(FTIR)在线追踪聚乙烯基苄基氯(PVBCl)与N,N,N′,N′-四甲基-1,6-己二胺(TMHDA)的交联反应历程,考察了反应时间与温度对交联程度的影响。实验结果表明,随着反应时间的延长,交联程度先迅速增大,而后趋于平缓直至不变;反应温度越高,交联程度越大。对反应进行动力学的研究计算结果显示,该交联反应的反应级数n=4,表观活化能Ea=97.2kJ/mol。     

无水AlCl_3作用下EPDM的交联与接枝性能

以无水AlCl3为催化剂,在溶液体系考察了温度、催化剂用量、溶剂品种等因素对乙丙三元橡胶(EPDM)交联与接枝性能的影响。结果显示,无水AlCl3可以引发EPDM间产生交联反应;温度较低时,EPDM交联反应困难,但乙丙三元橡胶与聚苯乙烯(PS)间产生了接枝反应;在苯与二甲苯溶剂中不易形成活性正碳离子;催化剂用量增大,凝胶含量与交联密度增大;PS进入EPDM凝胶网络,使PS相热稳定性提高,玻璃化温度提高。     

聚烯烃的硅烷交联技术

综述了硅烷接枝／交联烯烃的原理，原材料及其用量范围，工艺，影响因素及应用。     

交联聚乙烯滚塑容器专用料的研制

采用过氧化物交联方法研究了交联聚乙烯的工艺条件和性能,探讨了交联反应对交联聚乙烯力学性能和交联度的影响,并用差示扫描量热仪表征了交联聚乙烯的熔融行为。结果表明:交联剂双2,5用量(质量分数)为1.5%,交联温度为180℃,交联时间为5 min时,交联聚乙烯的交联度达到74.2%,拉伸强度为29.0MPa,断裂伸长率为480%,其熔融峰温度为108.7℃。     

Methods and benefits of crosslinking polyolefins for industrial applications

The silane grafting route to the crosslinking of polyolefins can open up wide areas of application not easily attained by the conventional techniques of peroxide addition or irradiation. The thermal limitations on processing and cure rates imposed by the former; and the high capital cost, thickness and shape limitations imposed by the latter are dispelled when a two step grafted system is employed. The technology involves the chemical grafting of an easily hydrolysable vinyl silane onto a polyolefin chain, crosslinking being achieved by post-hydrolysis condensation to yield a siloxane linkage. The technique can be applied to aliphatic polymers and copolymers ranging in stiffness from HDPE to EPR. As well as property improvements in creep, environmental stress cracking resistance, impact, chemical and crack growth resistance; the materials retain a useful strength and exhibit resistance to flow and irreversible distortion above the crystalline transition temperature (where applicable). The years of experience accrued by AEI in the formulation, manufacture and handling of silane grafted materials is now resulting in the production and development of a wide range of specialised high performance materials.This paper outlines property levels attainable with specific reference to well established as well as developing areas of application. A wide range of products is covered including electrical cable insulation, hot water pipe, adhesives, floorings, foams, heat shrink products and packaging; the application of crosslinking to all of which can be seen to be facilitated by the grafted silane route and more specifically by the thermoplastic processability afforded by this route.     

Grafting of PEG onto lanthanum hydroxide nanowires

Lanthanum hydroxide nanowires were synthesized by hydrothermal method. To reduce the aggregation among lanthanum hydroxide nanowires, an effective surface modification method was proposed by grafting polyethylene glycol (PEG) onto lanthanum hydroxide nanowires. That is, the surface of lanthanum hydroxide nanowires was firstly treated with aminopropyltrimethoxysilane (APTMS), which is a silane coupling agent and introduces functional amino group onto the surface of lanthanum hydroxide nanowires, followed by grafting reaction with PEG-COCl. The obtained nanocomposite was characterized by Fourier Transform Infrared Spectroscopy (FT-IR), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM). Results of FT-IR and TGA showed that the PEG chains had been covalently bonded to the surface of lanthanum hydroxide nanowires. It was found that the increase of molecular weight of the grafted PEG could increase the grafting percentage and hence promote the dispersibility.     

偶联剂改性纳米硅溶胶的接枝率及稳定性

为改善纳米硅溶胶与有机物间的亲和性及分散稳定性,用硅烷偶联剂对碱性纳米硅溶胶进行表面接枝改性。分析了偶联剂用量、反应温度和反应时间对接枝率、分散稳定性及微观形貌的影响。结果表明,偶联剂KH560更适合做碱性纳米硅溶胶的表面改性剂,且制备的改性纳米硅溶胶表面可接枝KH560;从接枝率变化梯度来看,KH560用量对接枝率影响最大,当KH560含量为12.5%、反应时间为5h、反应温度为60℃时,改性接枝率及Zeta电位绝对值最高,分别为7.37%和55.6mV。     

ABS高胶粉接枝马来酸酐及其对ABS/PET合金性能的影响

采用溶液法制备了丙烯腈-苯乙烯-丁二烯高胶粉(ABSHR)接枝马来酸酐(MAH),使用红外光谱表征了ABSHR接枝马来酸酐(ABSHR-g-MA)的结构;探究了MAH、BPO、ABSHR的用量及反应温度和反应时间对ABSHR-g-MA接枝率的影响,以及ABSHR-g-MA作为增容剂对ABS/PET合金性能的影响。结果表明:ABSHR-g-MA接枝率随着MAH和BPO用量的增加而增加,但添加量过高时,接枝率增加缓慢或有所降低;适当升高反应温度和延长反应时间有利于接枝反应的发生;ABSHR-g-MA作为ABS/PET合金增容剂,随着ABSHR-g-MA接枝率的增加缺口冲击强度和断裂伸长率明显增加,分别提高了127%和121%,而拉伸强度和弯曲强度稍有降低;同时随ABSHR-g-MA接枝率的增加合金的耐热性能提高,熔融流动速率有所降低。     

Synthesis and photopolymerization kinetics of linear alicyclic urethane acrylate macromonomer in presence of reactive diluents

This study deals with the photopolymerization of a macromonomer in the presence of reactive diluents using Photo Differential Scanning Calorimetry or Photo DSC. The kinetic profiles of these systems showed that the rate of photopolymerization rapidly increases at very early stages of the reaction. The rate of reaction was further found to increase with the addition of crosslinking agents. The addition of trifunctional crosslinking agent to the macromonomeric formulation resulted in a higher polymerization rate and conversion than that of a difunctional crosslinking agent. From the heat flow profiles, the kinetic parameters such as induction time, time to attain peak maximum, rate of maximum polymerization, and final conversion were noted for all the formulations. The initiation of photopolymerization was found to depend on the functionality while the in situ viscosity controlled the time scale for reaction diffusion which resulted in varying levels of conversions. Other parameters such as effect of temperature and concentration of photoinitiator on photocuring kinetics are also discussed.