超临界CO2协助多单体接枝改性聚丙烯

利用超临界CO2作为溶胀剂和携带剂,使小分子单体马来酸酐和苯乙烯单体(MAH与St)及引发剂过氧化苯甲酰(BPO)插嵌进入聚丙烯(PP)基质中,然后在100℃条件下反应4 h得到接枝产物。研究了不同超临界CO2条件及引发剂浓度对接枝率的影响,固定超临界流体压力,改变温度,42℃为最佳温度,接枝率达到2.2%;固定温度,改变压力,10 MPa为最佳条件,接枝率为2.3%。对样品的FT-IR和SEM分析表明,共单体确实接枝到了PP分子链上,而DSC分析表明,随着接枝率的提高,材料的熔点(Tm)及表观结晶度(Ca)下降。这可能是接枝破坏了PP链结构的规整性,同时扩大了分子链间的距离所致。     

甲基丙烯酸缩水甘油酯/苯乙烯固相接枝聚丙烯

以苯乙烯(St)为共单体，过氧化苯甲酰(BPO)为引发剂，采用固相接枝反应将甲基丙烯酸缩水甘油酯(GMA)接枝到聚丙烯(PP)大分子链上。研究了反应时间、单体用量、引发剂用量等因素对接枝率的影响。采用凝胶渗透色谱(GPE)测定了PP和接枝物PP-g-(GMA-St)的分子量和分子量分布。结果 表明固相接枝PP反应条件为[GMA／[St]=2，反应3．5h，加入GMA 10份，BPO 5份。St的加入有助于GMA与PP的接枝，同时在一定程度上抑制了PP的降解。     

聚丙烯熔融接枝马来酸酐反应机理的研究

改变聚丙烯（PP）熔融接枝马来酸酐（MAH）反应中的单体和引发剂的浓度以及添加适当助剂,考察了接枝产物的接枝率和恒定剪切应力（600kPa)及温度（210℃）下的剪切粘度,验证了作先前所提出的PP熔融接枝MAH的反应机理。即：在PP熔融接枝MAH的过程中,过氧化物自由基在熔融接枝过程中直接引发MAH单体及MAH单体在聚丙烯的大分子链段发生β断裂前直接被其引发而产生的接枝反应是影响产物的接枝率和分子量的关键。在不改变单体和引发剂浓度的情况下,降低过氧化物自由基在熔融接枝过程中直接引发MAH单体反应的程度而提高聚丙烯的大分子自由基直接引发MAH单体的反应趋势,是提高接枝产物接枝率和分子量的有效途径。     

马来酸酐-苯乙烯熔融接枝聚丙烯的影响因素及其性能研究

用单螺杆挤出机制备了马来酸酐 (MAH) 苯乙烯 (St)对聚丙烯 (PP)的多组分单体自由基熔融接枝体系 .研究证实了当两种单体物质的量比约为 1∶1时 ,接枝物的接枝率最高 ,而熔体流动速率 (MFR)最大 .对反应体系影响因素的研究表明单体用量和引发剂用量对不同单体用量比的系列接枝物的接枝率会产生不同的影响 ;另外 ,单体用量增加 ,接枝物的MFR减小 ,过氧化二异丙苯 (DCP)用量增加 ,接枝物的MFR增加 .对多单体熔融接枝聚丙烯PP g (MAH co St)的力学性能研究发现 ,选用合适的单体用量比、单体用量和DCP用量时 ,所制备的接枝物可具有与纯PP相当或更佳的力学性能     

双单体固相共聚改性聚丙烯技术及其机理研究

在马来酸酐(MAH)固相接枝改性聚丙烯(PP)的过程中加入合适比例的异氰脲酸三烯丙酯(TAIC)作为共聚单体,可以大大提高MAH在PP上的接枝率,同时可以有效抑制在普通固相接枝过程中PP的严重降解,得到了性能较好的高极性PP.与普通固相接枝法与熔体接枝法对比,双单体固相共聚接枝改性PP是一种得到高极性PP的有效方法.本文同时对双单体在固相接枝反应中的作用机理进行了探讨.     

纤维素纳米纤维接枝聚(N-异丙基丙烯酰胺)水凝胶的制备与表征

将具有温度响应的聚N-异丙基丙烯酰胺(PNIPAm)接枝到电纺纤维素纳米纤维膜上,制备温度响应型纤维素接枝聚N-异丙基丙烯酰胺(PNIPAm-g-Cell)纳米纤维水凝胶。 研究接枝单体(N)与纤维素(c)的质量比、反应温度、反应时间和引发剂浓度对产物接枝率、溶胀性和形貌的影响。 结果表明,最佳聚合反应条件为m(N):m(c)=15:1、反应温度40 ℃、反应时间3 h、引发剂浓度为10 mmol/L,得到PNIPAm-g-Cell接枝率和溶胀率分别为35%和31%。 与PNIPAm相比,PNIPAm-g-Cell水凝胶的低临界相转变温度(LCST)显著升高,说明亲水性纤维素的引入改变了体系的亲疏水平衡。 去溶胀动力学测试表明,0.5 min内接枝率为25%和35%的水凝胶保水率分别降低至93%和61%。 说明接枝率越高PNIPAm-g-Cell水凝胶对温度的响应速度越快,对温度越敏感。     

在超临界CO_2中进行的PP固相接枝改性研究进展

由于性价比高,聚丙烯(PP)成为增长最快的通用塑料,在汽车工业、家用电器和管材方面得到了广泛地应用。然而由于聚丙烯自身的非极性限制了其在某些领域的应用,向聚丙烯主链上接枝极性单体是改善其极性的有效方法。常用的接枝改性方法有:溶液接枝、熔融接枝、等离子体处理、表面可控活性聚合以及超临界CO2状态下接枝等。其中超临界CO2由于溶解单体能力强,对聚合物基体也有很好的溶胀能力,且阻燃性好、无毒以及价格相对低廉,克服了传统接枝方法存在的操作工艺复杂,溶剂不易回收等缺点,得到了广泛研究。本文从超临界CO2协助固相接枝改性机理、接枝单体的选择、影响过程的因素以及超临界CO2协助固相接枝的应用等方面出发,系统阐述了超临界CO2协助PP固相接枝改性近些年来的研究概况。     

GMA/苯乙烯多组分单体接枝聚丙烯结晶行为研究

使用差示扫描量热计 (DSC)研究了甲基丙烯酸缩水甘油酯 苯乙烯 (GMA St)多单体熔融接枝聚丙烯[PP g (GMA co St) ]的等温和非等温结晶行为 ,用偏光显微镜观察了结晶的形态 ,并利用Avrami方程对其结晶动力学进行了分析 .研究发现接枝聚丙烯的结晶模式与PP相似 ,属于异相成核控制的球晶三维生长 ;但接枝聚丙烯的结晶温度 (Tc)显著提高 ,幅度高达 16～ 19℃ ,总结晶速率与纯PP相比明显加快 .接枝聚丙烯上GMA co St支链的存在 ,降低了成核界面自由能 ,促进了聚丙烯结晶的异相成核 .在接枝率不太高的情况下 ,随着接枝率的提高 ,接枝聚丙烯的结晶温度升高 ,总结晶速率加快 .在高接枝率范围内 ,随着接枝率的提高 ,接枝PP的Tc 不再升高 ,且由于接枝链的增长严重阻碍了球晶生长 ,导致接枝PP的总结晶速率反而随接枝率的升高而下降     

pp-g-aa接枝共聚物的制备及表征

以部分预辐照聚丙烯(rPP)作为聚丙烯反应挤出接枝丙烯酸(AA)的引发剂,制备了PP-g-AA接枝共聚物。考察了预辐照剂量、预辐照聚丙烯用量以及单体浓度等因素对接枝反应的影响。采用红外光谱、差热扫描量热仪和偏光显微镜等测试技术对接枝产物的形态、结构及性能进行了研究。结果表明,这种新的PP-g-AA共聚物制备方法能有效抑制聚丙烯的降解并获得较高力学性能的接枝产物。研究发现,当rPP的预辐照剂量为4 kGy,反应原料的组成为m(PP)∶m(rPP)∶m(AA)=90∶10∶0.8时,得到的产物有较高的接枝率(0.19%),并且具有相对最佳的力学性能;这种接枝产物与铝板有很强的粘接效果,其剥离强度达4.88 kN/m。     

聚丙烯接枝改性及其挤出发泡研究

以有机过氧化物为引发剂,以双螺杆挤出机为反应器,将线型不饱和聚酯(ULP)接枝到聚丙烯(PP)分子链上。通过FTIR、DSC及凝胶含量测试,对MPP的结构和性能进行了研究,表明PP发生了接枝反应;泷变性能和熔体流动速率(MFR)测定表明,接枝反应有效地改善了PP流变性能,用双螺杆挤出机对未接枝和接枝的PP进行了发泡研究,SEM分析表明接枝PP具有更好的发泡效果。     

Study on grafting of different types of acrylic monomers onto natural rubber by γ-rays

 A comparative study of various acrylic monomers for grafting onto natural rubber was done. The stability of natural rubber latex (NRL) against coagulum with monomer, mechanical properties of grafted rubbers and percent of grafting were investigated. The NRL with monomers, methylacrylate (MA), ethylacrylate (EA) and n-butylacrylate (n-BA), is unstable but it is stable with methyl methacrylate (MMA), n-butyl methacrylate (BMA) and cyclohexyl methacrylate (CHMA). The mechanical properties and degree of grafting attained a maximum at a total radiation dose of 4 kGy. The values of tensile properties of MMA and CHMA grafted rubbers are almost similar, and higher than those of BMA grafted rubbers. On the other hand, the degree of grafting for CHMA is higher than those of MMA and BMA grafted rubbers. The infrared (IR) spectra of monomer grafted natural rubber were also studied.     

生物基超韧聚乳酸复合材料的制备与性能

采用来源于可再生资源的聚醚酰胺弹性体（PEBA）增韧聚乳酸（PLA）制备超韧聚乳酸（PLA/PEBA-GMA）复合材料.为了提高PEBA与PLA之间的相容性,选择极性单体甲基丙烯酸缩水甘油酯（GMA）、共接枝单体乙烯基吡咯烷酮（NVP）及引发剂过氧化二异丙苯（DCP）对PEBA进行接枝改性制备PEBA-GMA.研究了接枝单体组分的用量（m/g）对PLA/PEBA-GMA复合材料性能的影响.研究发现,随着接枝单体组分用量的提高,复合材料的缺口冲击强度逐渐增大,当接枝单体组分GMA,NVP和DCP的用量分别为2.5,2.5和0.25 g时,复合材料的冲击强度高达88.6 kJ/m²,断裂伸长率为164.1%.研究表明,在熔融共混过程中,聚乳酸的端基（—OH和—COOH）与PEBA-GMA上环氧基团发生反应,有效改善两相间的界面相容性,随着接枝单体组分比例的提高,分散相PEBA-GMA的粒子尺寸逐渐减小且分布均匀.     

Radiation-induced graft copolymerization of N-vinyl carbazole and methyl methacrylate onto cellulose acetate film

N-Vinyl carbazole methyl methacrylate, and the binary mixtures of these monomers were grafted onto cellulose acetate films by taking recourse to Co-60 simultaneous irradiation grafting technique. The effect of various parameters (e.g., solvents, radiation dose, compositions of the monomers, and concentration of the monomers) on the extent of grafting in unitary and binary systems were studied. The optimum conditions for grafting were evaluated. The sensitizing effect of one monomer in the presence of other in the binary system was identified. The relative molecular reactivity and reactivity ratios were computed and these were used in explaining sensitization and the effect of monomer compositions on the extent of grafting in the binary system.     

Surface-initiated ring-opening metathesis polymerization in the vapor phase: an efficient method for grafting cyclic olefins with low strain energies

Surface grafting of cyclic olefins with low strain energies, including cyclopentene (CP), 1,4-cyclohexadiene (CHD), cycloheptene (CHP), cis-cyclooctene (CO), cis,cis-1,5-cyclooctadiene (COD), 1,3,5,7-cyclooctatetraene (COT), cyclododecene (CD), and trans,trans,cis-1,5,9-cyclododecatriene (CDT), was explored using ring-opening metathesis polymerization in the vapor phase. These monomers do not polymerize when SiROMP is carried out in solution because of pronounced chain transfer on surfaces where chains are in close proximity to one another. In the vapor phase, however, chain transfer is suppressed at the solid-vapor interfaces, which permits the polymerization of most of these monomers. A minimal required strain energy of 2.2 kcal/mol was determined in this study, which is significantly lower than the estimated 13.3 kcal/mol for SiROMP carried out in solution, indicating that the enhancement in monomer polymerizability is significant using the vapor-phase approach. A series of polyalkenamers with a controlled fraction of unsaturation from 8 to 50% along the polymer backbone were grafted to solid substrates. It was observed that the logarithm of the largest grafted layer thickness obtained before the removal of chain-transfer products, which correlates with the extent of polymerization, scales with the monomer strain energy. This confirms that the release of ring strain is the thermodynamic driving force for SiROMP. It was also found that although chain transfer is suppressed in the vapor phase it is important in monomer/polymer systems where the fraction of unsaturated bonds is high. In these cases, the grafted polymer thickness is dominated by chain transfer rather than the monomer strain energy. A quantitative relationship is established for estimating the graft thickness of a particular monomer using its strain energy and fraction of unsaturated bonds in the monomer.     

Hydrophilic/hydrophobic character of grafted cellulose

Vinyl monomers with long paraffin chains were grafted onto two kinds of cellulose (cotton and cotton linter) by direct irradiation grafting technique. The effect of dose, monomer structure and concentration, as well as homopolymer suppressor (styrene) concentration on the grafting yield was studied and the optimal grafting conditions were established. Grafting decreased the swelling of the samples in water and increased their polymer compatibility in polypropylene matrix.     

Tailoring the surface properties of poly(dimethylsiloxane) microfluidic devices

Poly(dimethylsiloxane) (PDMS) is an attractive material for microelectrophoretic applications because of its ease of fabrication, low cost, and optical transparency. However, its use remains limited compared to that of glass. A major reason is the difficulty of tailoring the surface properties of PDMS. We demonstrate UV grafting of co-mixed monomers to customize the surface properties of PDMS microfluidic channels in a simple one-step process. By co-mixing a neutral monomer with a charged monomer in different ratios, properties between those of the neutral monomer and those of the charged monomer could be selected. Mixtures of four different neutral monomers and two different charged monomers were grafted onto PDMS surfaces. Functional microchannels were fabricated from PDMS halves grafted with each of the different mixtures. By varying the concentration of the charged monomer, microchannels with electrophoretic mobilities between +4 x 10(-4) cm2/(V s) and -2 x 10(-4) cm2/(V s) were attainable. In addition, both the contact angle of the coated surfaces and the electrophoretic mobility of the coated microchannels were stable over time and upon exposure to air. By carefully selecting mixtures ofmonomers with the appropriate properties, it may be possible to tailor the surface of PDMS for a large number of different applications.     

1,6-己二醇二丙烯酸酯和苯乙烯多单体熔融接枝制备长支链聚丙烯研究

采用哈克转矩流变仪制备了1,6-己二醇二丙烯酸酯(HDDA)和苯乙烯(St)多单体熔融接枝聚丙烯(PP)体系.红外测试结果表明St的加入能够促进HDDA接枝到PP主链,提高接枝率.动态流变行为研究结果也表明采用多单体熔融接枝PP更有利于体系在熔融接枝中生成长支链(LCB).随着St单体添加量的增加,HDDA的接枝率增大...     

The effect of monomer molecular weight of acrylate on radiation grafting of polyethylene

A series of condensed ethylene glycol acrylate monomers with differentmolecular weight was grafted to polyethylene films by means of pre-irradiation.The effect of the molecular weight of monomer and co-solvent system on thegrafting reaction and the properties of the grafted sample were studied. Theexperimental results showed that the initial rate of grafting reaction decreasedand the molar degrees of grafting linearly decreased with the increment ofmolecular weight of the monomer. The grafting degree was increased with theswelling degree of the grafted film. The biocompatibility and blood compatibilityof the grafted PE films were evaluated by the determination of hydrophilicityand anti-thrombus.     

聚丙烯熔融接枝中共单体的作用机理

聚丙烯树脂是当今最具发展前途的热塑性高分子材料之一,在聚烯烃与工程塑料,如与聚酰胺或聚酯的共混合金中,聚丙烯接枝共聚物则广泛地被用为相容剂．此外,聚丙烯接枝共聚物还广泛应用于极性添加物等,用于改善制品的表面喷涂性能．聚丙烯接枝共聚物是通过自由基熔融接...