GMA/St多组分单体熔融接枝高全同聚1-丁烯

采用Haake转矩流变仪研究了甲基丙烯酸缩水甘油酯(GMA)-苯乙烯(St)多组分单体熔融接枝高全同聚1-丁烯(iPB).考察了温度,过氧化二异丙苯(DCP),GMA,St用量对接枝的影响.结果表明:在180℃下,DCP用量为0.8 phr时,接枝率最高;DCP用量一定时,随着GMA用量增加,接枝率增加,熔体流动速率减...     

苯乙烯协助甲基丙烯酸缩水甘油酯固相接枝改性聚丁烯-1

以过氧化苯甲酰(BPO)为引发剂,甲基丙烯酸缩水甘油酯(GMA)为单体,苯乙烯(St)为共单体,通过固相接枝改性聚丁烯-1(PB-1),考察了反应温度、单体用量、共单体用量和引发剂用量对接枝反应的影响。实验研究表明:在GMA用量5%、BPO用量0.3%、n(GMA)/n(St)=1的条件下,100℃反应2 h后得到接枝率为4.8%的改性产物。共单体St的加入有利于GMA接枝到PB-1大分子链上,并在一定程度上抑制了PB-1的降解。     

多单体熔融接枝天然橡胶及其性能的研究

以甲基丙烯酸缩水甘油酯（GMA）为接枝单体，苯乙烯（St）为接枝共单体，过氧化二异丙苯（DCP）为引发剂，通过熔融接枝法制备接枝天然橡胶[NR-g-（GMA-co-St）]。研究了GMA、St及DCP用量和接枝温度对NR的接枝率及其力学性能的影响。结果表明，GMA、St和DCP质量分数分别为8％、4％和0．3％，接枝温度为160℃时，NR-g-（GMA—co—St）的接枝率最高，综合力学性能最好；St的加入能明显提高NR的接枝率，并能减轻NR的降解；红外光谱的分析证实了GMA已接枝到天然橡胶分子链上。     

GMA/St双组分单体熔融接枝聚丙烯的研究

分别以甲基丙烯酸缩水甘油酯（GMA）和马来酸酐（MAH）为接枝单体，苯乙烯（St）为接枝共单体，过氧化二异丙苯（DCP）为引发剂对聚丙烯（PP）进行熔融接枝，研究了接枝单体的种类、组分配比等因素对PP的接枝率和熔体流动速率等的影响，并研究了接枝PP的力学性能和耐热变形性能。实验结果表明：作为接枝单体，GMA比MAH更具有优越性；双组分单体熔融接枝PP的接枝率和性能优于单组分单体熔融接枝；接枝PP的结晶参数受其接枝率的影响；当PP／GMA／St／DCP=100／6／3／0、3时，PP—g^-（GMA—CO—St）的接枝率最高，力学性能和耐热变形性能最好。     

POE熔融接枝甲基丙烯酸缩水甘油酯的研究

采用同向双螺杆挤出机熔融法制备乙烯-1-辛烯共聚物接枝甲基丙烯酸缩水甘油酯（POE-g-GMA），利用红外光谱法和化学滴定法对接枝物进行表征及接枝率的测定。考察了GMA／St（苯乙烯）、St、引发剂用量以及反应温度和螺杆转速对接枝率的影响。结果表明。随着GMA／St用量、引发剂用量的增加。POE-g-GMA的接枝率随之增大。而熔体流动速率下降；St的加入有效地提高了GMA的接枝率；随着反应温度提高接枝率提高；螺杆转速提高接枝率下降。     

反应挤出法制备LLDPE-g-(GMA-co-St)的研究

以甲基丙烯酸缩水甘油酯(GMA)为接枝单体,苯乙烯(St)为接枝共单体,在双螺杆挤出机上对线型低密度聚乙烯(LLDPE)进行熔融接枝,制备了LLDPE-g-(GMA-co-St).研究了引发剂用量、单体用量、共单体用量和抑交联剂亚磷酸三苯酯等对LLDPE接枝物接枝率和熔体质量流动速率的影响,利用红外光谱对接枝物进行了表征.研究表明,St的加入能有效提高GMA的接枝率,亚磷酸三苯酯有效抑制了LLDPE的交联.最佳配方为:过氧化二异丙苯(DCP)为0.15份,GMA为3份,St为3份,亚磷酸三苯酯为1份.     

高密度聚乙烯接枝甲基丙烯酸缩水甘油酯的研究

研究了高密度聚乙烯 (HDPE)接枝甲基丙烯酸缩水甘油酯 (GMA)的反应工艺。探讨了引发剂(DCP)用量、GMA用量、苯乙烯 (St)用量及反应时间对接枝率的影响。在 180℃ ,引发剂DCP浓度为 0 .14phr ,GMA浓度为 3phr,St与GMA的质量比为 1∶1,反应时间为 15min时 ,制得接枝率为 1.2 7%的接枝物。红外光谱在 1730cm- 1、915cm- 1处分别显示出羰基和环氧基团的特征吸收峰 ;接枝物DTA曲线的熔融吸收蜂亦向低温方向偏移 ,从而证明了接枝反应的发生     

反应挤出法制备POE—g-（GMA—co—St）的研究

以甲基丙烯酸缩水甘油酯（GMA）为接枝单体,苯乙烯（St）为接枝共单体,在双螺杆挤出机上对乙烯-辛烯共聚物（POE）进行熔融接枝,制备了POE—g-（GMA—co—St）。研究了引发剂用量、单体用量、共单体用量和抑交联剂亚磷酸三苯酯等对POE接枝物接枝率和熔体流动速率的影响,利用红外光谱对接枝物进行了表征。研究袭明,St的加入能有效提高GMA的接枝率,亚磷酸三苯酯有效抑制了POE的交联。最佳配方为：过氧化二异丙苯（DCP）为0．15份,GMA为3份,St为3份,亚磷酸三苯酯为1份。     

溶液浸渍法协助二单体接枝改性聚乙烯

用接枝单体和引发剂的溶液浸渍聚乙烯(PE),然后除去有机溶剂,热引发接枝改性聚乙烯.考察了以甲基丙烯酸缩水甘油酯(GMA)为第一单体、苯乙烯(St))为共单体、过氧化苯甲酰(BPO)为引发剂时,单体投料量、浸渍时间和反应温度等因素对接枝反应的影响,并用红外光谱对接枝产物进行了表征.结果表明:当接技单体投料量为7.0％、界面剂用量为17.2％时,室温下浸渍6h,于100℃反应2h得到接枝率为6.43％的接枝产物.     

马来酸酐熔融接枝二元乙丙橡胶的研究

在转矩流变仪中,以过氧化二异丙苯(DCP)为引发剂,采用多单体熔融接枝技术,研究了二元乙丙橡胶(EPM)熔融接枝马来酸酐(MAH),考察了MAH含量、DCP用量、反应温度、反应时间、转子转速以及第二单体苯乙烯(St)的用量对接枝反应的影响,并用红外光谱(FTIR)对接枝产物进行了表征.研究结果表明:对于EPM-g-MAH体系,MAH和DCP最佳用量分别为3.0 phr和0.22 phr,最佳反应温度为170℃,反应时间8 min,转子转速60 r/min,此时接枝率最高达到0.46％;加入第二单体St后,当n(St) /n(MAH)为1/1时,EPM-g-(MAH-co-St)的接枝率为0.64％,接枝率明显提高.     

Styrene‐assisted melt‐free radical grafting of glycidyl methacrylate onto isotactic poly(1‐butene)

The melt‐free radical grafting of glycidyl methacrylate (GMA) onto powered isotactic poly(1‐butene) (iPB‐1) using styrene (St) as a comonomer in a Haake mixer was studied. The effects of temperature, initial GMA, and peroxide concentration, as well as the addition of St comonomer, on the final grafting degree, grafting efficiency, and the melt flow rate of grafted polymer were studied. It was shown that the addition of St as a comonomer could significantly enhance the grafting degree of GMA on iPB‐1 and reduce the extent of degradation of iPB‐1 to some degree. It has been found that the grafting degree of dual‐monomer melt‐grafted iPB‐1 was about twice that of single‐monomer‐grafted iPB‐1 for the same monomer and peroxide concentrations. The grafting of GMA onto iPB‐1 remarkably accelerated the crystal form II → I transformation of iPB‐1. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Styrene‐assisted grafting of maleic anhydride onto isotactic poly butene‐1

Grafting of maleic anhydride (MAH) onto isotactic poly butene‐1 (iPB‐1) was carried out by thermal decomposition of dicumyl peroxide (DCP) using electron‐donating monomer styrene (St), and were carried out in the molten state in a twin‐screw extruder according to an experimental design in which the content of MAH and St were varied. The calibration curve was constructed from FTIR measurements and titration which can obtain the absolute amounts of grafted MAH according to FTIR data. The proposed mechanism was that when St is added to the iPB‐1/MAH/peroxide grafting system, St reacted first with MAH to form a charge‐transfer complex (CTC). Then CTC react (or copolymerize) with macroradicals. The grafting of MAH onto iPB‐1 (iPB‐1‐MAH) accelerated crystalline transformation rate of form II to I. The contact angle decreased with the increase of grafting degree, which indicated that surface polarity increased. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

亚临界二甲醚协助双单体固相接枝改性聚丙烯

以亚临界二甲醚为溶胀剂,偶氮二异丁腈(AIBN)为引发剂,在聚丙烯(PP)上接枝甲基丙烯酸缩水甘油酯(GMA)和苯乙烯(St),制备了接枝产物PP-g-(GMA-co-St).考察了溶胀时间、溶胀温度、反应时间、反应温度、St用量和引发剂用量对接枝产物相对接枝率和水接触角的影响.采用傅里叶变换红外光谱对接枝产物进行定量...     

PP-g-GMA的制备及其改性PP/PA6合金性能

采用双螺杆熔融接枝的方法,在引发剂过氧化二异丙苯(DCP)作用下,将甲基丙烯酸缩水甘油酯(GMA)和共单体苯乙烯(St)接枝到聚丙烯(PP)上。通过傅立叶变换红外光谱仪确定了接枝物的生成,采用酸碱滴定法测定了接枝率。探讨了GMA,St,DCP不同用量对PP接枝物的接枝率和熔体流动速率的影响,并将接枝产物PP–g–(St–co–GMA)加入PP/尼龙6(PA6)的合金中,通过注塑成型样条,测定其力学性能,并观察微观结构。结果表明,St的加入能够提高接枝率,抑制副反应的发生。在PP/PA6合金中加入接枝物PP–g–(St–co–GMA),其拉伸强度可提高46.45%,弯曲强度可提高32.47%,但对冲击强度影响不大。     

HDPE熔融接枝GMA/St及其增容HDPE/PET合金性能的研究

利用HAAKE流变仪,采用熔融接枝法分别制备了甲基丙烯酸缩水甘油酯(GMA)、GMA/苯乙烯(St)接枝高密度聚乙烯(HDPE),将所得接枝物HDPE-g-GMA和HDPE-g-(GMA-co-St)作为HDPE/PET共混合金的反应性增容剂,研究了其对体系力学性能和热致形状记忆性能等的影响。结果表明:采用GMA/St双组分单体具有较高的接枝率,生成的接枝物对HDPE/聚对苯二甲酸乙二醇酯(PET)共混合金的增容效果较好;提高了体系的力学性能和热致形状记忆性能,且HDPE-g-(GMA-co-St)含量为5～10phr时,合金具有较好的综合性能。     

Styrene‐assisted melt free radical grafting of glycidyl methacrylate onto an ethylene and propylene rubber

This article deals with the efficiency of using styrene (St) as a comonomer to promote the melt free radical grafting of glycidyl methacrylate (GMA) onto an ethylene and propylene rubber (EPR) in a batch mixer and a corotating self‐wiping twin screw extruder. The addition of St to an EPR/GMA/peroxide system increases not only GMA's grafting yield but also its grafting rate. The time required for the EPR/GMA/peroxide system without St to reach a given amount of grafted GMA is at least 10 times that needed for the same system in the presence of an equimolar amount of St. For example, about 60 min are required for the EPR/GMA/dicumyl peroxide (composition: 100/3.0/0.3 by weight) to reach 1.5 phr (parts per hundred resin) GMA (i.e., 1.5 g grafted GMA per 100 g EPR). The same amount of grafted GMA is reached in < 3 min when 3.0 phr St is charged to the system. This significant reduction of reaction time is crucial for a successful free radical grafting of GMA on EPR in a corotating twin screw extruder, because the residence time in such a machine is typically on the order of 0.5–5 min. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 125–133, 1999     

聚丙烯熔融接枝改性研究

采用熔融接枝的方法,研究了多组分体系下不同单体熔融接枝聚丙烯的性能。结果表明:在共单体苯乙烯、引发剂和聚丙烯相同的条件下,接枝物的极性均较未接枝的聚丙烯极性增加;不同单体所得接枝物的接枝率不同;熔体流动速率的降低使接枝物的加工性能有不同程度的下降。接枝物极性增加的趋势依次按接枝单体MAH、MMA、GMA递增。接枝物的偏光显微镜分析表明,接枝支链的生成可以促进聚丙烯的异相成核,使晶粒细化。     

N-vinyl pyrrolidone-assisted free radical functionalization of glycidyl methacrylate onto styrene-b-(ethylene-co-butylene)-b-styrene

N-vinyl pyrrolidone (NVP)-assisted free radical functionalization of glycidyl methacrylate (GMA) onto styrene-b-(ethylene-co-butylene)-b-styrene (SEBS) was investigated to attempt to overcome the low grafting reactivity of GMA and the low efficiency of the styrene (St)-assisted functionalization method. By using the optimal amount of NVP, the degree of GMA grafting was increased by at least 7.5 and 2.5-fold when compared to GMA alone and the St-assisted grafting procedure, respectively. Also, no apparent cross-linking or degradation reactions of SEBS were observed. It was proposed that NVP reacted first with SEBS macroradicals, and then the resulting NVP-macroradicals copolymerized with GMA to produce high degrees of grafting of both GMA and NVP onto SEBS.     

Functionalization of high‐density polyethylene in the molten state by glycidyl methacrylate grafting

:This study concerns the melt‐free radical grafting of glycidyl methacrylate (GMA) onto high‐density polyethylene (HDPE). We studied the effect of two initiators (tert‐butyl cumyl peroxide and di‐tert‐butyl peroxide) onto HDPE. Crosslinking of polymer was observed in the presence of 0.3 wt % tert‐butyl cumyl peroxide but not with 0.3 wt % di‐tert‐butyl peroxide. The grafting was carried out in a Brabender batch mixer at 190 °C. The grafting yield of GMA onto HDPE (determined by infrared spectrometry) is weak (<1 wt % for an initial concentration in monomer of 6 wt %). Moreover, it was noted that the degree of grafting did not vary with the concentration and the nature of peroxide used. To increase the grafting yield of GMA, we added to the HDPE/peroxide/GMA system an electron‐donating monomer, such as styrene. Adding this comonomer multiplied the rate of grafted GMA 3‐ or 4‐fold, resulting in a ratio [styrene]_i/[GMA]_i = 1 mol/mol with [GMA]_i = 6 wt %. So, the copolymerization is favored compared with the homopolymerization. This kind of copolymer presenting reactive functions is very attractive in the field of compatibilizing immiscible polymers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 581–590, 2001     

Study of multi‐monomer melt‐grafting onto polypropylene in an extruder

Free‐radical melt‐grafting of the dual‐monomer systems glycidyl methacrylate–styrene (GMA‐St) and hydroxyethyl methacrylate–styrene (HEMA‐St) onto polypropylene (PP) has been studied using a single‐screw extruder. For single monomer grafting systems, degradation of PP was unavoidable and deterioration of the mechanical properties of the grafted PP subsequently occurred because of β‐scission of PP chains during the free‐radical melt‐grafting process. However, for the dual‐monomer systems, it is shown that the addition of styrene as a comonomer can significantly enhance the GMA or HEMA grafting levels on PP and reduce the extent of β‐scission of PP backbone. It has been found that the grafting degree of dual‐monomer melt‐grafted PP, such as PP‐g‐(GMA‐co‐St) or PP‐g‐(HEMA‐co‐St), is about quadruple that of single‐monomer grafted PP for the same monomer and dicumyl peroxide concentrations. Moreover, the melt flow rate of the dual‐monomer grafted PP is smaller than that of the unmodified PP. Hence, PP not only was endowed with higher polarity, but also kept its good mechanical properties. © 2000 Society of Chemical Industry