紫外光引发LDPE膜接枝含氟丙烯酸酯的研究

通过紫外光引发表面接枝聚合反应的方法 ,把含氟丙烯酸酯单体R 5 6 1 0引到LDPE薄膜上 .对经丁酮抽提后的接枝膜进行FTIR、ESCA、SEM和DSC等表征 ,证实含氟聚合物以化学键的方式接枝在LDPE基体膜上 .在一定范围内 ,增加紫外光强、引发剂和单体浓度以及反应温度等均有利于提高接枝率 .经计算R 5 6 1 0的紫外光引发接枝聚合反应总活化能为 5 4 2kJ mol.接枝膜的接触角随着接枝率的提高逐步增大 ,直至趋于恒定 .作者提出接枝膜存在一个在接触角测定时影响基体膜与探测水滴相互作用过程的边界层 .当接枝率较低、接枝层厚度小于边界层临界厚度时 ,基体LDPE影响接触角的大小 ,但随着接枝率提高 ,接枝层逐渐变厚 ,氟聚合物层对接触角的贡献逐渐占优势 ,导致接触角随之增大 .当接枝率超过一定值以后 ,接枝层厚度超过边界层临界厚度 ,接枝层对接枝膜的接触角起全部贡献 ,接触角测定值随之稳定     

聚β-羟基丁酸酯辐照接枝顺丁烯二酸酐及产物表征

探索了一种提高聚β羟基丁酸酯(PHB)热稳定性的方法,即用60Coγ射线辐照对PHB进行顺丁烯二酸酐(MAH)的接枝,采用1HNMR、13CNMR、TGA、DSC、XRD等方法对辐照接枝产物进行了表征.1HNMR、13CNMR谱图结果表明MAH单体接枝到了PHB上.TGA测试表明,辐照接枝产物的热稳定性显著提高,如接枝率为0.52%的样品热分解温度提高了36K.DSC研究表明辐照接枝产物的熔融温度和结晶温度均降低.此外,由于引入极性单体顺丁烯二酸酐,接枝产物的结晶度降低,同时亲水性提高.     

二步法聚丙烯/丙烯酸表面接枝聚合研究

研究了二步法聚丙烯膜表面的丙烯酸接枝反应 .实验发现 ,以醋酐为溶剂的反应体系所得接枝率明显好于以水为溶剂的体系 ;接枝率随光敏剂浓度、单体浓度增大而增加 ;提高反应温度 ,可使接枝率明显增大 ;接枝后的聚丙烯膜表面亲水性可明显改善 .并用红外光谱证实了丙烯酸在聚丙烯膜表面的接枝 .     

Self‐initiating performance of maleic anhydride on surface photografting polymerization

Maleic anhydride (MAH) was photografted onto low‐density polyethylene (LDPE) films with a grafting efficiency of about 70% in the absence of a photoinitiator. The self‐initiating performance was attributed to a mechanism of abstracting hydrogen atoms from LDPE chains by excited MAH dimers. The supporting experimental results were as follows: (1) the far‐UV radiation (200–300 nm) was indispensable for the graft polymerization and 2) the crosslinking reaction of LDPE inevitably accompanied the grafting of MAH. In addition, the initiation performance of MAH was further confirmed by surface photografting of acrylic acid in the presence of MAH, where MAH was used as the photoinitiator. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3246–3249, 2001     

Radiation-induced graft polymerization of maleic acid and maleic anhydride onto ultra-fine powdered styrene–butadiene rubber (UFSBR)

The functionalization of ultra-fine powdered styrene–butadiene rubber (UFSBR) was carried out using gamma radiation-induced graft polymerization of maleic acid (MA) and maleic anhydride (MAH), respectively. It was found that the graft yield of MA onto UFSBR increased rapidly up to the peak and then decreased with increasing MA content. Moreover, the peak shifted to the direction of lower MA content with increasing absorbed dose. Similarly, there was the peak of graft yield with increasing MAH content for grafting of MAH onto UFSBR, whereas the peak of graft yield was achieved at 10 wt% MAH content at different absorbed doses. On the other hand, increasing absorbed dose and decreasing monomer contents are useful to improve the graft efficiency of MA and MAH. At high dose and low monomer content, the graft yield of MAH onto UFSBR is higher than that of MA. FTIR spectra confirmed that both MA and MAH can be grafted successfully onto the UFSBR under gamma irradiation, respectively. Comparing with maleation of rubber by melt grafting, the graft yield of MAH on UFSBR is higher, which can be attributed to the network structure and nanometer size of UFSBR as well as high energy provided by radiation.     

Grafting copolymerization of styrene and maleic anhydride binary monomer systems induced by UV irradiation

Photografting copolymerization of maleic anhydride (MAH) and styrene (St) onto LDPE film was investigated by using a one-step method, and further thermally induced grafting copolymerization of them was carried out by using a two-step method. Regarding the photografting copolymerization of MAH/St binary monomer system, both conversion percentage (CP) and grafting efficiency (GE) increased with raising the content of MAH in the monomer feed. In addition, the content of MAH in the grafted copolymers also increased with increasing the fraction of MAH in the monomer feed. The formation of LDPE-g-P(MAH-co-St) grafted film was identified by FTIR and ESCA spectroscopy. In the case of grafting copolymerization of MAH/St by the two-step method, grafting copolymerization proceeded slowly compared with the non-grafting copolymerization. The apparent activation energy (E_a) for the non-grafting copolymerization in the solution and the grafting copolymerization on LDPE film was 24 and 82 kJ/mol, respectively, which were noticeably lower than those of MAH/vinyl acetate (MAH/VAC) binary monomer system under the similar grafting conditions. These data of E_a explained why the grafting copolymerization of styrene/MAH took place faster than that of MAH/VAC binary monomer system. The composition of the grafted copolymer chains was largely affected by the composition of the monomer feeds; however, the composition of the non-grafted copolymers nearly remained at 1/1 even in systems with largely different MAH/styrene ratios in monomer feeds. It is indicated that the non-grafting copolymerization proceeded predominantly following alternating copolymerization, but the grafting copolymerization performed random copolymerization.     

A study on melt grafting of maleic anhydride onto low‐density polyethylene and its blend with polyamide 6

Graft copolymerization of low‐density polyethylene (LDPE) with a maleic anhydride (MAH) was performed using intermeshing corotating twin‐screw extruder in the presence of benzoyl peroxide (BPO). The LDPE/polyamide 6 (PA6) and LDPE‐g‐MAH/PA6 blends were prepared in a corotating twin‐screw extruder. The melt viscosity of the grafted LDPE was measured by a capillary rheometer. The grafted copolymer was characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microcopy (SEM). The influence of the variation in temperature, BPO and MAH concentration, and temperature on the grafting degree and on the melt viscosity was studied. The grafting degree increased appreciably up to about 0.45 phr and then decreased continuously with an increasing BPO concentration. According to the FTIR analysis, it was found that the amount of grafted MAH on the LDPE chains was ～5.1%. Thermal analysis showed that melting temperature of the graft copolymers decreases with increasing grafting degree. In addition to this, loss modulus (E″) of the copolymers first increased little with increasing grafting and then obviously decreased with increasing grafting degree. Furthermore, the results revealed that the tensile strength of the blends increased linearly with increasing PA6 content. The results of SEM and mechanical test showed that the blends have good interfacial adhesion and good stability of the phase structure, which is reflected in the mechanical properties. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 267–275, 2010     

HDPE氯化原位接枝MAH及产物结构

HDPE氯化原位接枝MAH及产物结构;高密度聚乙烯;氯化原位接枝;CPE-g-MAH;接枝率;凝胶     

GRAFTING OF PEROXIDE-INITIATED MALEIC ANHYDRIDE ON SPHERICAL PE／PP IN-REACTOR BLEND GRANULES

Spherical polyethylene/polypropylene (PE/PP) in-reactor blend granules with various ethylene/propylene molar ratios and high porosity were synthesized using a high yield TiCl4/MgCl2 supported catalyst. A solution of benzoyl peroxide (BPO)/maleic anhydride (MAH)/xylene (interfacial reagent) or BPO/MAH/St (comonomer) was absorbed onto the PE/PP inreactor blend granules, and solid phase gratt polymerization of MAH on PE/PP was conducted. The amount of grafted MAH on PE/PP was measured through chemical titration. The results showed that solid phase graft polymerization of MAH in PE/PP in-reactor blend granules produced graft copolymer with high amount of grafted MAH, and the amount of grafted MAH was raised slightly when St was introduced as comonomer. The graft in-reactor blend was fractionated into five fractions through temperature-gradient extraction fractionation (TGEF), and the fractions were analyzed by FTIR. The results revealed that MAH is mainly grafted on the PE segments, whereas MAH was predominantly grafted on the PP segments when St was present in the graft polymerization system. In addition, the final product is still in the form of regular spherical granules, which is beneficial for industrial processing.     

非水滴定和傅立叶红外光谱在聚丙烯马来酸酐接枝物表征中的应用

采用非水滴定法中的无机碱直接滴定方法测定了马来酸酐在聚丙烯上的接枝率,并对该方法作了可行性验证,讨论了非水滴定中的两个难点：化学计量比的确定和滴定终点的判断。通过傅立叶红外光谱法(FTIR)对聚丙烯马来酸酐接枝物的纯化效果、自由基引发反应对非水滴定的影响及聚丙烯接枝马来酸酐的反应机理作了定性分析,并结合非水滴定的数据绘制了红外定量校准曲线。     

Surface‐confined photopolymerization of single‐ and mixed‐monomer systems to tailor the wettability of poly(L‐lactide) film

The major objective of this research was to modify the surface characteristics of poly(L ‐lactide) (PLA) by grafting a combination of hydrophilic polymers to produce a continuum of hydrophilicity. The PLA film was solvent cast, and the film surfaces were activated by ultra violet (UV) irradiation. A single monomer or combination of two monomers, selected from vinyl acetate (VAc), acrylic acid (AA), and acrylamide (AAm), were then grafted to the PLA film surface using a UV induced photopolymerization process. The film surfaces resulting from each reaction step were analyzed using ATR‐FTIR spectroscopy and contact angle goniometry. Results showed that AAm dominated the hydrophilicity of the film surface when copolymerized with VAc or AA, while the water contact angles for PLA films grafted with poly(vinyl acetate‐co‐acrylic acid) varied more gradually with feed composition. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6534‐6543, 2006     

Photoinduced grafting polymerization onto the surface with the use of radiation of high-power ultraviolet light-emitting diodes

The photoinduced grafting polymerization of acrylic acid onto the surface of a polypropylene film under the action of radiation with a wavelength of 365 nm and an intensity of 8–193 mW/cm² emitted by high-power UV light-emitting diodes is studied. Grafting is performed from a thin layer of the aqueous solution of the monomer onto the surface containing a photoinitiator (benzophenone) deposited from a solution in a volatile solvent. The amount of graft polymer is determined with the use of ATR FTIR spectroscopy. At an intensity of UV radiation of 193 mW/cm², the time of attainment of grafting-polymerization saturation is decreased by a factor of 6 relative to this time at an intensity of 8 mW/cm², typical for emitters based on mercury lamps. The rate of grafting polymerization in the studied UV-radiation-intensity range grows in proportion to the square root of intensity.     

Synthesis,characterization, and degradation behaviors of poly(D,L-lactide-co-glycolide) modified by maleic anhydride and ethanediamine

In order to improve hydrophilicity and settle the acidity in hydrolysis, a novel ethanediamine (EDA) and maleic anhydride (MAH) modified poly(D,L-lactide-co-glycolide) (PLGA) polymer (EMPLGA) was synthesized. Fourier Transform Infrared Spectrometer (FTIR), Gel Permeation Chromatography (GPC), Nuclear Magnetic Resonance (1HNMR), titration and the water contact angles were employed to characterize the synthesized polymer. The effects of various polymerization conditions on weight average molecular mass (Mw), polydispersity index (PDI) and anhydride content of MPLGA were investigated. The degradation behaviors of PLGA, MPLA and EMPLGA were also studied by observation of the changes of the pH value of incubation medium, molecular weight and weight loss ratio for a time interval of 25 days in-vitro, respectively. The results showed that MPLGA with high anhydride content was successfully obtained by directly ring-opening polymerization and ethanediamine was further grafted onto MPLGA, and there is almost unchanged in Mw between MPLGA and EMPLGA polymers. The introduction of anhydride and amino groups improved the hydrophilicity of PLGA. A uniform degradation of EMPLGA was observed in comparison with an acidity-induced auto-accelerating degradation featured by PLGA and MPLGA. The results revealed that the introduction of ethanediamine into PLGA has weakened or neutralized the acidity of PLGA degradation products.     

芴酮引发光接枝改性LDPE膜的研究

采用紫外光引发接枝表面改性的方法,以芴酮(FL)为引发剂,在低密度聚乙烯(LDPE)薄膜表面上接枝丙烯酸(AA)、甲基丙烯酸(MAA)、丙烯酸甲酯(MA)、甲基丙烯酸甲酯(MMA)、丙烯酰胺(AM)等单体,以赋予薄膜表面新的化学性质.考察了引发剂浓度、紫外光的辐照时间、辐照强度、单体种类对LDPE薄膜接枝程度的影响.结果表明,在一定范围内,增加芴酮浓度,可以提高单体的接枝率,但当芴酮浓度达到5%时,接枝率反而下降.延长辐照时间至4 min和提高紫外光的辐照强度达100 W/m2,均有利于接枝反应的进行.不同单体在LDPE膜上的接枝能力与单体的活性、单体与基材的相容性等因素有关.接枝后,LDPE与水的接触角下降程度不仅与单体在膜上的接枝量有关,还与接枝单体的亲水性能密切相关.     

血液相容材料的合成研究Ⅷ.磺铵两性离子单体在聚醚氨酯表面的臭氧活化接枝

生物相容性 ,特别是血液相容性是生物医用材料极其重要的性能[1] .提高不凝血性一直是生物材料研究与发展 (Ｒ Ｄ)的主要内容之一 ,半个多世纪来 ,不凝血材料的Ｒ Ｄ已取得了很大的发展[2 ] .但还不能满足心血管植入物 (Ｃａｒｄｉｏｖａｓｃｕｌａｒｉｍｐｌａｎｔｓ)及心血管医物 (Ｃａｒｄｉｏｖａｓｃｕｌａｒｄｅｖｉｃｅｓ)对不凝血性的需要 .Ｒａｔｎｅｒ[3 ] 在最近一次的血液相容性问题研讨会上再次强调了不凝血材料研究的紧迫性 .会议的报告也反映了该领域的研究现状 ,并提出了今后要研究的问题等 .目前不凝血性较好的材料仅有聚…     

马来酸酐-苯乙烯多组分单体熔融接枝高密度聚乙烯机理及性能研究

用单螺杆挤出机制备了马来酸酐-苯乙烯(MAH-St)多单体熔融接枝高密度聚乙烯(HDPE)体系,研究发现添加St共同接枝,可以显著提高接枝物的接枝率.随着St的增加,接枝率先增大后有所降低.当两种单体物质的量比约为1:1时,接枝物的接枝率最高,此时接枝物的熔体流动速率(MFR)最小.即MAH接枝率越高,接枝物的MFR越...     

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     

聚丙烯表面接枝PNIPAAm膜Ⅰ.光接枝反应和表面形态结构研究

以氧杂蒽酮或二苯甲酮为引发剂 ,通过紫外光引发表面接枝聚合的方法在聚丙烯薄膜表面引入了具有温度敏感特性的聚异丙基丙烯酰胺 (PNIPAAm)接枝聚合物层 .提高紫外光强度和接枝反应温度均有利于接枝率增大 ,而单体浓度对接枝率的影响存在最佳值 ,为 0 1 8mol L .在引发剂预浸渍引发接枝和休眠基引发接枝这两种方式中 ,后者能够实现更高的接枝率 .红外光谱 (FTIR)、X射线光电子能谱化学分析 (ESCA)和扫描电子显微镜 (SEM)等对接枝层组成的表征结果证实了接枝层的存在 .在不同温度下 ,接枝膜的FTIR谱图中酰胺I带和酰胺II带特征吸收峰发生位移 ,表明它具有温度敏感特性 .同时 ,SEM研究发现由于接枝膜的温度敏感特性而导致的球状表面形态结构     

Surface modification of an ethylene-acrylic acid copolymer film: grafting amine-terminated linear and branched architectures

Polymer films can be tailored for a specific application by modifying their surface properties. In this study, linear and branched architectures were grafted to ethylene-acrylic acid (EAA) copolymer films using the so-called grafting from approach. Dicyclohexylcarbodiimide was used to activate the carboxylic acid functionality on the surface of the EAA copolymer film before reacting it with selected di- and tri-amine compounds. The carboxylic acid functionality was subsequently regenerated by reacting the amine-grafted film with succinic anhydride. These reaction steps were then repeated to create the linear and branched architectures on the EAA film surface. The film surface resulting from each reaction step was analyzed using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and contact angle measurements. A systematic analysis of the ATR-FTIR results was performed to estimate the average conversion of the reaction schemes and to explain the observed contact angle results. A significant reduction in water contact angle for the EAA film grafted with a branched architecture was observed. The EAA film grafted with a linear architecture showed a marginal reduction in water contact angle when ethanol was used as a solvent for ethylenediamine. When the solvent for ethylenediamine was changed to water, the contact angle decreased noticeably. However, analysis of control films showed that the reduction in the contact angles was due to the solvent treatment. In the case of branched architectures, such reduction in contact angle due to the solvent treatment was not observed. Several control experiments were performed to ensure that the reduction in the contact angles was in fact due to the grafted species and not due to exposure to various solvents used in the reaction scheme.     

Ultrasonically Initiated Grafting of Maleic Anhydride onto Poly(propylene)

This paper presents the studies on the grafting of MAH onto PP performed in solution by means of ultrasonic initiation. The effect of sonic intensity and monomer concentration on the amount of grafted MAH was investigated. It was found that grafting reaction could be initiated by ultrasound at ambient temperatures in the absence of an initiator. The quantity of product grafted was found to be 1.35%. It has been shown that optimum conditions for grafting are reached at an ultrasonic intensity of 300 W and a MAH concentration of 30%. PP‐g‐MAH is characterized by FTIR and XRD. DSC shows that the crystallinity of PP‐g‐MAH is lower than that of pure PP.