Radiation grafting of acrylic acid on to polypropylene filaments. I: Effect of reaction conditions

Graft copolymerization of acrylic acid on to polypropylene filaments was investigated by a simultaneous irradiation technique. The effect of various solvents and solvent combinations on swelling behaviour and on percentage grafting was studied. At a constant dose, the percentage grafting was found to be higher at low dose rates and it increased linearly up to 0.25 Mrad and then saturated. It was also observed that grafting increases with increasing monomer concentration up to 2 mole/litre. Graft copolymers were characterized by infrared spectroscopy and colour formation with methylene blue.     

聚丙烯纤维接枝丙烯酸反应条件优化

The optimum conditions of grafting copolymerization reaction of acrylic acid (AA) onto polypropylene (PP) fiber was studied by using benzoyl peroxide (BPO) as initiator. The primary and secondary sequences of the grafting copolymerization reaction conditions was analysed. The results showed that grafting copolymerization reaction was greatly influenced by the temperature, reaction time, concentration of BPO and that of AA in the primary and secondary role as the above sequence. The optimum reaction conditions of gaining higher exchange capacity for the weak acidic cation-exchange fiber are as follows: the grafting temperature 80℃, the reaction time 7h, the concentration of BPO 2% and AA 80%.     

Surface modification of polypropylene sheets by UV‐radiation grafting polymerization

1,6‐Hexanediol diacrylate (HDDA) was grafted onto polypropylene (PP) substrates in the presence of benzophenone (BP) and isopropylthioxanthone (ITX) photoinitiators, and then polyurethane acrylate formulations were coated onto the HDDA‐g‐PP substrates, using UV radiation. The amount grafted and the grafting efficiency of the polymerizations were determined gravimetrically. The effects of the photoinitiator concentration and the UV radiation intensity on the physicochemical surface properties and the grafting efficiency of the UV‐radiation grafting polymerizations were characterized in detail using contact‐angle measurements, Fourier transform infrared spectroscopy with attenuated total internal reflection, and scanning electron microscopy. The results showed that the amount grafted and the surface polarity of the HDDA‐g‐PP substrates both increased linearly with increasing BP photoinitiator concentration and UV radiation intensity, and that the addition of a small amount of ITX markedly enhanced both parameters, probably due to photosensitization. The adhesion of the UV‐cured coating onto the HDDA‐g‐PP substrates was evaluated using the crosshatch adhesion test. The results indicated that the amount of HDDA grafted onto the PP substrates should exceed about 1 mmol/cm² for satisfactory adhesion with the UV‐cured coating. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1446–1461, 2006     

聚丙烯无纺布预辐射固相接枝丙烯酸的研究

以聚丙烯(PP)无纺布为基材,以丙烯酸为单体,进行预辐射固相接枝聚合,考察了外部环境、辐射剂量、温度、反应时间、单体用量、介质、阻聚剂、交联剂对接枝率的影响。结果表明,通过预辐射固相接枝聚合方法,可将丙烯酸单体接枝在PP无纺布上,辐射剂量增大可提高接枝率;反应时间对接枝率的影响在低、高温阶段有所不同。最佳反应条件为:氮气环境,辐射剂量大于50 kGy,反应温度65℃,反应时间3 h,单体浓度30%,反应介质为水,阻聚剂0.8 g,交联剂用量为5 mL。     

Plasma-induced hydrogel grafting of vinyl monomers on polypropylene

Polypropylene (PP) film was plasma-treated using a 13.56 MHz direct plasma with argon, nitrogen, and oxygen as the plasma-forming gases. The three gases induced very different changes on the PP film surface, which were studied using contact angle measurements. Because of its degrading and oxidative effect, oxygen plasma pretreatment was not used for the homogeneous grafting of acrylic acid and acrylamide. Nitrogen plasma treatment did not lead to the formation of stable peroxides on the film surface and did not undergo grafting reactions. This may be due to the types of radicals and functional groups created on the surface during the plasma treatment. Finally, argon plasma pretreatment was found to be the most effective for the grafting of vinyl monomers. The amount of grafted poly(acrylic acid) was shown to be proportional to the concentration of peroxides created by argon plasma treatment.     

Development of antimicrobial polypropylene sutures by graft polymerization. I. Influence of grafting conditions and characterization

Modification of polypropylene monofilament was carried out by the graft polymerization of 1‐vinylimidazole (VIm) using simultaneous radiation grafting method. The effect of radiation dose, monomer concentration, and the grafting medium on the degree of grafting was evaluated. It was observed that the presence of organics as additives in the reaction medium had significant influence on the graft levels. These grafted sutures were characterized using several techniques, such as infrared spectroscopy (IR), X‐ray diffraction, and differential scanning calorimetry (DSC). It was found that the grafts are confined to the amorphous region of the monofilament and the crystalline regions remain intact. The surface morphology of sutures was evaluated by scanning electron microscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3895–3901, 2006     

超声波在丙烯酸固相接枝聚丙烯中的应用

利用超声波促进固相接枝反应的原理，研究丙烯酸（AA）接枝聚丙烯（PP）的反应条件：超声波作用时间、接枝反应温度、引发剂过氧化苯甲酰（BPO）及AA用量等对接枝率的影响。研究表明：超声波能有效地促进固相接枝反应的进行。其最佳反应条件是：超声波的作用时间为30min，BPO与AA的用量分别为4％和15％，反应温度为110℃。在上述反应条件下，可以得到接枝率为6％的接枝产物AA接枝PP（PP－g－AA）；并用硅灰石填充含有PP-g-AA的PP复合材料，其力学性能明显优于不含PP－g－AA的硅灰石填充的PP复合材料。     

利用反应挤出的聚丙烯熔融接枝改性

系统简介了聚丙烯熔融接枝体系的组成、机理及实现熔融接枝的反应挤出技术。介绍了聚丙烯接枝物的表征和应用状况，并指出了熔融接枝体系中存在的问题。     

Improving foamability of polypropylene by grafting modification

Polypropylene (PP) foam has been considered as a potential substitute for other thermoplastics foams in industrial applications. However, the key concern is the weak melt strength of PP, which leads to a high content of open‐cell structure in PP foams; and, thus, unsatisfactory for a number of applications. In this work, PP was modified by grafting with unsaturated linear polyester (ULP) in a twin‐screw extruder in attempt to improve the melt strength of PP. The grafting reaction on PP and the modified PP were characterized using FT‐IR, DSC, and TGA. The improved foamability was verified by SEM observation. In addition, the rheological behavior of modified PP was investigated using a Hakke rheometer. The results indicated that the melt strength of grafted PP was significantly enhanced, facilitating the foam formation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4114–4123, 2006     

聚丙烯无纺布预辐射法固相接枝甲基丙烯酸甲酯的研究

研究了以预辐射聚丙烯无纺布为基材,甲基丙烯酸甲酯为单体,采用固相接枝聚合的方法制备接枝共聚物的接枝反应过程。详细讨论了反应温度、反应时间、阻聚剂、单体浓度和交联剂等对接枝率的影响。结果表明,该接枝反应的最佳条件为:温度65℃、时间2 h、单体浓度20%、交联剂5%、阻聚剂(FeSO4.7H2O)0.3 g,在此条件下的接枝率为6.64%。     

Study of suspension grafting process of polypropylene

Grafting efficiency is an important indicator of polypropylene grafting reaction. A series of studies have been accomplished, including the conditions of free radical presence on PP backbone during peroxide initiation, the effect of preheat treatment and reaction time on PP suspension grafting results, and the effect of peroxide residue on properties of modified PP. An optimized grafting process was proposed by mixing and preheating polypropylene (PP) and the initiator benzoyl peroxide (BPO) before adding the grafting monomer glycidyl methacrylate (GMA),resulting in an increase in grafting efficiency from 50.0% to 78.2%. With initiator residue removed by alternating temperature treatment, the suspension grafting reaction time could be substantially reduced.     

PP无纺布预辐射法固相接枝4-VP的研究

以预辐射聚丙烯无纺布为基材,4-乙烯基吡啶为单体,二乙烯基苯为交联剂,采用固相接枝聚合的方法制备接枝共聚物。讨论了反应温度、反应时间、阻聚剂、单体浓度和交联剂等对接枝率的影响。结果表明,接枝反应的最佳条件为:温度50℃,时间3 h,单体浓度10%,交联剂5%,阻聚剂(FeSO4.7H2O)0.08%,最佳条件下的接枝率为7.5%。     

Antibacterial activities of acrylic acid-grafted polypropylene fabric and its metallic salt

Acrylic acid (AAc) was grafted onto polypropylene (PP) fabric by a preirradiation method using a ⁶⁰Co gamma ray. The effects of the absorbed dose, the reaction temperature, reaction time, storage time, as well as the addition effect of ferrous ion and sulphuric acid on the degree of grafting, were determined. It was shown that the synergistic effect of a strong acid with ferrous sulfate can increase the grafting yield. Antibacterial activities on metallic complexes of acrylic acid-grafted polypropylene (AAc-g-PP) fabric were evaluated by a viable cell counting method. An Ag complexed fabric had strong biocidal effect for all bacteria. Fe, Cu, and Zn complexed fabrics had different antibacterial activities depending on each bacterium. However, AAc-g-PP fabric and Ni-complexed fabric did not have bactericidal effect. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2213–2220, 1998     

聚丙烯后功能化接枝改性研究进展

聚丙烯（PP）是一种重要的通用树脂,然而由于缺乏极性导致其染色性、抗静电性、亲水性以及与极性聚合物、无机填料的相容性差,限制了它的进一步推广应用。提高PP极性和相容性行之有效的方法是在PP大分子链上接枝极性侧基。本文综述了PP后功能化接枝改性的动力学模型、接枝机理,为从分子水平来设计接枝物结构,提高接枝效果以及产品性能提供了理论上的依据;同时,对PP接枝改性时单体的选择及复配加以介绍,并对助剂的加入及合成方法加以说明。简单阐述了新型多功能接枝单体的研究近况,为PP接枝物的制备提供借鉴。     

Proton exchange membranes by grafting of styrene–acrylic acid onto FEP by preirradiation technique. I. Effect of synthesis conditions

Grafting of styrene–acrylic acid (sty–AA) polymer onto fluorinated ethylene propylene copolymer (FEP) was carried out by preirradiation of FEP with γ‐rays. Effect of reaction conditions on the degree of grafting such as total radiation dose, monomer concentration, temperature, and time of grafting has been studied. From the study, it is seen that the degree of grafting is strongly dependent on the reaction conditions. The rate dependence of 0.53 (～0.5) and 1.03 (～1) have been obtained with respect to total dose and monomer concentration, respectively indicating that radiation induced grafting follows free radical polymerization. The activation energy for the grafting in the temperature range of 60–90°C is found to be 33 kJ/mol. The results indicate that the grafting takes place by the front mechanism where the grafting starts at surface and slowly proceeds inwards by diffusion of the monomer through the swollen grafted chains. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2572–2577, 2003     

聚丙烯纤维接枝苯乙烯的研究

采用化学接枝法以苯乙烯(St)为接枝单体、过氧化苯甲酰(BPO)为引发剂,1,2-二乙烯苯(DVB)为交联剂、甲醇和正辛醇为溶剂,对聚丙烯(PP)纤维进行接枝改性。研究了原料配比和反应条件对其接枝的影响。结果表明,PP纤维上接枝St,适宜的原料配比和操作条件为:St质量与PP体积比(St/PP)为4,BPO质量与St体积比(BPO/St)为0.025,DVB与St体积比(DVB/St)为0.025,溶剂与St体积比为5,浸渍24～30h,在85℃恒温水浴中反应6～8h。在较佳条件下可得到导入率为110%-160%的接枝纤维。     

聚丙烯无纺布预辐射接枝改性及胺化研究

采用丙烯酸(AA)、二乙烯三胺(DETA)依次对聚丙烯(PP)无纺布进行预辐射接枝改性及胺化处理,研究了接枝反应及胺化反应的影响因素,并用红外光谱对产物进行表征。结果表明:随着AA用量的增加,接枝率呈先增长后下降趋势;随着反应温度的升高,反应时间的延长,接枝率增加;随着接枝率的增大,胺化反应温度的升高及反应时间的增加,胺化率增加。接枝反应温度为95℃,25 mL AA与无纺布反应2 h,接枝率可达到276%;接枝率为250%的无纺布与50 mL DETA反应7 h,胺化温度205℃,胺化率可达到73%。红外光谱分析表明,经辐射接枝及胺化处理后的PP无纺布有胺基基团。     

聚丙烯无纺布接枝改性研究

采用Co射线辐射后的聚丙烯(PP)无纺布为原料,通过接枝改性制备PP接枝共聚物。研究了接枝条件对接枝率的影响。结果表明:选择丙烯酸为接枝单体,其质量分数为30%,交联剂质量分数5%,阻聚剂用量0.30 g,接枝反应温度65℃,反应时间3 h,PP无纺布的接枝改性效果显著,接枝率达84.95%。     

丙烯酸改性氯化聚丙烯的合成和粘接性能的研究

氯化聚丙烯是聚丙烯的氯化改性产物，通过改性，其硬度、耐磨性、耐酸性、耐盐水性能比聚丙烯都好，耐热、耐老化性也优于聚丙烯。但其性能尤其是粘接性能还不能满足其在胶粘刺等方面的需要，为了进一步提高氯化聚丙烯的粘接性能，拓宽其应用领域，需对氯化聚丙烯改性。接枝共聚法是一种很好的化学改性方法。本文以丙烯酸(AA)作为接枝单体，以过氧化苯甲酰(BPO)为引发剂，以甲苯为溶刺，采用液相接枝共聚法，将丙烯酸单体接枝到氯化聚丙烯大分子链上，得到丙烯酸改性氯化聚丙烯产物。系统研究了反应温度、反应时间、引发剂过氧化苯甲酰用量和丙烯酸单体用量等因素对丙烯酸接枝改性的氯化聚丙烯产物粘接性能的影响，得出了较佳的工艺条件是反应温度T=100℃，反应时间t=3．5h，原料质量配比为100份氯化聚丙烯、3份丙烯酸和0．3份的过氧化二苯甲酰。研究还表明，丙烯酸改性的氯化聚丙烯的粘接性能优于氯化聚丙烯的粘接性能。     

马来酸酐熔融接枝聚丙烯的研究

在双螺杆挤出机上研制马来酸酐（MAH）接枝的聚丙烯（PP）。主要讨论了聚丙烯（PP）与马来酸酐（MAH）在熔融挤出反应中,引发剂DCP、MAH的用量以及反应温度、物料的停留时间对接枝物的影响。