Free‐radical grafting of acrylic acid onto isotactic polypropylene using styrene as a comonomer in supercritical carbon dioxide

Free‐radical grafting of acrylic acid (AAc) onto isotactic polypropylene (iPP) using styrene (St) as a comonomer in supercritical carbon dioxide (SCCO₂) medium was studied. The effects of temperature and pressure of reaction on functionalization degree (grafting degree of AAc) of the products were analyzed. The increase of reaction temperature increases the diffusion of monomers and radicals in the disperse reaction system of SCCO₂. In addition, the increase of temperature accelerates the decomposition rate of 2,2′‐azobisisobutyronitrile (AIBN), thus promoting grafting reaction. It was also observed that functionalization degree of the products decreases with the increase of pressure of SCCO₂ in the range of experiment. The effects of comonomer St on the functionalization degree of the products were investigated. The AAc graft degree of the resulting polymer was drastically higher in the present of St. It reached a maximum when the mass ratio of St and AAc was about 0.7 : 1. Because AAc is not sufficiently reactive toward iPP macroradicals, it would be helpful to use a second monomer that can react with them much faster than AAc. St preferentially reacts with the iPP macroradicals to form more stable styrene macroradicals, which then copolymerize with AAc to form branches. The highest functionalization degree was obtained when the AIBN was 0.75 wt %. When the initiator was used excessively, the functionalization degree decreased because of severe chain degradation of the iPP backbone. The morphologies of pure iPP and grafted iPP are different under the polarizing optical microscope. The diameter of the pure iPP spherulites is 20–38 μ and that of the grafted iPP spherulites is reduced with the increase of the functionalization degree of the products. This is proposed to be because the polar grafts formed during the reaction would have a tendency to associate in the hydrophobic PP environment. This might preserve some of the local crystalline order that existed during the reaction in the swollen iPP phase. It can be proven by a DSC cooling investigation that the crystallization temperature increased as the functionalization degree increased. This is proposed to be because the side‐chain of grafting polymer helps to bring about the heterogeneous nucleation in grafting polymer. Therefore, a large number of nuclei can emerge to a lesser supercooling degree. It can be also proven that the percent crystallization decreased as the functionalization degree increased, probably due to the grafted branches, which disrupted the regularity of the chain structure and increased the spacing between the chains. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2203–2210, 2004     

Development of antimicrobial polypropylene sutures by graft copolymerization. II. Evaluation of physical properties,drug release,and antimicrobial activity

Polypropylene (PP) sutures are prepared by the simultaneous radiation grafting of 1‐vinylimidazole (VIm) onto PP monofilament sutures. The tenacity slightly decreases whereas the elongation increases with the increase in the degree of grafting. Thermogravimetric analysis shows that the stability of the sutures is enhanced by the grafting process. The grafted sutures have reasonably good water uptake. They are subsequently immobilized with an antimicrobial drug, ciprofloxacin. The modified suture releases the drug over a period of 4–5 days. The antimicrobial activity of the modified suture is determined against Esherichia coli by the zone of inhibition technique. A clear zone of inhibition is observed around the drug‐containing suture. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3534–3538, 2007     

Dynamic Mechanical Properties and Adhesive Joint Strengths of Emulsion Polymers Produced by Power Feed Technique. III. Adhesive Joint Strengths of Grafted Power Feed Copolymer

Power feed copolymers were synthesized using styrene and n-butyl acrylate through non-uniform feeding emulsion polymerization. Poly(vinyl alcohol) (PVA) was used as a protective colloid, onto which vinyl monomers were grafted. Power feed copolymer had a very broad glass transition temperature compared with random copolymer, even if grafting and/or crosslinking were introduced to the system. This tendency was almost the same as the non-grafted power feed copolymer where only low molecular weight surfactant was used.

Adhesive joint strengths of power feed copolymers were evaluated compared with random copolymers. In the case of usual linear power feed copolymer, the adhesive joint strengths were not higher than those of random copolymer, which was considered to be due to the lower film strengths of the power feed copolymer. Power feed copolymer having grafting showed slightly higher adhesive joint strengths over a wide range of temperatures than random copolymer. When crosslinking was introduced to the system, power feed copolymer showed much higher adhesive joint strengths over a wide temperature range.     

丙烯酸接枝线形低密度聚乙烯的热学行为及结晶形态

利用差示扫描量热仪研究了丙烯酸接枝线形低密度聚乙烯（PE-LLD-g-AA）的热学行为，结果表明，与纯线形低密度聚乙烯（PE—LLD）相比，PE-LLD-g-AA的熔融温度（Tm）略有增加，结晶温度（Tc）增加大约4℃，熔融焓（AHm）随AA含量的增加而降低。还利用差示扫描量热仪研究了PE—LLD和PE—LLD-g—AA的等温结晶动力学，用扫描电子显微镜观察了PE—LLD-g—AA等温结晶形态。结果表明，PE-LLD-g-AA的结晶速率大于纯PE—LLD的，随着接枝率的增加，PE-LLD的球晶半径减小，接枝到PE—LLD分子链上的AA分子起到了成核剂的作用。     

Preparation,characterization, and some physical properties of polypropylene/poly(methyl acrylate)‐grafted glass wool composites

Polypropylene/poly(methyl acrylate)‐grafted glass wool (PMA‐g‐GW) mixes were prepared. The polymerization process was carried out using potassium persulfate (PPS) and PPS/acetone sodium bisulfite (ASBS) as a redox‐pair initiation system at 60 and 70°C. The effect of using PPS or PPS/ASBS on the grafting percent and conversion percent reveals that the conversion percent values on using PPS as an initiator are higher than those of PPS/ASBS, while in the case of grafting, the inverse is true, that is, using PPS as an initiator gives grafting percent values lower than those that can be obtained using PPS/ASBS. The dielectric properties, thermal diffusivity, specific heat capacity, and thermal conductivity of PP loaded with modified glass wool as a function of different types and concentrations of initiators—used in the grafting polymerization process, namely, PPS and the redox initiating system—were also studied. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 723–732, 2003     

乳液聚合中单体醋酸乙烯酯与保护胶体聚乙烯醇的接枝反应研究

研究了以聚乙烯醇为保护胶体的醋酸乙烯乳液聚合中,聚乙烯醇与单体的接枝反应。探讨了引发剂用量、聚合反应温度、保护胶体聚合度等因素对接枝反应的影响。     

POE-g-MAH及其在增韧尼龙6中的应用

利用熔融接枝法制备了马来酸酐接枝乙烯-辛烯共聚物（POE-g—MAH），探讨了各个因素对POE-g—MAH接枝率和熔体流动速率（MFR）的影响，并得出了最佳配方、最佳工艺条件。将POE与接枝产物POE-g—MAH同时作为弹性体改性PA6时，体系的缺口冲击强度较纯尼龙提高近9倍，而其他力学性能改变不大。     

马来酸酐接枝聚丙烯研究进展

介绍了马来酸酐接枝聚丙烯的方法、机理,并重点介绍了溶液法和共单体熔融法影响接枝率的因素。     

Effects of cobalt and potassium doping on thermal stability and electrical properties of radiation grafted acrylic acid onto poly(tetrafluoroethylene ethylene) copolymer films

Grafted copolymer of poly(tetrafluoroethylene ethylene) (ET) with acrylic acid (AAc) was prepared by direct radiation method. The obtained films were modified by treating with small amounts of Co²⁺ and K⁺ ions (1.0 wt %). The effects of such treatment on the thermal stability and electrical conductivity of these films were studied. Cobalt treatment did not much affect the thermal degradation of the films. The results obtained revealed that k⁺ treatment enhanced the thermal degradation of ET‐g‐PAAc, which started 273 K lower than that observed in the case of the untreated and Co²⁺‐treated films. Potassium and cobalt treatment of the investigated films increased their electrical conductivity (σ) and decreased the activation energy ΔE_σ. The increase in σ values was, however, more pronounced in the case of K⁺‐treated film. These results were discussed in terms of the effective increase in the hydrophilicity of the films, especially those treated with potassium. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 867–871, 2005     

聚烯烃接枝马来酸酐的反应挤出研究

研究了聚乙烯（PE），聚丙烯（PP）接枝马来酸酐（MAH）的反应挤出，进行了反应体系的热分析，讨论了引发剂过氧化二异丙苯（DCP）和PE／DCP和PP／DCP体系的影响，以及DCP、MAH和电子给予体（EDA）和LDPE／DCP／MAH和PP／DCP／MAH两种接枝体系的影响。