Study of Vinyl Acetate Partitioning in Emulsion Copolymerization of Vinyl Chloride-Vinyl Acetate by FTIR and HNMR Spectroscopy

Emulsion copolymerization of vinyl chloride with vinyl acetate comonomer was performed. Potassium persulfate, a mixture of stearyl alcohol and sodium lauryl sulfate, was used and reactions were performed at 55 °C in a pressurized reactor. By sampling during the reaction in different intervals copolymer composition was investigated using FTIR and NMR spectroscopy. The results showed that the partitioning of vinyl acetate in the copolymerization in general follows the Mayo-Lewis copolymerization equation with some discrepancy. This was attributed to the gaseous nature of vinyl chloride monomer and the differences between polymerization in heterogeneous and homogeneous systems. Both FTIR and NMR spectroscopy showed two peaks in vinyl acetate content of copolymer beyond 65% conversion which was attributed to the elimination of vinyl chloride droplets in the media and replacing them with vinyl acetate monomer. The first increase is related to the consumption of vinyl chloride droplets and the second is related to the consumption of gaseous vinyl chloride; in both instances vinyl acetate governs the polymerization.     

PVA/接枝改性淀粉热塑性生物降解材料的制备及应用

以过硫酸铵为引发剂,采用固相法合成了乙酸乙烯酯(VAC)/玉米淀粉接枝共聚物.将其与聚乙烯醇(PVA)、加工助剂在流变仪中共混,制备了PVA/接枝改性淀粉热塑性生物降解材料;分别研究了淀粉接枝共聚物对PVA/淀粉/接枝改性淀粉共混物的加工流动性、耐水性、力学性能和生物降解性能及形态结构的影响.结果表明,PVA/淀粉/接...     

Grafting of vinyl acetate onto low density polyethylene—starch biodegradable films for printing and packaging applications

Starch‐based biodegradable low‐density polyethylene (LDPE) films were used for graft copolymerization of vinyl acetate with ceric ammonium nitrate (CAN) in aqueous acidic medium as redox initiator with nitric acid. The extent of grafting was examined by Fourier‐transform infrared (FTIR) spectroscopy, attenuated total reflectance (ATR) spectroscopy, X‐ray diffraction (XRD) and scanning electron microscopy (SEM). The objective behind the grafting of vinyl acetate onto the LDPE–starch biodegradable films is to make these suitable for printing and packaging applications without affecting the biodegradability of the original films. Copyright © 2004 Society of Chemical Industry     

木薯双醛淀粉制备木材用胶粘剂的研究

以木薯淀粉为原料、高碘酸钠为氧化剂,在一定条件下制得双醛淀粉(DAS);然后以过硫酸铵(APS)为引发剂、聚乙烯醇(PVA)为保护胶体和醋酸乙烯酯(VAc)为DAS的接枝单体,再配合其他助剂制得双醛接枝淀粉基木材用胶粘剂。结果表明:当w(DAS中醛基)=20%、m(DAS)∶m(VAc)=1∶2.5、w(PVA)=75%、VAc为25 mL、接枝反应温度为65℃和反应时间为3 h时,胶粘剂的干、湿强度分别为3.0、2.4 MPa。     

Silane‐modified poly(ethylene‐co‐vinyl acetate): influence of comonomers on peroxide‐initiated vinylsilane grafting

Functionalization of poly(ethylene‐co‐vinyl acetate) (EVA) with vinyltriethoxysilane (VTEOS) has been carried out by a free‐radical melt‐grafting procedure in the presence of added comonomers. The influence of comonomers on silane graft yield and crosslink density has been assessed. Experiments were performed on masterbatches of EVA, VTEOS (5 wt %), peroxide initiator (L‐231, 0.05 wt %), and comonomer (0–1 comonomer : VTEOS mole ratio) prepared at 90°C. Melt‐grafting experiments were carried out at 145°C in an oscillating disk rheometer (ODR), which measured crosslink density during the grafting process. Silane graft yields were determined by proton NMR spectroscopy. Comonomers evaluated were maleic anhydride (MAn), 1‐vinyl‐2‐pyrrolidone (VP), and 1‐dodecene (DD). At the comonomer ratios examined, MAn suppressed both silane grafting and peroxide‐initiated crosslinking. Both VP and DD, however, exhibited greater selectivity in suppressing crosslinking than silane grafting; optimum performance was found at a comonomer : vinylsilane mole ratio of 0.2. None of the comonomers studied enhanced the level of silane grafting. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1308–1314, 2000     

Preparation and thermal characterization of graft copolymer obtained by radiation grafting of individual and binary monomer systems

Graft copolymers were obtained by radiation-induced grafting of vinyl acetate (VAc) and N-vinylpyrrolidone (NVP) individually and in binary mixture on to polypropylene (PP) films. The effect of some grafting conditions on the grafting yield was determined. The addition of Cu₂Cl₂ as inhibitor to the reaction medium inhibited the homopolymerization of the comonomer. The grafting process was remarkably enhanced by using dioxan as a diluent compared with other solvents used. The addition of some inorganic salts has a great influence on the individual grafting of both monomers. The gel percent in the graft copolymer was determined; it increased as the grafting yield increased. The swelling behaviour and electrical conductivity for the grafted films slightly increased by grafting. The changes in thermal parameters such as glass transition (T_g), melting (T_m) and recrystallization (T_rc) temperatures and heats of melting (ΔH_m) and recrystallization (ΔH_rc) of the graft copolymers were also followed by differential scanning calorimetry (DSC). These thermal parameters of PP were varied by grafting with VAc and NVP and depend on the graft yield, which reflects the change in its crystalline domains and formation of crosslinks in the graft chains. The heat of recrystallization of the graft copolymer by cooling from the molten state decreases by grafting which is a good indication of crosslink formation, since crosslinking decreases the crystallizability of the polymer matrix.     

Investigation of radiation grafting of vinyl acetate onto (tetrafluoroethylene–perfluorovinyl ether) copolymer films

A study has been made of radiation-induced grafting of vinyl acetate (VAc) on to (tetrafluoroethylene–perfluorovinyl ether) copolymer (PFA). Effects of grafting conditions such as inhibitor and monomer concentrations and irradiation dose on the grafting yield were investigated. In this grafting system, ammonium ferrous sulphate (Mohr′s salt) was added to the monomer-solvent mixture to minimize the homopolymerization of VAc and the most suitable concentration was found to be 2.0 wt%. It was found that the dependence of the initial grafting rate on monomer concentration is of the order 1.5. The degree of grafting tends to level off at high irradiation doses due to the recombination of formed free radicals without initiating graft polymerization. Some properties of the prepared graft copolymer such as swelling behaviour, electrical conductivity, thermal and mechanical properties were also investigated. The electrical conductivity was improved by hydrolysis of poly(vinyl acetate) in the grafted chains to their respective vinyl alcohols. The tensile properties were improved by grafting; however, the elongation percent decreased. The DTA data showed thermal stability of such graft copolymers for temperatures up to 300°C, but stability decreased at higher temperatures.     

VAc/VoeVa/DAAM三元共聚乳液的制备与性能研究

以VAE[醋酸乙烯酯(VAc)-乙烯共聚物]为种子乳液、聚乙烯醇(PVA)为保护胶体、叔碳酸乙烯酯(VoeVa10)为VAc的共聚单体、OP-10为乳化剂、己二酰肼(ADH)/双丙酮丙烯酰胺(DAAM)为交联体系和叔丁基过氧化氢/甲醛次硫酸钠为氧化还原型引发剂,采用种子乳液聚合法制备了VAc/VoeVa10/DAAM共聚乳液;然后在反应后期加入后交联剂(ADH),得到改性聚醋酸乙烯酯(PVAc)乳液。结果表明:当w(PVA1788+PVA1799)=3%、m(PVA1788)∶m(PVA1799)=1∶1、m(VoeVa10)∶m(VAc)=(10～15)∶100、w(氧化剂)=0.3%、w(VAE)=10%、w(OP-10)=2%、m(ADH)∶m(DAAM)=(0.5～1.5)∶1.0且w(DAAM)=2%时,相应乳液具有优异的耐水性和稳定性,并且其涂膜柔韧性和粘接性能俱佳。     

Synthesis and evaluation of some fatty esters as plasticizers and fungicides for poly(vinyl acetate) emulsion

n-Fatty alcohols (average molecular weight 187), prepared from n-paraffins, were treated with a series of dibasic acids such as malonic, succinic, glutaric, adipic and phthalic anhydride to give the corresponding fatty esters. The prepared fatty esters were formulated with poly(vinyl acetate) emulsion and used as films or textile coatings. Tests such as rate of drying, mechanical properties and resistance to micro-organisms were carried out. Samples of poly(vinyl acetate) plasticized with dibutyl phthalate were also prepared and evaluated for the purpose of comparison. The antifungal activity of these compounds was studied. The results obtained indicate that the prepared fatty esters can be used not only as plasticizers but also as fungicides and in some respects they are better than the conventional dibutyl phthalate plasticizer.     

酯溶性氯乙烯-醋酸乙烯酯共聚树脂的研发生产

对比进口与国产氯乙烯-醋酸乙烯酯共聚树脂的常规性能和应用性能,查找了国产氯醋树脂质量差距;针对氯乙烯和醋酸乙烯酯悬浮聚合过程提出了优化措施,改善了氯醋树脂的颗粒形态和分子组成的均匀度,进而提升了酯溶性等应用性能.     

马来酸酐改性聚醋酸乙烯酯乳液的研究

以马来酸酐(MA)作为醋酸乙烯酯(VAc)的改性共聚单体,采用半连续种子乳液聚合法合成了改性聚醋酸乙烯酯(PVAc)乳液,并考察了MA含量对VAc/MA共聚乳液性能的影响。结果表明:当w(MA)=0.3%～0.4%(相对于VAc质量而言)时,改性乳液的聚合稳定性、储存稳定性和稀释稳定性良好;随着MA含量的不断增加,种子反应阶段回流时间延长,共聚速率变慢,最终合成的改性乳液黏度逐渐增大;当w(MA)=0.4%时,改性乳液的综合性能相对最好,其粘接强度(9.70 MPa)比VAc均聚乳液增加了70%。     

醋酸乙烯生产技术发展综述

详细介绍了醋酸乙烯生产技术的发展历程,对醋酸乙烯主要的生产工艺路线进行了对比,认为乙烯气相法Leap工艺和VAntage工艺是目前最先进的生产工艺,指出醋酸乙烯生产技术未来的发展趋势。分析了我国醋酸乙烯的研究、生产和发展情况,并对我国醋酸乙烯工业的发展提出了建议。     

羧甲基甲壳素与醋酸乙烯酯接枝共聚反应研究

以过硫酸铵为引发剂,合成了醋酸乙烯酯接枝羧甲基甲壳素共聚物,采用红外光谱对接枝共聚产物进行了表征。考察了溶剂用量、反应温度、反应时间、引发剂用量、单体用量等因素对反应接枝率和接枝效率的影响,获得了最佳反应条件。结果表明：羧甲基甲壳素0．4g,溶剂水50．0mL,醋酸乙烯酯1．5g,过硫酸铵60．0mg,在70℃反应3．0h时接枝效率最高,可达65．1％。接枝共聚改性反应可以扩展羧甲基甲壳素的应用价值。     

高速卷烟胶的研制

研究了以醋酸乙烯－丙烯酸丁酯－丙烯酸三元共聚体系合成高速卷烟胶；讨论了聚乙烯醇、共聚单体、温度、乳化剂对卷烟胶性能的影响。     

氯乙烯-丙烯酸酯-醋酸乙烯酯三元共聚乳液的研究开发

采用乳液接枝共聚和核壳聚合相结合的工艺，用十二烷基硫酸钠作为新型种子乳化剂合成氯乙烯－丙烯酸酯－醋酸乙烯酯接枝共聚乳液，该乳液经Autosizeu IIC型激光粒径仪和DSC曲线测定具有核壳结构特征，用于纺织织物涂层，各项指标完全达到产品所规定的标准，效果很好。     

Synthesis,characterization, and properties of poly(vinyl acetate)‐ and poly(vinyl alcohol)‐grafted chitosan

Graft copolymers of chitosan and vinyl acetate were synthesized by free radical technique using cerium (IV) as the initiator. Under controlled conditions, as much as 92% grafting with a grafting yield of 30–40% could be achieved. Chitosan‐g‐poly(vinyl alcohol) copolymers were derived by the alkaline hydrolysis of the chitosan‐g‐poly(vinyl acetate) precursor. Thermogravimetric, FTIR, and X‐ray diffraction analyses of chitosan and the copolymers confirmed the grafting reaction between chitosan and vinyl acetate and also the subsequent hydrolysis. Both the copolymers possessed very good film‐forming properties. Grafting resulted in a significant increase in mechanical strength of both the copolymers in the dry condition. Chitosan‐g‐poly(vinyl acetate) (CH‐PVAc) proved more hydrophobic than did pure chitosan, whereas chitosan‐g‐poly(vinyl alcohol) (CH‐PVOH) exhibited enhanced hydrophilicity as evident from their swelling characteristics and contact angle measurements. The enhanced swelling of CH‐PVOH was ascribed to the presence of the pendant poly(vinyl alcohol) group. At pH 1.98, the CH‐PVAc copolymer films showed greater stability than do pure chitosan films, which is highly beneficial for specific biomedical applications. Both the copolymers showed lower glass transition temperature than do pure chitosan. Grafting did not affect the overall thermal stability, and the differential thermogram substantiated the grafting. The investigations indicate that the synthetic–natural hybrid copolymers having desirable mechanical properties and tailored hydrophilic/hydrophobic characteristics are realizable. These polymers could be exploited for varied biomedical applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1852–1859, 2007     

Effects of hydrophobic unit and its distribution on solution properties of vinyl pyrrolidone and vinyl acetate copolymer

A series of vinyl pyrrolidone and vinyl acetate copolymers with different monomer ratios and homogeneity in backbone distribution were synthesized and their solution properties studied. In water, the phase diagram curve is concave, with the lower critical solution temperature, due to the cooperation of hydrophobic and hydrophilic hydration. In order to make a substantially homogeneous copolymer, a new method to determine the monomer mole fraction is suggested. When the vinyl pyrrolidone to vinyl acetate mole ratio in the copolymer is close to unity, sequence distribution plays an important part in solution behavior. The more homogeneous the structure, the better the solubility in water, and the higher the cloud point. This is attributed to the balance between hydrophobic and hydrophilic forces in solution. Copolymerization kinetic analysis on monomer conversions and turbidity measurement on poly(vinylpyrrolidone/vinyl acetate) solutions give consistent results to confirm this interpretation. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 345–352, 1999     

氯乙烯/丙烯酸酯二元及多元共聚物的研究进展

介绍了氯乙烯/丙烯酸酯多元共聚物、聚氯乙烯树脂/丙烯酸酯/顺丁烯二酰亚胺接枝共聚物、聚氯乙烯树脂/N-取代马来酸胺/丙烯酸酯接枝共聚树脂、氯乙烯/乙酸乙烯/丙烯酸羟丙酯共聚物、氯乙烯/乙酸乙烯/丙烯酸丁酯共聚乳液、聚丙烯酸酯-氯乙烯接枝共聚物、氯乙烯/乙烯/丙烯酸羟乙酯共聚涂料树脂、氯乙烯/丙烯酸甲酯共聚乳液的特点、生产工艺及其性能和用途.     

Effects of preparation conditions on the morphology and gas permeation properties of polyethylene (PE) and ethylene vinyl acetate (EVA) films

In this study, the effect of film preparation conditions on the gas permeation properties of polyethylene (PE) and ethylene vinyl acetate (EVA) films (containing 18 and 28 wt% vinyl acetate) was investigated. Film blowing and phase inversion methods were applied in the production of PE and EVA films, respectively. The permeation of pure oxygen and carbon dioxide gases was measured at room temperature. The results indicated that with the increase of PE film thickness, permeability and solubility of O₂ and CO₂ in these films decreased; but the diffusivities of gases through PE films increased. In addition, in the case of EVA copolymers, by increasing the content of vinyl acetate, the permeability of CO₂ increased. The rate of increase in CO₂ permeability was different for samples having different preparation conditions. For example, the samples prepared using chloroform as the solvent instead of THF, showed lower CO₂ permeability. Also, the morphological studying of film structure indicated that the higher CO₂ permeability for the samples made from THF solvent is due to the existing of higher porosity in the under layer polymer area. Also scanning electron microscopy (SEM) micrographs showed that with the usage of phase inversion method, there will be a thin dense layer near to the glass substrate.     

醋酸乙烯酯与丙烯酸酯共聚乳胶涂料的研制

以醋酸乙烯酯和丙烯酸酯单体为原料,制备了醋丙共聚乳液及乳胶漆,并对某些性能做了测试。讨论了单体的配比等因素对乳液聚合反应及涂膜性能的影响,确定了适宜的反应条件及较佳的配方。