H-complex formation and influence on the radical copolymerization of acrylic acid and 1-vinyl-2-pyrrolidone in tetrahydrofuran

The association constant of the H-complex formation between acrylic acid and 1-vinyl-2-pyrrolidone in tetrahydrofuran at 22°C (K₁ = 1350 mol 1^?1) was determined by means of ¹H NMR spectroscopy. A detailed equation for the copolymer composition, accounting for the participation in the chain propagation of the above complex and that between acid and solvent molecules, was derived. It was used for evalution of the relative reactivities of the complexes discussed and of the uncomplexed 1-vinyl-2-pyrrolidone molecules.     

A qualitative criterion proving the participation of comonomer complexes in the chain propagation of radical copolymerization

The juxtaposition of the equations for copolymer composition for chain propagation following the terminal (T), penultimate (P) and complex (C) mechanisms shows that the copolymer composition depends on the total co-monomer concentration only when a comonomer complex participates in the pro-pagation. This makes it possible to define an easily applicable criterion proving comonomer complex participation yet not excluding propagation according to the T and P mechanisms. The criterion has been tested for the copolymerization of 1-vinyl-2-pyrrolidone with acrylic and methacrylic acids, and of styrene with maleic anhydride. It has been shown that such a dependence cannot be claimed for styrene–methyl methacrylate copolymerization. © 1998 SCI.     

Dependencies of the first and second moments of copolymer composition on conversion – a new discrimination tool of radical copolymerization mechanisms

A method discriminating between terminal and complex copolymerization mechanisms based on the comparison of the experimentally-determined dependences of the average and the instantaneous copolymer composition and its dispersion on conversion with those derived from the model schemes is suggested. The analysis of the conversion dependences allows the assessment of the copolymer compositional homogeneity and the dominating mechanism of chain propagation. An easily applicable criterion proving monomer complex participation for the cases when the composition curve crosses the azeotropic line has been defined on the dependence of the monomer feed composition at which dispersion has minimum value on conversion. It is also shown that conversion curves carry information about changes in the kinetic, hydrodynamic and thermodynamic characteristics of the reaction medium. The efficiency of the suggested methods has been tested for the copolymerization of acrylic acid and 1-vinyl-2-pyrrolidone. © 1999 Society of Chemical Industry     

等规聚丙烯-丙烯酸接枝共聚

详细研究了等规聚丙烯细粒子在丙烯酸水溶液中,以过氧化苯甲酰为引发剂的液－固相接枝共聚反应和十氢化萘乙醇溶液对等规聚丙烯的膨化预处理作用,检测了等规聚丙烯－聚丙烯酸的某些性质,发现随接枝率提高,其吸湿性和碱性染料染色性均提高,熔点略有降低,但熔体流动性下降,按本研究获得的最佳膨化预处理条件和最佳接枝共聚反应条件,接枝产物等规聚丙烯－聚丙烯酸的接枝率可超过13％。     

Graft copolymerization of acrylic acid on cellulose: Reaction kinetics of copolymerization

Acrylic acid (AA) was grafted to cellulose by using ceric ammonium nitrate (CAN) initiator in aqueous nitric acid solution at 30, 50, 70, and 90°C during reaction periods of 30 to 180 minutes. About 45% of the AA was polymerized at 90°C after 180 minutes. The grafted polymer and homopolymer were isolated by acetone from the reaction mixture, dried, and subjected to Soxhlet extraction with dioxane to separate the homopolymer, poly(acrylic acid), from the graft copolymer. The water absorption capacities and grafting values of grafted cellulose were also determined. The maximum grafting yield was obtained at 30°C. It was also observed that polyacrylic acid-grafted cellulose produced at 30°C had the highest water retention capacity. The time dependence of AA conversion allowed calculation of first-order reaction rate constants. These rate constants were then used to determine apparent activation energies. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 929–934, 1997     

Effect of medium pH on the reactivity ratios in acrylamide acrylic acid copolymerization

The copolymerization reactivity ratios of acrylic acid and acrylamide are found at pH 5 and pH 2. Automatic continuous online monitoring of polymerization reactions (ACOMP) has been used for the first time to monitor the synthesis of polyelectrolytic copolymers. The composition drift during the reactions revealed that at pH 5, the acrylamide participates more in the copolymer, and at pH 2, the acrylic acid incorporates in the system at a higher ratio. The copolymerization data were analyzed by a recent error in variables (EVM) type calculation method developed for obtaining the reactivity ratios by on‐line monitoring and gave at pH 5 reactivity ratios r_Aam = 1.88 ± 0.17, r_Aac = 0.80 ± 0.07 and at pH 2 r_Aam = 0.16 ± 0.04, r_Aac = 0.88 ± 0.08. The results show that the reactivity ratios depend strongly on the pH of the medium. The effect of polyelectrolytic interactions on the reactivity ratios is discussed in detail. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 968–974, 2007     

醋酸乙烯-丙烯酸无皂乳液共聚的研究

研究了以醋酸乙烯(VAc)为主单体,丙烯酸(AA)为改性功能单体,以“半连续”加料方式进行无皂乳液共聚合过程,得到了稳定的乳液。并探讨了功能单体AA含量、反应温度等对共聚的影响。采用FTIR、粒度分析等方法对共聚物的组成、乳胶粒子的尺寸及分布进行了分析表征。结果表明:在(65±2)℃的温度下聚合,所得乳液稳定性好、转化率高,反应完全,且随着功能单体AA含量的增加,乳液粘度上升,单体转化率下降,乳胶粒粒径变小且粒径呈单分散性。     

用低温等离子体诱导PET织物接枝丙烯酸

运用氧气等离子体表面改性技术对PET织物进行处理后接枝丙烯酸,探讨了处理时放电功率、单体浓度、反应温度、处理时间等对接枝率的影响,并对接枝率与织物的吸湿性进行了研究。     

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%.     

Graft copolymerization of acrylic acid onto guar gum

The graft copolymerization of acrylic acid (AA) onto guar gum (GOH) was carried out by a peroxydiphosphate (PDP)–silver(I) system. Grafting ratio, efficiency, add‐on, and conversion increase upon increasing the concentration of PDP and acrylic acid, whereas they decrease upon increasing the concentration of guar gum. Upon increasing the concentration of silver and hydrogen ions up to 2.0 × 10⁻³ and 4.87 × 10⁻² mol dm⁻³, respectively, the grafting ratio and efficiency increase but decrease upon further increasing the concentration. The increase in temperature from 30 to 45°C increases the grafting ratio but the conversion efficiency decreases. The optimum time period for graft copolymerization was found to be 2 h. The graft copolymers were characterized by infrared spectroscopy and thermogravimetric analysis. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 39–44, 2000     

Graft copolymerization of PU membranes with acrylic acid and crotonic acid using benzoyl peroxide initiator

To improve water wettability of polyurethane (PU), graft copolymerization with acrylic acid (AA) and crotonic acid (CA) was performed using a benzoyl peroxide (BO) initiator. The grafting reaction was carried out by placing the membranes in aqueous solutions of AA and CA at constant temperatures. Variations of graft yield with time, temperature, initiator, and monomer concentrations were investigated. The optimum temperature, polymerization time, monomer, and initiator concentrations for AA were found to be 70°C; 3 h; 1.5 M; 5.0 × 10^?2 M, and for CA 70°C; 1 h; 1.5 M; 4.0 × 10^?2 M, respectively. The grafting membranes were characterized by FTIR spectroscopy and scanning electron microscopy (SEM) analysis, and the effect of grafting on equilibrium water content (EWC) of PU membranes was obtained by swelling measurements. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2690–2695, 2001     

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     

醋酸乙烯-丙烯酸无皂乳液共聚的研究

研究了醋酸乙烯(VAc)与丙烯酸(AA)以“半连续”加料方式进行无皂乳液共聚合。探讨了功能单体AA用量、反应温度等对共聚的影响。采用FTIR、粒度分析等测试方法对共聚物的组成、乳胶粒子的粒径及分布进行了分析表征。结果表明,在(65±2)℃的温度下聚合,所得乳液稳定性好、转化率高,反应完全,且随着功能单体AA用量的增加,乳液黏度上升,单体转化率下降,乳胶粒粒径变小且粒径单分散性好。     

丙烯酸类共聚破乳剂的研究

合成了丙烯酸类共聚破乳剂，研究了温度、溶剂用量、时间和单体配比、引发剂用量、pH调节剂用量、有无阻聚剂等因素对反应的影响。最佳手件下合成的产品加药量50mg／L，在80℃，8h内，脱水原油含水7．01％。     

Graft copolymerization of acrylic acid onto polystyrene using the solid phase grafting technique

Graft copolymerization of acrylic acid (AAc) onto polystyrene (PS) by the solid phase graft copolymerization technique was studied. Benzoyl peroxide (BPO) was used as the free radical initiator. Acrylic acid was introduced into the reactor as an aqueous solution. Optimum reaction conditions to obtain maximum grafting were evaluated. The variables studied were temperature, initiator concentration, monomer concentration, acrylic acid-to-water ratio, and reaction time. The graft copolymer was characterized by infrared (IR) spectroscopy, and the graft level was quantified by the IR absorbance ratio technique and titration. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1001–1007, 1998     

麦秸秆纤维素与丙烯酸接枝共聚制备耐盐性吸水树脂的研究

应用小麦秸秆与丙烯酸接枝共聚制备了耐盐性吸水树脂,进行了结构表征,研究了单体配比、丙烯酸中和度、引发剂和交联剂用量以及反应温度对吸盐水倍率的影响。研究发现,接枝共聚的适宜条件为:丙烯酸单体与麦秸秆质量比为8∶1,丙烯酸中和度为70%,引发剂过硫酸钾-硫代硫酸钠的用量为单体的3.5%,交联剂N,N-亚甲基双丙烯酰胺用量为单体质量的0.24%,反应温度为70℃。在此条件下制备的树脂吸盐水倍率最高,吸盐水(CNaC l=0.9%)可达68 g/g,可应用于医疗卫生等方面。     

AN-VAc-AMPS三元共聚合研究

介绍了丙烯腈 ( A N) -醋酸乙烯 ( VAc) (或丙烯酸甲酯 ( MA ) -2 -丙烯酰胺基 -2 -甲基丙磺酸 (英文缩写 AMPS)三元共聚合体系各组分竞聚率的测定方法 ,并比较三元共聚体系和二元共聚体系的AN /VAc竞聚率 ,对三元连续共聚进行了试验 ,讨论 A MPS含量与染色性的关系 ,聚合工艺条件与转化率关系。对聚合物溶液的流变性能及纺丝工艺 ,纤维的性能作了简单介绍。聚合及纺丝试验结果证明 ,以 AMPS为第三单体的三元共聚体系可纺性良好 ,所得纤维的物理性能、染色性能、吸水性和抗静电性均优于一般腈纶     

丙烯酸与异形聚酯共混纤维接枝共聚研究

以过氧化苯甲酰为引发剂,丙烯酸为单体与碱处理后的异形聚酯共混纤维接枝共聚,井对接枝后的异形聚酯共混纤维进行了结构和性能研究。结果表明:BPO浓度在0．01 moL／L,丙烯酸浓度1．50 mol/L,聚合温度85℃,时间90 min,所获得的接枝率为12％。随着接枝率的上升,热稳定性下降,回潮率增加,抗静电性能增加。     

Graft copolymerization of acrylic acid onto cellulose: Effects of pretreatments and crosslinking agent

The graft copolymerization of acrylic acid (AA) and 2‐acrylamido 2‐methylpropane sulfonic acid (AASO₃H) onto cellulose, in the presence or absence of crosslinking agent N,N′‐methylene bisacrylamide (NMBA), by using different concentrations of ceric ammonium nitrate (CAN) initiator in aqueous nitric acid solution at either 5 or 30°C was investigated. To investigate the effect of pretreatment of cellulose on the copolymerization, before some grafting reactions cellulose was pretreated with either 2 or 20 wt % NaOH solutions or heated in distilled water/aqueous nitric acid (2.5 × 10^?3 M) at 55°C. To determine how the excess of initiator affects the grafting and homopolymerization, separate reactions were carried out by removing the excess of ceric ions by filtration of the mixture of initiator solution and cellulose before the monomer addition. Extraction‐purified products were characterized by grafting percentage and equilibrium swelling capacity. Pretreatment of cellulose with NaOH solutions decreased the grafting percentage of copolymers. In the case of AA–AASO₃H mixtures, nonpretreated cellulose gave a higher grafting percentage than NaOH‐pretreated cellulose. Filtration also lowered the grafting of AA on the cellulose in the cases of pretreatment with either water or nitric acid. Copolymers with the highest grafting percentage (64.8%) and equilibrium swelling value (105 g H₂O/g copolymer) were obtained in grafting reactions carried out in the presence of NMBA at 5°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2267–2272, 2001