松香中海松酸型树脂酸在酸作用下的组成变化规律

详细研究了在溶液状态下酸催化作用引起松香中海松酸型树脂酸组成变化的特征及规律,以甲苯、醋酸等作为溶剂,醋酸、盐酸、硫酸等作为催化剂,反应温度为保持良好回流,反应时间1～8h。研究结果表明,松香中的海松酸型树脂酸在醋酸作用下比较稳定,其组成没有发生明显的变化。在盐酸、硫酸作用下,松香中原有的海松酸、异海松酸、山达海松酸明显减少,初始质量分数越高、酸作用时间越长,减少越明显,与此同时产生了原料中没有的8,15-异海松酸、8,15-海松酸和7,15-海松酸,且随酸作用时间延长而增多。在质量分数为51.4%的硫酸催化作用下于甲苯中回流8h后,湿地松松香中的海松酸型树脂酸质量分数变化为:异海松酸由13.77%降至10.53%,山达海松酸由1.78%升至1.98%,8,15-异海松酸则从0升至5.05%;马尾松松香中的海松酸型树脂酸质量分数变化为:海松酸由7.45%降至3.02%,7,15-海松酸由0升至0.67%,8,15-海松酸则从0升至3.99%。海松酸型树脂酸主要发生以环内双键位置变化为主的异构反应,很少发生分解反应,而环外乙烯基则没有参与反应,松香中各海松酸型树脂酸总质量分数基本不变。对海松酸型树脂酸各成分的立体结构分析及异构体之间的相关性分析结果表明,8,15-异海松酸应来源于异海松酸和山达海松酸的异构化,而8,15-海松酸和7,15-海松酸应来源于海松酸的异构化反应。     

Synthesis of semi interpenetrating network hydrogel [(GrA‐Psy)‐cl‐Poly (AA)] and its application for efficient removal of malachite green from aqueous solution

In the present study, the synthesis of novel semi‐interpenetrating network (Semi‐IPN) hydrogel based on gum rosin alcohol‐psyllium (GrA‐Psy) has been reported. (Gum rosin alcohol‐psyllium)‐crosslinked‐poly(acrylic acid) [termed as (GrA‐Psy)‐cl‐poly (AA)] was synthesized using potassium persulphate (KPS) as an initiator and N, N^′? methylene‐bis‐acrylamide (MBA) as crosslinker by free radical graft co‐polymerization technique. The prepared semi‐IPN was characterized using FTIR, XRD, and FE‐SEM. Further, the synthesized hydrogel was evaluated for the removal of malachite green (MG) dye from aqueous solution. Dye adsorption data was analyzed through various isotherm and kinetic models. Thermodynamic parameters and reusability of the synthesized adsorbent were also assessed. POLYM. ENG. SCI., 59:1416–1427 2019. © 2019 Society of Plastics Engineers     

松香改性丙烯酸酯乳液的合成及其在PVC地板胶的应用

采用半连续种子乳液聚合的方法制备了一种具有核壳结构的松香树脂改性PVC地板胶用丙烯酸酯聚合物乳液,讨论了松香树脂质量分数、松香树脂加入方式、核壳质量比等因素对聚合物乳液性能的影响。结果表明,当松香树脂质量分数为2%,核壳单体的质量比为1∶2时,乳液的初黏性(#33)达到1.3 cm,粘接强度达到0.32 MPa。     

Preparation and polymerization of vinyl monomers containing a heterocyclic pendant group

New vinyl monomers having an isoxazole heterocyclic group were synthesized and were polymerized in dimethylformamide using azobisisobutyro-nitrile as a free radical initiator. The dependence of the rate of polymerization on monomer and initiator concentrations was determined, as well as the activation energy of polymerization. The addition of Lewis acid was found to affect the rate of polymerization. The prepared monomers were copolymerized with styrene, vinyl acetate, acrylonitrile and methyl methacrylate. The monomer re-activity ratios of all the systems were determined by linear and non-linear methods, and the Q and e values for the monomers were calculated by considering the four copolymerization systems in each case. ©1997 SCI     

松香树脂酸的单离与应用

分别综述了枞酸、左旋海松酸、脱氢枞酸、新枞酸等松香树脂酸在医药、农药、表面活性剂制备以及在其他精细化学品合成中的应用,指出纯粹的松香树脂酸作为绿色化学合成的原料有广阔的工业应用前景。介绍了松香树脂酸单离的胺盐结晶方法,提出对松香树脂酸单离的研究重点是加快胺化反应速度、强化结晶传递过程、采用反应与分离耦舍的方法,以提高松香树脂酸的提取率。     

Preparation and characterization of polyacrylate/polymerized rosin composite emulsions by seeded semicontinuous emulsion polymerization

Polyacrylate/polymerized rosin composite emulsions were prepared by seeded semicontinuous emulsion polymerization of acrylate monomers in which polymerized rosin was dissolved. The effects of polymerized rosin content on the polymerization stability, monomer conversion, polymer structure, and adhesive properties were studied. Polyacrylate/polymerized rosin composites were characterized by gel permeation chromatograph (GPC), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and thermogracvimetry (TG). The results showed that with an increase of polymerized rosin content from 0 to 6 wt %, gel fraction and sol molecular weight decreased obviously but monomer conversion was basically unchanged. In contrast, with a further increase of polymerized rosin content, the decreasing rates of gel fraction, and sol molecular weight were slowed down. Meanwhile, monomer conversion decreased remarkably. Moreover, interface failure changed into cohesive failure after the addition of polymerized rosin, and the peel adhesion and shear resistance of composite latex films declined with the increase of polymerized rosin content. Thermal analysis showed that polymerized rosin and polyacrylate were compatible and the composite latex films had good thermal stability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

丙烯海松酸的合成研究

通过松香与丙烯酸的Diels-Alder加成反应制备了丙烯海松酸,考察了原料摩尔比对反应的影响。实验结果表明,随着丙烯酸用量的增加,产物的酸值和软化点逐步升高至不变;紫外光谱研究发现,随着丙烯酸用量的增长,枞酸型树脂酸相对含量下降,而海松酸型树脂酸的含量未见显著变化;气相色谱-质谱联用分析显示,在松香树脂酸与丙烯酸的加成反应中,树脂酸中的海松酸、异海松酸、脱氢枞酸等不参与反应,而长叶松酸、枞酸和新枞酸异构化为左旋海松酸,与丙烯酸发生加成反应;即使丙烯酸过量,长叶松酸和枞酸转化率最高也只可以达到91%和86%;研究还发现,加成产物丙烯海松酸有二种构造异构体,分别占丙烯海松酸量的20%和80%。     

气相色谱用马尾松松香标准样品的定值

系统地介绍了气相色谱用马尾松松香标准样品的定值方法。采用单一方法通过6家实验室联合定值,得到标准样品中7种树脂酸的GC含量(%)的特性值和扩展不确定度:海松酸8.2683±0.3203;山达海松酸:1.7433±0.3199;异海松酸:0.7652±0.3118;长叶松酸:30.8201±1.3668;去氢枞酸:3.2731±0.8693;枞酸:34.9275±1.2664;新枞酸:18.7469±1.8494。     

影响硬丁腈橡胶3604聚合反应速率的因素

采用松香酸皂、油酸皂和萘磺酸钠甲醛(NSF)缩合物为复合乳化体系替代拉开粉热法合成丁腈橡胶3604,在水相pH值为10～12的条件下,考察聚合温度、引发体系、复合乳化剂的用量和配比等因素对聚合反应速率的影响.结果表明,在聚合温度为30℃,过硫酸钾与三乙醇胺的质量比为4.00/1,复合乳化剂中NSF缩合物为0.5份、松香...     

Graft copolymerization of methyl methacrylate and other vinyl monomers onto cotton fabric using ferrous cellulose thiocarbonate–N-bromosuccinimide redox initiation system

The cellulose thiocarbonate, in the fabric from, was treated first with a freshly prepared ferrous ammonium sulphate (FAS) solution. The sotreated fabric formed, with N-bromosuccinimide (NBS), an effective redox system capable of initiating grafting of methyl methacrylate (MMA) and other vinyl monomers onto the cotton fabric. The effect of the polymerization conditions the polymer criteria, namely, graft yeild, homopolymer, total conversion, and grafting efficiency, was studied. These polymer criteria were found to depend extensively upon concentrations of the Fe²⁺ ion (activator), NBS (initiator), and MMA; pH of the polymerization medium, and duration and temperature of polymerization. Based on detailed investigation of these factors, the optimal conditions for grafting were as follows: Fe²⁺, 1 × 10⁻³ mol/L; NBS, 1 × 10⁻² mol/L; MMA, 4%; pH, 2: polymerization time, 150 min; polymerization temperature, 60°C; material/liquor ratio, 1: 100. Under these optimal conditions, the rates of grafting of different vinyl monomers were in the following sequence: methyl methacrylate ≫ methyl acrylate > acrylonitrile. Other vinyl monomers namely, acrylic acid, and methacrylic acid have no ability to be grafted to the cellulosic fabric using the said redox system. A tentative mechanism for the polymerization reaction is suggested. © 1996 John Wiley & Sons, Inc.     

Disubstituted p-phenylene monomers. α-methyl- and α-phenyl-vinyl derivatives of benzene,biphenyl, p-terphenyl,and p,p′-diphenoxiybiphenyl

The high-yield syntheses of bis [p-(α-methylvinyl)] monomers of benzene, biphenyl, p-terphenyl, and 4,4′-diphenoxybiphenyl are reported. Also described are the syntheses of new bis[p-(α-phenylvinyl)] monomers of biphenyl, p-terphenyl, and 4,4′-diphenoxy-biphenyl. Infrared spectral data for the diolefinic monomers and their precursors are presented, together with brief details for the polymerization of the diolefins by means of free radical and Lewis acid catalysts.     

Preparation of ultrahigh molecular weight polyacrylonitrile and its terpolymers

The synthesis of high molecular weight (in excess of 10⁶ million Daltons) poly(acrylonitrile) and poly(acrylonitrile-co-methylacrylate-co-itaconic acid) is described. An inverse emulsion polymerization formulation with AIBN as the initiator was used. However, polymer precipitation occurred early in the polymerization. In each case, the molecular weight distribution was surprisingly narrow (M?_w/M?_n ～ 1.5). Conversion vs. time plots with monomers containing the inhibitor had the “S” shape typical of emulsion polymerizations. The terpolymer composition and molecular weight were quite uniform throughout the polymerization. With inhibitor-free monomers, the initial molecular weights were very high (～ 3 × 10⁶ Daltons), but gelation occurred at ca. 50% conversion. There was an inverse relationship between the monomer inhibitor content and the polymer molecular weight. It is suggested that the growing polymer radicals are occluded in the precipitated polymer particles and are terminated by inhibitor diffusing into the particles, accounting for the narrow molecular weight distribution. © 1995 John Wiley & Sons, Inc.     

Graft copolymerization of p‐acryloyloxybenzoic acid and p‐methacryloyloxybenzoic acid onto isotactic polypropylene and their thermal properties: Part I

The polymerization and grafting of the monomers p‐acryloyloxybenzoic acid and p‐methacryloyloxybenzoic acid were studied. Poly(acryloyloxybenzoic acid) was obtained by γ‐radiation‐induced solution polymerization and bulk melt polymerization initiated by dicumyl peroxide. Poly(methacryloyloxybenzoic acid) could be obtained only by bulk melt polymerization. The graft copolymerization of the monomers onto isotactic polypropylene was carried out in bulk. The maximum grafting was reached in shorter times at higher temperatures, and it also increased with the concentration of the monomers in the reaction medium. The thermal and crystallization behavior of the graft copolymers was studied with differential scanning calorimetry and wide‐angle X‐ray diffraction. The graft copolymerization of p‐acryloyloxybenzoic acid did not have any influence on the formation of both α forms (monoclinic) of polypropylene, whereas p‐methacryloyloxybenzoic acid led to the α₂ form. The β‐crystalline modification (hexagonal) formed in poly(acryloyloxybenzoic acid)‐g‐polypropylene products at 185°C and at higher grafting temperatures and also in the second run of differential scanning calorimetry studies after fast cooling. The β form was not observed in graft copolymers of poly(methacryloyloxybenzoic acid). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

改性溶剂型聚丙烯酸酯压敏胶的研制

以丙烯酸丁酯(BA)为软单体、丙烯酸甲酯(MA)为硬单体、2-丁酮(MEK)为溶剂和偶氮二异丁腈(AIBN)为引发剂,采用溶液聚合法合成了溶剂型聚丙烯酸酯PSA(压敏胶);然后以交联单体丙烯酸(AA)和丙烯酸羟乙酯(HEA)作为化学交联改性剂、增黏树脂松香作为共混改性剂,考查了各单体用量对PSA综合性能的影响。结果表明:当w(MA)=43.0%、w(AA)=14.0%、w(HEA)=4.9%和w(松香树脂)=18.0%(均相对于BA质量而言)时,PSA胶带的综合性能相对最好,其180°剥离强度为0.917 kN/m、剪切强度为0.651 MPa、初粘力为6#号钢球和持粘力为7.0 h。     

SYNTHESIS,CHARACTERIZATION, AND THERMAL STABILITY OF HOMOPOLYMER AND COPOLYMER OF SOME 3-ARYL-2-HYDROXYPROPYL METHACRYLATES

Three new hydroxypropyl methacrylates having three different aryl rings were synthesized by addition of 2,3-epoxypropyl aromatic hydrocarbon to methacrylic acid. The monomers prepared are 3-phenyl-2-hydroxypropyl methacrylate, 3-tolyl-2-hydroxypropyl methacrylate, (THPMA), and 3-naphtyl-2-hydroxypropyl methacrylate. The homopolymers of these monomers and two different copolymers, [poly(THPMA-co-BMA)], were obtained from polymerization at 60°C in 1,4-dioxane solution using AIBN as initiator. All the monomers and the polymers were characterized by FT-IR and ¹H and ¹³C NMR techniques. Solubility parameters of the polymers and average molecular weight of poly(THPMA) were determined. Thermal stabilities of the polymers were given as comparing with each other by using TGA curves. Thermal degradation of poly(THPMA60%-co-BMA40%) was studied in detail.     

Studies on the kinetics of free-radical bulk polymerization of multifunctional acrylates by dynamic differential scanning calorimetry

The course and kinetics of nonisothermal bulk polymerization of multifunctional acrylates were studied by dynamic differential scanning calorimetry (DSC). Measurements were carried out for four straight-chain monomers, diethylene glycol diacrylate (DEGDA), triethylene glycol diacrylate (TEGDA), tetraethylene glycol diacrylate (TTGDA), and poly(ethylene glycol)diacrylate (PEGDA) (mol. wt. 600), to study the effect of the backbone chain length, atmosphere, and type of initiator on the crosslinking kinetics. 4,4′-Azobis(4-cyanovaleric acid) (1.0%, w/w) was used as a free-radical initiator. From the dynamic scanning of polymerization of DEGDA at five heating rates (2–30°C/min), the average heat of polymerization (ΔH_p) was found to be 524.2 J/g. An activation energy of 108.8 kJ/mol and preexponential factor 5.34 × 10¹² s^?1 were obtained from the Arrhenius plot, In dα/dt. The rate of polymerization was found manyfold greater at 20–60% conversion than at the initial stage (2–8% conversion). Polymerization was studied under both nitrogen and air atmosphere. The results corresponded well with the theory of oxygen inhibition. Different types of initiators, e.g., 4,4′-azobis(4-cyanovaleric acid) (ABCVA), 2,2′-azobisisobutyronitrile (AIBN), and benzoyl peroxide (BPO) were used for polymerization and ABCVA was found to be the most efficient among all. © 1995 John Wiley & Sons, Inc.     

Synthesis and properties of carboxymethyl cellulose‐graft‐poly(acrylic acid‐co‐acrylamide) as a novel cellulose‐based superabsorbent

A new cellulose‐based superabsorbent polymer, carboxymethyl cellulose‐graft‐poly(acrylic acid‐co‐acrylamide), was prepared by the free‐radical grafting solution polymerization of acrylic acid (AA) and acrylamide (AM) monomers onto carboxymethyl cellulose (CMC) in the presence of N,N′‐methylenebisacrylamide as a crosslinker with a redox couple of potassium persulfate and sodium metabisulfite as an initiator. The influences of reaction variables such as the initiator content, crosslinker content, bath temperature, molar ratio of AA to AM, and weight ratio of the monomers to CMC on the water absorbency of the carboxymethylcellulose‐graft‐poly(acrylic acid‐co‐acrylamide) copolymer were investigated. The copolymer's structures were characterized with Fourier transform infrared spectroscopy. The optimum reaction conditions were obtained as follows: the bath temperature was 50°C; the molar ratio of AA to AM was 3 : 1; the mass ratio of the monomers to CMC was 4 : 1; and the weight percentages of the crosslinker and initiator with respect to the monomers were 0.75 and 1%, respectively. The maximum water absorbency of the optimized product was 920 g/g for distilled water and 85 g/g for a 0.9 wt % aqueous NaCl solution. In addition, the superabsorbent possessed good water retention and salt resistance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1382–1388, 2007     

Characteristics of methacrylic acid‐grafted polyethylene films prepared by photografting in the presence of polyfunctional monomers

Photografting of methacrylic acid (MAA) on low‐density polyethylene film (thickness = 30 μm), on which xanthone photoinitiator was coated earlier, in the presence of polyfunctional monomers such as N,N′‐methylenebisacrylamide, ethylene glycol dimethacrylate, and trimethylol propane triacrylate was examined at 60°C in water/acetone (3:1 v/v) mixture solvent. The photografting was retarded at the earlier stage of polymerization, and then accelerated when small amounts of the polyfunctional monomers (1–3 mol % of MAA monomer used) were added to the system. Addition of the polyfunctional monomers did not affect distribution of the grafted chains in the cross section of the resultant MAA‐grafted PE film, which was measured by electron probe microanalysis. The MAA‐grafted samples were subjected to adsorption of cupric ions at 25°C for 24 h in the system of pH = 5. The adsorption was considerably suppressed for the grafted samples prepared at the earlier stage of polymerization in the system with the polyfunctional monomers. The phenomenon was discussed in terms of the formation of crosslinked and branched structures in the MAA‐grafted chains depending on the polymerization stage in the system with polyfunctional monomers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1262–1268, 2006     

Preparation and characterization of molecularly imprinted polymer of bovine serum albumin

Molecularly imprinted polymer beads of bovine serum albumin (BSA) were prepared via inverse phase suspension polymerization, using BSA as the template molecule, a combination of acrylamide and methacrylic acid (MAA) as double functional monomers, and N, N′‐methylene bisacrylamide as the crosslinker. The effect of different monomer ratios and degrees of crosslinking were investigated. When both selectivity and physical properties of the resultant polymer beads were taken into account, the ratio of MAA in the total monomers was chosen at 40% (m/m) and the degree of crosslinking at 30% (n/n), the resultant polymer beads had good selectivity (α = 2.77) and good physical properties. The effects of pH and temperature were studied. It turned out that the functionalization of polymers of BSA prepared via inverse‐phase suspension polymerization exhibited specific recognition for BSA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The in situ polymerization of vinyl monomers in polyester yarns

The effects of a pretreatment of polyester (PET) yarns with a strongly interacting solvent such as dimethylformamide (DMF) on vinyl monomer incorporation were investigated. When the DMF pretreatment is carried out at high temperatures (above 120°C), the swollen PET structure is stabilized by solvent-induced secondary crystallization. This substrate is highly suitable for the incorporation of vinyl monomers. In situ polymerization of vinyl monomers in DMF-treated PET was investigated using chemical and γ-irradiation polymerization techniques, both in the presence and in the absence of excess monomer outside the PET fibers. When polymerization was carried out in a system in which a constant supply of free radicals was available from the outside of the PET fibers, lower initiator concentrations and smaller γ-irradiation doses were necessary. These results are attributed to a low efficiency of the initiator inside the PET fiber due to mobility restrictions. Water uptake and moisture regain of PET yarns containing poly(hydroxyethyl methacrylate) and poly(acrylic acid) were also investigated. When most of the vinyl polymer was inside the PET fiber, water absorption was limited. The changes in mechanical properties of the PET yarns resulting from the DMF pretreatment were partially reversed by in situ polymerization of vinyl monomers.