氯乙烯/丙烯腈共聚物组成和溶解性及影响因素

以十二烷基硫酸钠(SDS)为乳化剂,过硫酸钾(KPS)和亚硫酸氢钠(SBS)为氧化还原引发体系,通过乳液聚合方法制备了氯乙烯(VC)/丙烯腈(AN)共聚物.采用氧瓶燃烧法测定了共聚物的氯含量,并计算了共聚组成,通过抽提测定了共聚物在丙酮中的溶解性.考察了一步法聚合过程中共聚物组成及溶解性随聚合时间的变化,研究了初始单体投料比、引发剂用量、聚合温度等工艺条件对共聚物组成及溶解性的影响.结果表明,由于AN活性高,VC/AN共聚组成和溶解性随聚合时间变化较大;共聚物在丙酮中的溶解性与共聚组成相关,受初始单体投料比影响最大,在VC/AN投料物质的量比为7.6:1时可以获得在丙酮中全部溶解的共聚物.     

Water‐swellable hydrophobic porous copolymer resins based on divinylbenzene and acrylonitrile. I. Water‐swelling behavior

Hydrophobic porous copolymer resins based on divinylbenzene (DVB) and acrylonitrile (AN) could be prepared as directly swellable in water by using purified DVB (98.8%) and technical DVB (79.3%) in the presence of 1,2‐dichloroethane as porogen. Compared with the resins based on DVB and methyl acrylate (MA/DVB resins), the AN/DVB resins thus obtained are water‐swellable over a wider range of copolymer compositions, and the swelling ability of the AN/DVB resins in water was further confirmed by investigating the water‐swelling behavior of the AN/DVB resins undergoing solvent treatment. The copolymer composition (AN and DVB contents) of the resins and the property of the porogen affect the water‐swellable behavior of the AN/DVB resins profoundly. The results in this paper provide additional evidence to support the hypothesis that the swelling ability of a hydrophobic porous copolymer in water originates from the existence of the inner stresses in the strained polymer network of the resins and the weak interaction between polymer and water that is negligible in the case of a conventional hydrophobic polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2041–2049, 2004     

偏氯乙烯/丙烯腈/苯乙烯悬浮共聚合动力学

本文研究了偏氯乙烯（ＶＤＣ）／丙烯腈（ＡＮ）／苯乙烯（Ｓｔ）三元悬浮共聚合体系的聚合机理、共聚速率、非聚物组成及其特性粘度的影响因素。实验表明随着投料配比的改变,可分成四个不同聚合机理区域。Ｓｔ对ＶＤＣ／ＡＮ／Ｓｔ三元悬浮共聚有缓聚作用。ＶＤＣ三元悬浮共聚速率可用半经验模型,ｄＣ／ｄｔ＝αＣ＾β「Ⅰ」ｏ＾γｅｘｐ（－γｋｄｔ）描述,由实验得到模型参数γ值为２．２４,模型参数α、β是聚合温度与引发剂浓度的函数。ＶＤＣ－ＡＮ－Ｓｔ三元悬浮共聚物存在着较宽的ＶＤＣ组成分布,并受到单体ＡＮ水溶性的影响,经ＡＮ动态相平衡校正后,可预测ＶＤＣ三元共聚物组成。ＶＤＣ－ＡＮ－Ｓｔ共聚物的特性粘度随着转化率的升高而增大。在相同引发剂用量下,高转化率ＶＤＣ－ＡＮ－Ｓｔ共聚物特性粘度的对数与温度的倒数成线性关系。     

偏二氯乙烯-丙烯腈悬浮共聚动力学

研究了单体配比、引发剂浓度、聚合温度、转化率等因素对偏二氯乙烯(VDC)-丙烯腈(AN)悬浮共聚树脂的组成、相对分子质量和聚合速率的影响,建立了动力学模型,讨论了AN的水溶性对树脂组成的影响,提出了相对分子质量与聚合温度及引发剂浓度关系的模型。     

丙烯腈/丙烯酸甲酯/衣康酸三元共聚物序列结构的Monte Carlo模拟

以丙烯腈(AN)、丙烯酸甲酯(MA)、衣康酸(IA)为共聚单体,合成碳纤维用聚丙烯腈原丝的三元共聚物,利用Monte Carlo法模拟了AN／MA／IA三元共聚物的组成和序列结构,讨论了共聚单体对共聚物分子链序列结构的影响,探讨了增加序列结构均匀性的方案。结果表明:Monte Carlo法可以较为准确的模拟该共聚物的序列结构;AN／MA／IA以98／0.7／1.3的单体配比可以得到序列结构比较理想的共聚物;采取分批加入IA的方法,使共聚物的序列结构均匀性得到提高。     

Vinyl-POSS/St/AN复合材料的制备及性能研究

以1,3,5,7,9,11,13-苯基-15-乙烯基笼型倍半硅氧烷(Vinyl-POSS)、苯乙烯和丙烯腈为原料,AIBN为引发剂,用溶液聚合法制备出一种新型共聚物Vinyl-POSS/St/AN。采用傅里叶转变红外光谱(FTIR)、核磁共振(1H-NMR)等表征手段对产物进行结构表征;利用X-射线衍射(XRD)研究了POSS分子在Vinyl-POSS/St/AN中的分散性;并利用热失重分析(TGA)技术、差示扫描量热(DSC)及拉伸试验机研究了共聚物的热性能。结果表明:Vinyl-POSS的引入对共聚物的热稳定性和力学性能都有一定程度的提高。     

Influence of the copolymer architecture and composition on the response and mechanical properties of pH‐sensitive fibers

A series of copolymers based on acrylonitrile (AN) and acrylic acid (AA) with varying architecture and composition were synthesized using free radical polymerization. The distribution of monomers in the copolymer chains could be successfully controlled by regulating the addition of more reactive monomer (AA). Copolymers having nearly random distribution of comonomer moieties to block type distribution with different composition (10–50 mol % AA) were synthesized to investigate the effect of polymer architecture and composition on pH response and mechanical properties of resultant structures. These copolymers were solution spun from dimethylformamide‐water system, drawn in coagulation bath, and annealed at 120°C for 2 h to make pH‐sensitive fibers which were structurally stable without the need of chemical crosslinking. The fibers from block copolymers showed significantly better tensile strength (34.3 MPa), higher retractive forces (0.26 MPa), and enhanced pH response (swelling 3890%) in comparison with fibers from random copolymer (13.55 MPa, 0.058 MPa, and 1723%, respectively). The tensile strength and retractive forces could be further improved to a value of 72 MPa and 0.36 MPa, respectively, by changing the composition of the block copolymer while retaining the swelling percentage similar to the random copolymer mentioned above. It is proposed that on processing to fibers, the block copolymers could form a segregated domain structure with separate domains of AA and AN, where AN domains were responsible for high structural integrity by providing connectivity among polymer chains, while AA domains showed improved response to changing pH of the environment. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

pH值对超声辐照下聚乙烯醇-丙烯腈体系共聚反应影响的研究

<正>聚乙烯醇(PVA)是制造维纶纤维的原料.维纶是棉型纤维,具有高强、耐磨和高吸湿性特点,但是染色性差,回弹性低.腈纶具有高回弹性和优良染色性,素有合成羊毛之称,但是强度较低,吸湿性差.通过嵌段共聚可使腈纶和腈纶在分子基础上结合,制得兼具维纶和腈纶优异性能的新型合成纤维.有关在超声辐照下PVA与丙烯腈(AN)的嵌段共聚反应已有报道,为进一步提高共聚反应速率、共聚物产率及共聚物中AN含量,本文对体系PH值的影响进行了研究.     

悬浮法EPM—g—SAN的合成与表征

以悬浮法实施二元乙丙橡胶（EPM）与单体苯乙烯（St）和丙烯腈（AN）的接枝共聚反应。合成了EPM—g—SAN,用其与SAN树脂共混制备了高抗冲塑料乙丙橡胶与苯乙烯及丙烯腈的三元共聚物（AES）。研究了AN／St—AN和EPM／St-AN的配料比对接枝反应体系的单体转化率、接枝率和接枝效率及AES缺口冲击强度的影响。用FTIR对EPM—g—SAN所含g—SAN（包括接枝链和非接枝共聚物）的组成进行了定量分析。结果表明,当AN质量分数为35％、EPM质量分数为60％,接枝反应体系的单体转化率、接枝率和接枝效率分别为92％、45％和27．6％。在此条件下合成的EPM—g—SAN对SAN树脂的增韧效率最高,用其制备的AES的悬臂梁缺口冲击强度达到53．2kJ／m^2。FTIR定量分析表明,在EPM—g—SAN的g—SAN中AN单元的平均组成比小于AN单体的配料比,而AN单元在接枝链SAN中的组成比小于在非接枝共聚物SAN中的组成比;当g—SAN所含接枝链的组成与非接枝共聚物的组成相等时,其EPM—g—SAN对SAN树脂有更高的增韧效率。     

Copolymers of starch and polyacrylonitrile: The dilution effect

In the ceric ammonium nitrate-initiated graft polymerization of acrylonitrile (AN) with starch, grafting frequencies and molecular weights of grafted polyacrylonitrile changed from 600 anhydroglucose units (AGU)/graft and 120000 to 280 AGU/graft and 36000 when concentrations of starch and AN were varied from 0.27 and 1.20 to 0.023 and 0.235 moles/l. of water, respectively. The influence of variety of starch, size of the starch granules, and reaction time was studied, and possible reasons for the influence of reactant concentration on the composition of the copolymer are considered.     

Redox copolymerization of acrylonitrile with fumaronitrile as a precursor for carbon fibre

Redox copolymerization of acrylonitrile (AN) with fumaronitrile (FN) was carried out in water at 40 °C using potassium persulphate (KPS) and sodium bisulfite (SBS) as initiators. Monomers feed used were 100:0, 97:3, 95:5, 90:10, 85:15 and 80:20 (AN:FN). Copolymers were characterized by Fourier transform infrared spectroscopy (FT-IR), Differential scanning calorimetry (DSC) and Thermogravimetric analysis. The effect of monomer composition on conversion and thermal properties of copolymer was studied. The DSC thermograms of copolymer samples are different from that of the homoPAN sample in the sense that the thermogram of the copolymer shows a doublet appearance and broad exothermic peak indicating that incorporation of fumaronitrile into copolymer system reduces the cyclization propagation rate with lower heat liberation (510 Jg⁻¹) as compared to that of homo(PAN) (758 Jg⁻¹). DSC thermograms also show that initial cyclization occurred at lower temperatures in copolymers as compared to homoPAN. The incorporation of 10% fumaronitrile into copolymer results the highest char yield (53%).     

Self-Compatibilization of poly(butyl methacrylate)/acrylonitrile-co-styrene blends via concentrated emulsion polymerization

Two concentrated emulsions in water were prepared: one from weakly polymerized butyl methacrylate (BMA) and the other one from a weakly polymerized mixture of acrylonitrile (AN) and styrene (St). Each of the concentrated emulsions also contained a small amount of a vinyl-terminated macromonomer (VTM). After the concentrated emulsions were partially polymerized, they were mixed and subjected to complete polymerization. This generated a blend of poly(butyl methacrylate) (PBMA), binary copolymer AN-co-ST (AN—St), and networks containing chains of VTM and those formed from different monomers. The networks constitute compatibilizers between the PBMA and AN—St. Such a preparation method, in which the components and compatibilizer are generated simultaneously, was called self-compatibilization. The blend possesses excellent tensile properties and toughness compared with the ternary copolymer AN—St—BMA and with the solution blends of PBMA/AN—St. The generation of the compatibilizers and the compatibilization mechanism were investigated via kinetic studies. The effects of the VTM, polymerization conditions, and the weight ratio of AN/St were also examined. © 1996 John Wiley & Sons, Inc.     

Effect of acrylonitrile water solubility on the suspension copolymerization of acrylonitrile and styrene

Effect of acrylonitrile water solubility on the suspension polymerization of acrylonitile and styrene was investigated. It was found that the copolymer composition produced in the suspension polymerization of acrylonitrile and styrene was significantly different from that in the bulk polymerization at the same monomer feed ratio, since acrylonitrile is partially soluble in water. To predict accurately and then control the copolymer composition in the suspension polymerization, a model to calculate the copolymer composition was proposed based on considering the phase partition of actylonitrile between monomer and aqueous phases. The results calculated by the model are in agreement with the experimental data. The real reactivity ratios in monomer phase used in the model are the same as that in the bulk polymerization, but the apparent reactivity ratios used in the classical theory for the suspension polymerization vary significantly with water/oil ratio. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4270–4274, 2006     

Monte Carlo simulation of sequential structure control of AN-MA-IA aqueous copolymerization by different operation modes

The regulation of polyacrylonitrile (PAN) copolymer composition and sequence structure is the precondition for producing high-quality carbon fiber high quality. In this work, the sequential structure control of acrylonitrile (AN), methyl acrylate (MA) and itaconic acid (IA) aqueous copolymerization was investigated by Monte Carlo (MC) simulation. The parameters used in Monte Carlo were optimized via machine learning (ML) and genetic algorithms (GA) using the experimental data from batch copolymerization. The results reveal that it is difficult to control the aqueous copolymerization to obtain PAN copolymer with uniform sequence structure by batch polymerization with one-time feeding. By contrary, it is found that the PAN copolymer with uniform composition and sequence structure can be obtained by adjusting IA feeding quantity in each reactor of a train of five CSTRs. Hopefully, the results obtained in this work can provide valuable information for the understanding and optimization of AN copolymerization process to obtain high-quality PAN copolymer precursor.     

Poly(MAA-AN-DM)两性聚合物复鞣剂的制备及性能

以甲基丙烯酸(MAA)、丙烯腈(AN)和甲基丙烯酸二甲基氨基乙酯(DM)为原料,过硫酸铵(APS)为引发剂,水为反应介质,经自由基共聚合制备了Poly(MAA-AN-DM)两性聚合物复鞣剂,并将其用于皮革的复鞣。用红外光谱、核磁共振氢谱、凝胶渗透色谱、胶体电荷滴定等对聚合产物的结构和性能进行了表征。用多功能材料实验机和色度计考察了聚合物组成对复鞣革性能的影响。较佳合成条件为:聚合温度80℃,单体量比n(MAA)∶n(AN)∶n(DM)=0.9∶0.3∶0.3,引发剂w(APS)=1.5%,w(单体)=30%,反应时间5.0 h。胶体电荷滴定测出共聚物的等电点为4.36,凝胶渗透色谱分析出共聚物的数均相对分子质量为84 688,分散系数为2.07。用w〔Poly(MAA-AN-DM)〕=2%的聚合物对猪蓝湿革进行复鞣,可使蓝湿革收缩温度提高5.5℃,抗张强度增加76.5%,增厚13.2%,革身饱满、无败色现象。     

High char‐yielding poly[acrylonitrile‐co‐(itaconic acid)‐co‐(methyl acrylate)]: synthesis and properties

Polyacrylonitrile terpolymers of various compositions consisting of acrylonitrile (AN), itaconic acid (IA) and methyl acrylate (MA) were synthesized by solution polymerization in dimethylsulfoxide. Increase in concentration of either IA or MA retarded the overall polymerization rate and the polymer molecular weight. The system consisting of AN + MA and varying IA concentration was more prone to retardation in comparison with the system composed of AN + IA with variable MA concentration. The retardation factors were quantified. Minor quantities of MA boost the reactivity of IA in the terpolymer system. The terpolymer was richer in MA vis‐à‐vis the feed. The thermal characteristics of the terpolymer were examined as a function of its composition. In contrast to the copolymer of AN and IA requiring 1–1.5 mol% IA, the terpolymer required an IA content of approximately 2.5 mol% for optimum thermal stability. The polymer with 90 mol% AN, 2.5 mol% IA and 7.5 mol% MA exhibited reasonably good char‐forming characteristics and thermal stability. The overall crystallinity and crystallite size of the polymers were found to decrease on incorporation of the comonomers. The ‘aromatization index’ of the copolymer increased with the temperature of pyrolysis through re‐organization of the tetrahydropyridine ladder structure. Copyright © 2005 Society of Chemical Industry     

Compatibility of poly(ϵ-caprolactone) (PCL) and poly(styrene-co-acrylonitrile) (SAN) blends. II. The influence of the AN content in SAN copolymer upon blend compatibility

The compatibility of polymer blends of poly(?-caprolactone) (PCL) and poly(styrene-co-acrylonitrile) (SAN) containing various acrylonitrile (AN) contents was studied to evaluate the influences of copolymer composition and PCL concentration upon blend compatibility. Blend compatibility was characterized by the occurence of a single glass transition intermediate between the transitions of the respective pure components. The glass transitions were determined by differential scanning calorimetry (DSC) and dynamic mechanical measurement (Rheovibron). It was found that SAN and PCL form compatible blends when the AN content of SAN ranges from 8% to 28% by weight. These blends are compatible in all proportions except for SAN 28 (AN wt % = 28) and PCL blends containing 70 or 85 wt % PCL. Blends of PCL and SAN were found to be incompatible when the AN content in SAN is greater than 30 wt % or less than 6 wt %. Lower critical solution temperature (LCST) behavior, which can be attributed to phase separation, was found to occur when these blends were heated to elevated temperatures. The cloud point, or phase separation, was found to vary with AN content in SAN and the concentration of SAN in the blend.     

Monte Carlo simulation of sequence distributions of acrylonitrile copolymers

A Monte Carlo simulation examining the effect of monomer ratios on the composition and sequence distribution of acrylonitrile(AN) copolymers with N‐vinyl pyrrolidone (NVP), itaconic acid (IA), and acrylic acid (AA) as comonomers has been developed. The Kelen–Tudos method was used to estimate monomer reactivity ratios. The results of the simulation are consistent with the academic conclusion and are as foreseen by the experimental data. The average number of NVP identical monomers in a sequence length of AN/NVP copolymer chain increases continuously and the average number of AN identical monomers in a sequence length shows a prominent decrease with an increase of NVP concentration in the feed. Changes in the monomer average number of AN/IA and AN/AA copolymers in a sequence length were the same as those of AN/NVP copolymer with an increase of comonomer concentration in the feed. The optimum weight ratio of AN with comonomers for manufacturing carbon fibers is 98/2. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 483–488, 2005     

Melting point depression in poly(ɛ-caprolactone) / poly(styrene-co-acrylonitrile) blends

Summary The melting point depression of poly(-caprolactone)/poly(styrene-co-acrylonitrile) (PCL/SAN) blends with changes in acrylonitrile content of SAN and in blend ratio was investigated by differential scanning calorimetry. For the melting points at a constant blend ratio occur a minimum in dependence on the copolymer composition for blends containing about 20 wt% acrylonitrile in SAN. From melting point depression data a negative, binary interaction parameter was obtained for PCL/SAN blends containing a SAN with 19.2 wt% AN. By optical microscopy it can be shown that the shape of the spherulites changes with copolymer composition of SAN and blend ratio.     

氯乙烯—丙烯腈乳液共聚

本文简述以氯乙烯(VC)——丙烯腈(AN)共聚,通过乳液聚合制取AN含量50％左右,平均分子量为6～8万供纺丝用的共聚体。本文主要讨论以上两种单体的初始投料比,反应过程中AN补加方式和速度对共聚体组成的影响;讨论乳化剂用量、种子含量、反应温度等工艺条件对共聚体平均分子量的影响;以及乳液后处理,即破乳、离心、干燥方法和过程。