复合可聚合乳化剂制备高固含量低黏度聚丙烯酸酯乳液

以DNS-86和F-6为复合可聚合乳化剂APS为引发剂,MMA、BA为单体采用半连续法制备20%固含量种子乳液,以种子乳液为介质,选用4种不同类型乳化剂:非离子可聚合乳化剂F-6,阴离子可聚合乳化剂DNS-86、常规非离子乳化剂OP-10、常规阴离子乳化剂SDS进行不同组合,同时滴加预乳化液、引发剂、缓冲剂直接二次成核制备62%固含量二元粒径分布乳液。重点研究了乳化剂复合方式、用量及配比、反应温度等对聚合稳定性、乳液流变性等的影响。,     

补加乳化剂提高丁二烯/苯乙烯的聚合速率

以丁二烯/苯乙烯乳液聚合反应10h、转化率达到70%为研究目标,在分析了标准配方条件下提高转化率对反应时间影响的基础上,考察了补加乳化剂对反应后期聚合速率及胶乳黏度、粒径和机械稳定性的影响,与采用增加初始乳化剂法进行了对比,并探讨了补加乳化剂提高反应后期聚合速率的作用机理。结果表明,增加初始乳化剂用量可以显著提高聚合速率,但胶乳黏度明显增大,且机械稳定性降低;补加乳化剂有利于提高反应后期的聚合速率和胶乳的机械稳定性;乳化剂补加量越大,反应后期的聚合速率越快;当乳化剂补加量相同时,在反应时间为2～4h,补加时机越早,反应后期聚合速率越快;补加乳化剂的最佳工艺条件为:乳化剂初始量100%,补加量10%,补加时机为反应2h。     

高固含量丙烯酸酯无皂乳液的合成及性能研究

采用少量自制的可聚合乳化荆M-OP10,通过预乳化半连续滴加工艺成功合成了一种高稳定性、固含量达50%的甲基丙烯酸甲酯/丙烯酸丁酯/丙烯酸-2-乙基己酯[P(MMA/BA/EHA)]的无皂乳液.探讨了反应温度、反应时间、可聚合乳化荆用量等条件对合成的影响,并且对不同可聚合乳化剂用量的乳液及胶膜性能进行了研究.结果表明,当反应温度80℃、滴加时间1 h、保温时间1 h、可聚合乳化剂为单体质量分数0.4%时.制备的无皂乳液各项性能较好.     

二甲基二烯丙基氯化铵—丙烯酰胺共聚物反相乳液合成工艺研究

以Span80-Tween80为复合乳化剂,以液体石蜡为分散介质,制备了二甲基二烯丙基氯化铵—丙烯酰胺共聚物反相乳液。研究了影响乳液稳定性及产物分子量的因素。结果表明,复配乳化剂比单一乳化剂使用效果好,在复配乳化剂的质量配比为Span80∶Tween80=2.7∶1、油水体积比为1.2∶1的情况下,反相乳液产品的稳定性较高;共聚物的分子量与聚合反应条件密切相关,当单体质量分数(占总质量)25%、反应温度35℃、搅拌速率300～400r/min、乳化剂质量分数为6%的工艺条件下,产品的特性黏数可达到800mL/g;并通过透射电镜对聚合物胶乳粒子的形貌进行了表征。     

以聚四氟乙烯乳胶粒子为种子的丙烯腈/苯乙烯乳液共聚合

以工业聚四氟乙烯(PTFE)乳胶粒子为种子,进行苯乙烯/丙烯腈(St/AN)种子乳液聚合,研究了单体加入方式、OP-10和十二烷基硫酸钠(SDS)复合乳化剂组成和用量对聚合稳定性、复合乳胶粒子平均粒径及粒径分布和形态的影响。结果表明,单体预乳化半连续乳液聚合稳定性高于间歇乳液聚合,两者又高于单体未乳化半连续乳液聚合;当OP-10/SDS复合乳化剂(OP-10/SDS质量比为2～1/2)用量小于4%质量分率时,采用间歇和半连续乳液聚合得到的复合乳胶粒子的平均粒径均大于PTFE种子;当复合乳化剂用量大于4%质量分率时,复合乳胶粒子平均粒径小于PTFE种子,与St/AN共聚物(SAN)二次粒子形成有关。PTFE粒子呈棒状或鹅卵状,而种子间歇乳液聚合和单体预乳化半连续乳液聚合得到的PTFE-SAN复合粒子均呈球状,PTFE被SAN包覆较完全。     

大粒径丁苯胶乳(SBR)的合成研究

研究了影响丁苯胶乳粒径大小的因素:乳化剂、引发剂、固含量、电解质及单体加入方式。研究表明乳化剂浓度、固含量、电解质浓度及单体加入方式是控制丁苯胶乳粒径的关键性因素。通过适时补加乳化剂,选取适宜的电解质浓度,适当的固含量及采用种子半连续加料方式有利于增大丁苯胶乳(SBR)粒径。     

影响MMA—BA—DMAEMA三元共聚物乳胶粒径及其分布的因素

采用间歇及半连续乳液聚合合成了甲基丙烯酸甲酯-丙烯酸丁酯-甲基丙烯酸二氨基乙酯三元共聚物乳胶。系统研究了复合乳化剂配比及用量、聚合温度、聚合方式和官能团单体含量对共聚物乳胶粒径及其分布的影响。结果表明，随着乳化剂体系中阴离子成分的增加、乳化剂用量的增加、官能团单体含量的减少和聚合温度的降低，乳胶的粒径减小，粒径分布变宽。无种子半连续乳液聚合所得乳胶粒径比间歇聚合和相同单体滴加速率下种子半连续聚合得到的乳胶粒径更大，分布也较宽。乳化单体的滴加速率在一定范围内对乳胶粒径及其分布没有影响，只有当乳化单体滴加速率低至使体系达到“饥饿”状态时，乳胶的粒径才相应增大。     

可聚合乳化剂DNS-6对丙烯酸酯乳液稳定性的影响

使用可聚合乳化剂烯丙氧基壬基酚丙醇聚氧乙烯（10）醚硫酸铵（DNS-86）,通过半连续聚合工艺制备了水基丙烯酸酯乳液。考查了DNS-86对乳液的固含量、转化率、乳胶粒的大小及形态、Zeta电位以及各种稳定性（聚合稳定性、化学稳定性及冻融稳定性）的影响。与常规乳化剂十二烷基硫酸钠（SDS）制备的丙烯酸酯乳液性能进行了对比。结果表明,DNS－86因反应活性大,能与丙烯酸酯单体进行共聚,制得的乳胶粒大小均一,形态规整,乳液的稳定性得到改善。     

高固含量有机硅改性丙烯酸酯微胶乳的合成及性能

用自制的由阴离子乳化剂十二烷基硫酸钠(SDS)、非离子乳化剂辛基酚聚氧乙烯醚(OP-10)、反应型乳化剂WH-100以及非离子表面润湿剂所组成的混合乳化剂体系,通过半连续单体滴加法合成了平均粒径为59·8nm、粒径分布窄、总固物质量分数达40%的有机硅改性丙烯酸酯微胶乳,并对微胶乳及胶膜的性能进行了研究。结果表明,与间歇预乳化法制备的乳液相比,有机硅改性丙烯酸酯微胶乳的钙离子稳定性较差,其胶膜的吸水率较小,凝胶含量相当;随着乙烯基三乙氧基硅烷(A151)用量的增加,对转化率的影响不明显,微胶乳的钙离子稳定性、胶膜的吸水率下降,乳胶粒子的粒径变大,A151的质量分数宜为4%;随着功能单体甲基丙烯酸-2-羟乙酯(HEMA)用量的增加,微胶乳的钙离子稳定性先提高后降低,而胶膜的吸水率先降低后增大,HEMA的质量分数不宜超过3%。     

稳定的阳离子型聚合物纳米粒子胶乳的研制

以甲基丙烯酸甲酯 ( MMA)和丙烯酸乙酯 ( EA)为主单体 ,甲基丙烯酰氧乙基三甲基氯化铵( DMC)为功能单体 ,分别采用 4种阳离子乳化剂和阴离子引发剂过硫酸铵 ( A PS)进行自由基乳液共聚合。探讨了乳化剂种类和用量、聚合温度及加料方式对乳胶粒大小、胶乳稳定性和胶膜耐水性的影响。研究发现 ,当采用十六烷基三甲基氯化铵 ( 16 31)作乳化剂 ,用量为 1.75%～ 2 .0 % ,聚合温度为 70℃ ,采用种子半连续法可以成功研制出粒径为 57.5nm、稳定的耐水性较好的阳离子型聚合物纳米粒子胶乳     

苯乙烯可逆加成-断裂链转移聚合动力学

为了实现可逆加成-断裂链转移(RAFT)聚合过程中,苯乙烯均聚、高分子量聚苯乙烯的合成及苯乙烯与其他单体共聚时,对苯乙烯转化率、共聚时组成和分子量大小的控制,进行了二硫代苯乙酸-1-苯基乙酯(PEPDTA)调控苯乙烯本体和细乳液聚合动力学分析。在本体聚合中,反应速率慢,链增长自由基与"中间态"自由基的终止反应对聚合速率影响较小,很难合成窄分布、高转化率、高分子量的聚苯乙烯;在细乳液聚合中,反应速率快、转化率高,随着PEPDTA含量增加,乳胶粒数量减少、粒径分布变宽,诱导期和缓聚现象明显;聚合物的数均分子量随转化率线性增长,RAFT试剂浓度越高,分子量分布越窄,反应时间越长,分布越宽。以Smith-Ewart方程为基础,建立了苯乙烯RAFT细乳液聚合动力学模型,模型动力学曲线与实验数据相符合,能较好地预测实验过程。     

球形TiCl4/MgCl2催化剂引发丙烯气相聚合动力学

采用微机在线控制的半连续烯烃聚合反应器,在加压条件下进行了球形TiCl₄/MgC_l2催化剂催化的丙烯气相聚合,测定了单体瞬时聚合速率等重要的动力学数据,考察了不同聚合条件对聚合动力学的影响,并用Flory-Huggins方程估算了聚合物非晶区中的单体浓度C_m.研究表明聚合速率与C_m成正比;丙烯聚合速率在反应一开始就迅速衰减,之后是缓慢的衰减.提出了一个n级衰减的丙烯气相聚合动力学模型,根据实验数据拟合得到了模型的各个参数,其中活性中心的衰减级数为2.5,气相聚合的表观增长活化能为77.1 kJ•mol^-1.用该模型可以较好地模拟加压条件下的丙烯气相聚合动力学行为.     

Reversible addition fragmentation transfer (RAFT) polymerization of styrene in a miniemulsion: A mechanistic investigation

The RAFT polymerization of styrene in miniemulsion using 1-phenylethyl phenyl-dithioacetate (PEPDTA) as a RAFT agent was investigated, in attempt to reveal the mechanism for the often observed inferior performance such as low polymerization rate, broad molecular weight distribution and particle size distribution in the RAFT miniemulsion polymerization with regular levels of surfactant and co-stabilizer (1 wt% sodium dodecyl sulfate and 2 wt% hexadecane). It is strongly evident that a few of large oligomer particles consisting of oligomer, RAFT agent (RAFT agent refers to the original RAFT agent), and monomer would be formed in the early stage of the polymerization due to the superswelling of the first nucleated droplets. With the regular levels of surfactant and co-stabilizer, the observed low polymerization rate, broadened molecular weight distribution, slow conversion of the RAFT agent, lower N_p, and broadened particle size distribution could be well explained by the formation of these large oligomer particles and their prolonged existence. When the formation of the oligomer particles was suppressed by increasing surfactant and co-stabilizer levels and wise selection of types of RAFT agent, the molecular weight distribution could be narrowed to around 1.3 and particle size distribution could be close to that of the conventional non-living miniemulsion polymerization.     

双硫酯作为链转移剂的苯乙烯本体聚合研究

研究了二硫代苯甲酸苄基酯（BDB）、二硫代苯甲酸苯乙基酯（PEDB）及二硫代苯甲酸异丙苯基酯（CDB）三种RAFT试剂作为链转移剂的苯乙烯本体聚合。动力学研究表明,当BDB及PEDB浓度和偶氮二异丁腈（AIBN）浓度同时增大时,AIBN浓度提高所导致的聚合反应速率提高起主导作用：当CDB和AIBN浓度同时提高时,CDB浓度提高所导致的聚合速率降低作用影响更显著。对CDB体系,随转化率提高分子量分布变宽。对BDB体系,当其浓度较高时,随转化率提高分子量分布变窄;当其浓度较低时,不利于实现可控,活性聚合,反应后期分子量分布变宽。动力学和GPC分析均表明以BDB为链转移剂时苯乙烯本体聚合的可控性最好。在同时考虑链转移剂和引发剂作用的基础上,提出了修正的聚合物分子量预测模型,该模型可有效预测以双硫酯为链转移剂的苯乙烯RAFT聚合体系的分子量。     

Surfactant-free aqueous RAFT polymerization of styrene in the presence of CaCO3 particles

A new method to achieve well-controlled surfactant-free aqueous RAFT polymerization of styrene initiated by K₂S₂O₈ in the presence of CaCO₃ particles was proposed. It was found that the hydrophobic monomer of styrene was adsorbed on the surface of CaCO₃ particles and well-controlled surfactant-free aqueous RAFT polymerization mediated with the RAFT agent of S,S′-bis(α,α′-dimethyl-α″-acetic acid) trithiocarbonate (BDMAT) was achieved. The weight ratio of the feeding CaCO₃ to the styrene monomer on the aqueous RAFT polymerization was investigated, and it was found that high CaCO₃/styrene weight ratio led to fast aqueous RAFT polymerization. The aqueous RAFT polymerization kinetics was checked, and the fast RAFT polymerization rate at low molar ratio of styrene/BDMAT/K₂S₂O₈, the linear ln([M]_o/[M])–time plot, the linear increase in the number–average molecular weight with the monomer conversion, and the relatively low PDI values (1.1～1.3) were demonstrated. The surfactant-free aqueous RAFT polymerization was compared with the general emulsion RAFT polymerization in the presence of the sodium dodecyl sulfate (SDS) surfactant. It was found that the surfactant-free aqueous RAFT polymerization seemed more valid than the emulsion RAFT polymerization. The proposed method is believed to be a new strategy to achieve well-controlled surfactant-free aqueous RAFT polymerization.     

Poly(dimethylsiloxane‐b‐styrene) diblock copolymers prepared by reversible addition‐fragmentation chain transfer polymerization: Kinetic model

Well‐defined polydimethylsiloxane‐block‐polystyrene (PDMS‐b‐PS) diblock copolymers were prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization using a functional PDMS‐macro RAFT agent. The RAFT polymerization kinetics was simulated by a mathematical model for the RAFT polymerization in a batch reactor based on the method of moments. The model described molecular weight, monomer conversion, and polydispersity index as a function of polymerization time. Good agreements in the polymerization kinetics were achieved for fitting the kinetic profiles with the developed model. In addition, the model was used to predict the effects of initiator concentration, chain transfer agent concentration, and monomer concentration on the RAFT polymerization kinetics. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

RAFT miniemulsion polymerization of methyl methacrylate

It has been well documented that RAFT miniemulsion polymerization has broader molecular weight distribution, compared with its bulk polymerization counterpart. Interestingly, it was found that the PDI value of RAFT miniemulsion polymerization of methyl methacrylate (MMA) mediated by 2-cyranoprop-2-yl dithiobenzoate (CPDB) was still as low as its corresponding bulk polymerization did. PDI could be as low as 1.13 even with typical sodium dodecyl sulfate (SDS, 1 wt%, surfactant) and n-hexadecane (HD, 2 wt%, costablizer) concentrations. When the polymerization was carried out at 60 °C, a dramatic increase in PDI (>1.4) was observed after 80% monomer conversion since RAFT addition reaction became diffusion-controlled. Increasing the polymerization temperature to 80 °C could reduce the PDI to 1.2 even at 100% monomer conversion. The compartmentalization effect of radicals was surprisingly absence before 30% monomer conversion but became pronounced afterwards in the miniemulsion polymerization. Thus, it still took less time to finish the miniemulsion polymerization with the increase of the surfactant levels.     

Controlled synthesis of vinyl-functionalized homopolymers and block copolymers by RAFT polymerization of vinyl methacrylate

Reversible addition-fragmentation chain transfer (RAFT) polymerization of an asymmetrical divinyl monomer, vinyl methacrylate (VMA), was investigated under various conditions. RAFT polymerization of VMA using a dithioester-type chain transfer agent (CTA) under suitable conditions afforded soluble polymers with a high content of pendant vinyl ester side chains in sufficient yields (>70%). The monomer concentration, the nature of the CTA, and the CTA/initiator ratio were found to affect the polymerization reaction and the structure of the resulting polymers; this behavior is attributed to the relative propensities for intermolecular propagating/cross-linking reactions and intramolecular cyclization. A kinetic study of the RAFT polymerization of VMA with the dithioester-type CTA 1 suggested that the propagation reaction of the methacryloyl group proceeded predominantly with a certain level of intramolecular cyclization during the early stage of the polymerization and intermolecular cross-linking during the final stage of the polymerization. Block copolymers with one segment featuring pendant vinyl functionality were synthesized by RAFT polymerization of VMA using poly(methyl methacrylate) as a macro-chain transfer agent (macro-CTA).     

RAFT‐mediated graft polymerization of glycidyl methacrylate in emulsion from polyethylene/polypropylene initiated with γ‐radiation

The successful reversible addition‐fragmentation (RAFT)‐mediated graft polymerization of glycidyl methacrylate (GMA) in emulsion phase from polyethylene/polypropylene nonwoven fabric using 4‐cyano‐4‐[(phenylcarbonothioyl)thio]pentanoic acid under γ‐irradiation at ambient condition is reported. While conventional graft polymerization in emulsion phase yielded grafted materials with low of grafting (Dg) values [<7.5% at 10% (wt/wt) GMA], addition of RAFT agent to the graft polymerization system allowed the synthesis of polyethylene/polypropylene‐g‐poly(GMA) with more tunable Dg (8% ≤ Dg ≤ 94%) by controlling the grafting parameters. Relatively good control (PDI ～1.2 for selected grafting conditions) during polymerization was attained at 100:1 monomer‐to‐RAFT agent molar ratio. The number average molecular weight of free poly(glycidyl methacrylate) (PGMA) increased as a function of monomer conversion. NMR analyses of the free PGMA homopolymers indicate the presence of dithiobenzoate group from 4‐cyano‐4‐((phenylcarbonothioyl)thio) pentanoic acid on the polymer chain. The reactive pendant oxirane group of the grafted GMA can be modified for various environmental and industrial applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45270.     

Comparison of RAFT polymerization of methyl methacrylate in conventional emulsion and miniemulsion systems

In this study, we have conducted the reversible addition-fragmentation chain transfer (RAFT) polymerization of methyl methacrylate (MMA) in two heterogeneous systems, i.e. conventional emulsion and miniemulsion, with identical reaction conditions. The main objective is to compare the living character in both systems according to the nucleation mechanism, the latex stability, the particle sizes and particle size distributions of latexes, the molecular weights and molecular weight distributions (or polydispersity index, PDI) of PMMA, and the kinetics of the RAFT polymerization. The RAFT agent used in both systems was 2-cyanoprop-2-yl dithiobenzoate (CPDB). The effects of an oil-soluble initiator 2,2′-azobisisobutyronitrile (AIBN) and a water-soluble initiator kalium persulfate (KPS) on the RAFT/emulsion and RAFT/miniemulsion polymerizations were investigated. Methyl-β-cyclodextrin (Me-β-CD) was used as a solubilizer. The average molecular weights and molecular weight distributions (PDIs) of dried PMMA samples were characterized by gel permeation chromatography (GPC). The experimental results showed that the RAFT/miniemulsion polymerization of MMA exhibited better living character than that of RAFT/emulsion polymerization under the conditions of our experiment. The PDI of PMMA in RAFT/miniemulsion polymerization was decreased with the addition of Me-β-CD. However, Me-β-CD did not have influence on the PDI of PMMA prepared in RAFT/emulsion polymerization.