叔碳酸乙烯酯改性醋酸乙烯酯乳液的研制

采用半种子连续乳液聚合的方法，以过硫酸钾为引发剂，以十二烷基硫酸钠和OP—10复配为乳化剂，合成了叔碳酸乙烯酯／醋酸乙烯酯共聚乳液。研究了乳化剂的用量、阴离子／非离子质量比和叔碳酸乙烯酯用量对乳液性能的影响；引发剂用量、聚合温度、种子单体加入量以及单体进料速率对聚合过程的影响。乳化剂用量为3％、阴离子／非离子为1：1、叔碳酸乙烯酯用量为30％；聚合温度为76℃、引发剂用量为0．4％、种子加入量为10％、进料周期为4h，聚合过程稳定，乳液性能良好。     

甲基丙烯酸甲酯-丙烯酸乙酯乳液共聚动力学研究

为了合成适于药物包衣用的甲基丙烯酸甲酯-丙烯酸乙酯(MMA-EA)共聚物胶乳,对以非离子型乳化剂OP-10为乳化剂、过硫酸钾为引发剂的MMA-EA乳液共聚动力学进行了研究。发现初期共聚速率随着乳化剂浓度、引发剂浓度和聚合温度的增加而增大,这是由于共聚物乳胶粒子平均粒径随着乳化剂、引发剂浓度和聚合温度的增加而减小,乳胶粒子数目增加所致。通过调节乳化剂、引发剂以及反应温度可以达到合适的聚合反应速率,最终合成出转化率大于95%的MMA-EA共聚乳液。     

丙烯酰胺-N-羟甲基丙烯酰胺反相乳液共聚合

以 Span- 4 0为乳化剂 ,过硫酸铵为引发剂 ,进行了丙烯酰胺 - N-羟甲基丙烯酰胺反相乳液共聚反应。研究了反应温度、单体浓度、引发剂浓度、乳化剂浓度等因素对聚合动力学的影响 ,并讨论了其聚合机理。     

丙烯酸酯微乳液的聚合研究

运用OP-10／JFC非离子复合乳化剂成功合成了丙烯酸酯微乳液,以聚合过程的现象为基础,从紫外光谱分析、聚合温度、单体时间-转化率、体系时间-粘度关系、pH值等方面系统研究了聚合过程中的相分离和凝胶现象。结果表明:聚合温度75-76℃,聚合结束后pH值控制在7-8,聚合过程中补加助乳化剂戊醇和引发剂KPS溶液,能有效抑制凝胶和相分离现象。     

N-苯基马来酰亚胺/苯乙烯/丙烯腈/ɑ-甲基苯乙烯乳液共聚动力学

以十二烷基硫酸钠(SDS)为乳化剂,过硫酸钾(KPS)引发剂引发N-苯基马来酰亚胺/苯乙烯/丙烯腈/ɑ-甲基苯乙烯(PMI/St/AN/-ɑMeSt)进行四元乳液共聚,考察了聚合温度,引发剂浓度,乳化剂浓度,-ɑMeSt浓度对聚合速率的影响。结果表明,共聚体系的表观活化能为84.14 kJ/mol,聚合初始速率同引发剂浓度的0.46次方和乳化剂浓度的0.57次方成正比。乳化剂浓度8.4 m mol/L,引发剂浓度1.8m mol/L,聚合温度75℃,聚合1 h,85℃熟化2 h是较为合理的反应条件。-ɑMeSt的浓度对聚合速率有很大的影响,应控制在0.35 mol/L以下。     

N-苯基马来酰亚胺/苯乙烯/丙烯腈/α-甲基苯乙烯乳液共聚动力学

以十二烷基硫酸钠（SDS）为乳化剂,过硫酸钾（KPS）引发剂引发N-苯基马来酰亚胺／苯乙烯／丙烯腈／α-甲基苯乙烯（PMI／St／AN／α-MeSt）进行四元乳液共聚,考察了聚合温度,引发剂浓度,乳化剂浓度,α-MeSt浓度对聚合速率的影响。结果表明,共聚体系的表观活化能为84．14kJ／mol,聚合初始速率同引发剂浓度的0．46次方和乳化剂浓度的0．57次方成正比。乳化剂浓度8．4mmol／L,引发剂浓度1．8mmol／L,聚合温度75℃,聚合1h,85℃熟化2h是较为合理的反应条件。α-MeSt的浓度对聚合速率有很大的影响,应控制在0．35mol／L以下。     

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。,     

有机硅-丙烯酸酯乳液聚合稳定性研究

采用种子乳液聚合工艺,以过硫酸铵为引发剂、十二烷基二苯醚二磺酸钠(DOWFAX2A1)/辛基酚聚氧乙烯(40)醚(TRIONX-405)为复合乳化剂合成了乙烯基 三(2 甲氧基乙氧基)硅烷(A-172)改性丙烯酸酯聚合物。研究了单体加入方式、乳化剂用量、聚合温度、pH值等对聚合稳定性的影响。结果表明,当总乳化剂质量分数为3 0%、聚合温度为75～80℃、pH=6 5～7 5时,采用净单体滴加法制备聚合物的聚合过程稳定性较好;增加A-172用量,聚合稳定性降低。     

可聚合琥珀酸双酯磺酸钠乳化合成聚丙烯酸酯纳米乳液

采用半连续种子乳液聚合工艺,在可聚合乳化剂十六烷基烯丙基琥珀酸双酯磺酸钠(Ⅰ)和辛基酚聚氧乙烯醚烯丙基琥珀酸双酯磺酸钠(Ⅱ)存在下,合成了聚丙烯酸酯纳米乳液,探讨了可聚合乳化剂种类及用量、聚合温度、引发剂用量、聚合时间对丙烯酸酯乳液聚合及性能的影响,通过FTIR、TEM和DSC对聚合产物进行了表征分析。结果表明,可聚合乳化剂参与了与丙烯酸酯的共聚反应,所得聚合物乳胶膜的玻璃化温度为23.5℃;与传统乳化剂十二烷基硫酸钠(SDS)相比,可聚合乳化剂可提高乳胶膜的耐水性;当m(Ⅰ)∶m(Ⅱ)=1∶2,乳化剂质量分数2%,聚合温度85℃,引发剂质量分数0.5%,聚合时间2 h时,所得乳液的固体分质量分数为32.70%,平均粒径72.3 nm,分布指数0.143,吸水率4.57%。     

反相乳液聚合合成聚丙烯酰胺

以甲苯为介质,Span80/Span20为乳化剂,叔丁基过氧化氢/亚硫酸氢钠氧化还原体系为引发剂,采用反相乳液聚合制备了分子量高达9.4×106的聚丙烯酰胺乳液。研究了乳化剂种类及用量、引发剂种类及用量、油水比、单体浓度,反应温度对共聚物相对分子量、聚合转化率以及聚合反应速率的影响。其最佳聚合配方及工艺条件为:油水体积比为1.4,单体浓度30%,引发剂用量0.003%,乳化剂用量12%,聚合温度30℃。     

Monte Carlo Simulation of Droplet Nucleation in RAFT Free Radical Miniemulsion Polymerization

Abstract

The early stages of the reversible addition/fragmentation transfer (RAFT) miniemulsion polymerization were simulated, focusing on the effect of the RAFT agent on droplet nucleation. For highly reactive RAFT agents, a large number of free radicals (N_c ) needed to be captured by a droplet in order to initiate polymerization in the droplet, which was totally different from the behavior of regular miniemulsion polymerization. More interestingly, it was found that droplet size had a significant influence on N_c value. It was shown that the RAFT agent has a significant influence on miniemulsion polymerization, leading to long induction periods and retardation of polymerization. In addition, miniemulsion droplets with different sizes are nucleated at different times, which could lead to very low nucleation efficiency. The results would be very helpful in understanding and designing a RAFT miniemulsion polymerization system.     

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.     

黄原酸酯调控的氯乙烯的可逆-加成断裂链转移聚合

以三种不同结构的黄原酸酯为调控剂,进行氯乙烯（VC）溶液和细乳液可逆加成-断裂链转移（RAFT）聚合,发现O-乙基黄原酸丙酸乙酯对VC聚合的调控效果良好,氯乙烯RAFT细乳液聚合速率明显大于溶液聚合,VC聚合12 h转化率大于90%,但聚氯乙烯（PVC）的分子量分布宽于溶液聚合产物。核磁共振和紫外可见吸收光谱分析证明合成的PVC具有黄原酸酯基端基结构,结构缺陷少。含黄原酸酯基PVC可进一步调控VC及醋酸乙烯酯聚合,进行扩链或得到嵌段共聚物。结合聚合动力学,说明黄原酸酯调控的氯乙烯聚合具有活性特征。     

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.     

Comparison of styrene reversible addition–fragmentation chain‐transfer polymerization in a miniemulsion system stabilized by ammonlysis poly(styrene‐alt‐maleic anhydride) and sodium dodecyl sulfate

In this study, we conducted the reversible addition–fragmentation chain‐transfer (RAFT) polymerization of styrene (St) in a miniemulsion system stabilized by two different stabilizers, ammonlysis poly(styrene‐alt‐maleic anhydride) (SMA) and sodium dodecyl sulfate (SDS), with identical reaction conditions. The main objective was to compare the polymerization kinetics, living character, latex stability, and particle morphology. The macro‐RAFT agent used in both systems was SMA, which was obtained by RAFT solution polymerization mediated by 1‐phenylethyl phenyldithioacetate. The experimental results show that the St RAFT miniemulsion polymerization stabilized by SDS exhibited a better living character than that stabilized by ammonlysis SMA. The final latices were very stable in two systems, but different stabilizers had an obvious effect on the polymerization kinetics, living character, and particle morphology. All of the particles obtained by RAFT miniemulsion polymerization stabilized by SDS were solid, but an obvious core–shell structure was observed in the miniemulsion system stabilized by ammonlysis SMA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.     

Nanoencapsulation via interfacially confined reversible addition fragmentation transfer (RAFT) miniemulsion polymerization

Oligomer of styrene and maleic anhydride synthesized by bulk RAFT polymerization (SMA-RAFT) was used to construct a novel strategy for robust nanoencapsulation via interfacially confined controlled/living radical miniemulsion polymerization. After ammonolysis, SMA-RAFT becomes amphiphilic and can be used as a surfactant to prepare miniemulsion. The ammonolyzed SMA-RAFT molecules would self-assemble on the interface of water/droplets. This self-assembly property combining with the RAFT living polymerization chemistry demands the polymer chains to grow inwards gradually in particles, leading to the formation of a polymer shell. The hydrophilicity of ammonolyzed SMA-RAFT agent tuned by the ammonolyzed degree or structures of SMA-RAFT agent was found to play a key role in the final morphology. The well-defined nanocapsules with little solid particles can be obtained by using partially ammonolyzed SMA-RAFT with 0.5 wt% SDS as a co-surfactant.     

Kinetics of reversible addition–fragmentation transfer (RAFT) miniemulsion polymerization of styrene using dibenzyl trithiocarbonate as RAFT reagent and costabilizer

The roles of dibenzyl trithiocarbonate (DBTTC) as both costabilizer and reversible addition–fragmentation transfer (RAFT) reagent in RAFT miniemulsion polymerizations of styrene were investigated. The effectiveness of DBTTC costabilizer in retarding Ostwald ripening involved in the storage stability of miniemulsion is comparable to that of conventional low‐molecular‐weight costabilizers such as cetyl alcohol, but inferior to that of hexadecane. The major variables chosen for studying kinetics of RAFT miniemulsion polymerizations include the type of initiators and levels of DBTTC and surfactant. At a constant level of DBTTC, the rate of polymerization for benzoyl peroxide (BPO)‐initiated polymerization is slower than that for sodium persulfate (SPS)‐initiated polymerization. Furthermore, the polymerization rate decreases with increasing level of DBTTC for polymerizations initiated by BPO (or SPS). It is the monomer droplet nucleation that governs BPO‐initiated polymerizations. In contrast, for SPS‐initiated polymerizations, the probability for homogeneous nucleation to take place is greatly increased, especially for polymerizations with lower levels of DBTTC and higher levels of surfactant. © 2015 Society of Chemical Industry     

活性/可控自由基细乳液聚合的研究及工业化进展

综述了活性/可控自由基细乳液聚合方法的研究进展,主要包括稳定自由基细乳液聚合、原子转移自由基细乳液聚合和可逆加成-断裂链转移自由基细乳液聚合3种"活性"/可控自由基聚合方法,介绍了近年来这些领域的工业化进程,并指出了该体系的发展与不足。     

Synthesis and characterization of PMMA/SiO2 organic–inorganic hybrid materials via RAFT‐mediated miniemulsion polymerization

In this article, we first carried out the surface modification of SiO₂ using silane coupling agent KH570, and then prepared PMMA/SiO₂ organic–inorganic hybrid materials by conventional free radical polymerization and RAFT polymerization in miniemulsion, respectively. The kinetics comparisons of these two polymerizations were studied. PMMA/SiO₂ hybrid materials were characterized by gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis. Experimental results indicated that the polymerization behavior of MMA in miniemulsion showed controlled/living radical polymerization characteristics under the control of RAFT agent. Incorporation of RAFT agent and SiO₂ nanoparticles improved the thermal properties of polymers, the thermal stability of polymers increased with increasing content of SiO₂ nanoparticles. The structures and morphologies of SiO₂, modified SiO₂, and PMMA/SiO₂ hybrid materials were characterized by FT‐IR and TEM. TEM results showed that the addition of modified SiO₂ nanoparticles to miniemulsion polymerization system obtained different morphology latex particles. Most of modified SiO₂ nanoparticles were wrapped by polymer matrix after polymerization. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers