Effect of aqueous comonomer solubility on the surfactant-free emulsion copolymerization of methyl methacrylate

Surfactant-free emulsion copolymerization was used to prepare methyl methacrylate-hydroxyethyl methacrylate (MMA-HEA) and methyl methacrylate-hydroxypropyl methacrylate (MMA-HPMA) latex particles. Also, glycidyl methacrylate (GMA) was grafted onto the surface of the preformed MMA-HPMA latex particles by seeded surfactant-free emulsion copolymerization. The copolymerization reactions were conducted at 75 °C using a water-soluble initiator, potassium persulfate (KPS). The morphologies of copolymer latex particles were observed using Scanning electron microscopy (SEM). The influence of different reactions parameters (the MMA saturation concentration (Sr), the KPS concentration and the aqueous solubility of the comonomers (HEA or HPMA)) on the particles average diameter and particles size dispersity was investigated. The experimental results showed that the increase of initiator concentration induces in all investigated cases the increase of particles average diameter, while the presence of HEA or HPMA as comonomers in the copolymerization reaction of MMA (1,000% Sr) lead to a decrease of particles average diameter. At small KPS concentration the latex is monodisperse, the increase of the initiator concentration leading to the formation of polydisperse latex. In the case of grafting reaction of GMA onto the monodisperse preformed MMA-HEA latex particles, although the average diameter of the final particles doubles the latex remains quasi-monodisperse.     

MMA/N-对甲苯基马来酰亚胺乳液共聚的研究

通过乳液共聚得到N－对甲苯基马来酰亚胺（NPTMI）,甲基丙烯酸甲酯（MMA）的二元共聚物,用扭辫分析,热重分析和维卡软化点测定仪研究了不同NPTMI含量对共聚物热性能的影响,以及共聚物的力学性能,流变性能,研究结果表明,共聚物初始分解温度（Tini),失重50％时的温度,玻璃化转变温度（Tg)及维卡软化点（TViout)都随NPTMI的含量增加而提高,当NPTMI含量为15％时,Tg提高14．1℃,Tini提高23．2℃,TVicut提高8．9℃,工聚物熔体呈假塑性流体,同时共聚物熔体非牛顿指数随NPTMI含量的增加而增大。     

Semibatch emulsion copolymerization of methyl methacrylate and butyl acrylate

The concentration of sodium lauryl sulfate (SLS) in the initial reactor charge is the most important parameter in determining the particle size of a semibatch emulsion copolymerization of methyl methacrylate (MMA) and butyl acrylate (BA). The number of particles formed is proportional to the concentration of SLS to the 0.5–1.2 power and it is proportional to the concentration of the nonyl phenol–40 mol ethylene oxide adduct to the 0.014–0.72 power. The number of particles is almost independent of the concentration of the initiator. The solubility of monomer in water has an important effect on the nucleation mechanism according to the literature. However, the ratio of MMA to BA does not show any significant effect on the latex particle size in our laboratory. The particle size also increases with increasing ionic strength or agitation speed. Experimental data of particle-size distribution and molecular weight distribution support the coagulative nucleation mechanism when the concentration of SLS is way below its critical micelle concentration (CMC). © 1995 John Wiley & Sons, Inc.     

Study on soapless emulsion copolymerization methyl methacrylate and n-butyl acrylate

The soapless emulsion copolymerization of methyl methacrylate (MMA) and n-butyl acrylate (n-BuA) at four levels of monomer feed composition (f₁₀) was studied. Conversion (X), average particle diameter (D_p), molecular weight distribution (MWD), surface charge density, and glass transition temperature (T_g) of the copolymer as a function of reaction time (t) were measured. The copolymers obtained even at low conversion, except for the run of (f₁₀) = 90 wt. percent MMA, exhibit two T_gs in their DSC thermograms. Phase separation is found to occur in the latex particles during polymerization. The heterogeneous distribution of monomers in particles, in which a relatively rich MMA region exists in the shell and a relatively rich n-BuA region exists in the core of the particles, is assumed to arise from phase separation. The average copolymer composition and the fraction of the two domains are estimated. The polymerizatrion course and particle size growth follow the linear X vs. t² and D_p^3/2 vs. t relationships, respectively. Although the coagulation of particles happens after around 30 percent conversion, the polymerization behaviors, except for increasing rates, are not affected.     

Efficiency of ligands in atom transfer radical polymerization of lauryl methacrylate and block copolymerization with methyl methacrylate

Atom transfer radical polymerization of lauryl methacrylate (LMA) was carried out in the presence of various ligands using ethyl-2-bromoisobutyrate as initiator and CuBr as catalyst in toluene at 95 °C. The ligands used were 2,2′-bipyridyl,4,4′-dimethyl-2,2′-bipyridyl, N,N,N′,N′,N″-pentamethyldiethylenetriamine (PMDETA) and N-(n-propyl)-2-pyridylmethanimine (PPMI). Controlled polymerization was observed with PMDETA and PPMI ligands and poly(LMA)s with narrow molecular weight distribution (MWD) (M_w/M_n≤1.2) were obtained. The first-order time-conversion plot showed the presence of termination in the presence of PMDETA. A linear first-order time-conversion plot with a small induction period (∼10 min) was observed in the presence of PPMI ligand. Di-block copolymers of LMA and methylmethacrylate with controlled molecular weight and narrow MWDs were synthesized via sequential monomer addition.     

Kinetics and mechanism of emulsion copolymerization. IV. Kinetic modeling of emulsion copolymerization of styrene and methyl methacrylate

Based on the micellar nucleation theory, a mathematical kinetic model for an unseeded emulsion copolymerization system is developed, where the radicals with and without electric charge are discriminated from each other in view of the role in the particle nucleation process. In order to demonstrate the validity and utility of this kinetic model, the experiments of the unseeded emulsion copolymerization of styrene (ST) and methyl methacrylate (MMA) are carried out varying the initial initiator (potassium persulfate) and emulsifier (sodium lauryl sulfate) concentrations and the monomer composition in the initial monomer feed, and various kinetic features observed are compared with the model predictions. It is concluded from this comparison that in this system, almost all the polymer particles are generated by the charged radicals stemming from the initiator, and further that this mathematical kinetic model can provide a satisfactory explanation of the various kinetic features observed.     

Kinetics of emulsion copolymerization. II. Effect of free radical desorption on the rate of emulsion copolymerization of styrene and methyl methacrylate

The rate coefficient for radical desorption from the polymer particles is derived for an emulsion copolymerization system, assuming, for simplicity, that only monomer radicals can desorb from the particles. The effect of free radical desorption on the rate of emulsion copolymerization and the copolymer composition is theoretically analyzed, using the rate coefficient for radical desorption developed in this paper and a mathematical reaction model proposed earlier by the present authors for an emulsion copolymerization system where the average number of total radicals per particle does not exceed 0.5. The validity of the analysis is demonstrated experimentally using the seeded emulsion copolymerization of styrene (ST) and methyl methacrylate (MMA). Radical desorption from the particles does not affect the copolymer composition, but the desorption of MMA—monomer radicals plays an important role in determining the rate of emulsion copolymerization, while the desorption of ST—monomer radicals from the particles can be neglected from a kinetic point of view.     

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。     

Graft copolymerization of methyl methacrylate on holocellulose

Graft copolymerization of methyl methacrylate initiated by ceric ion in aqueous medium on bleached holocellulose was studied at 29°C. It was found that an increase in the concentration of ceric ion and oxidation of the holocellulose with aqueous potassium dichromate solution resulted in increased levels of incorporation of poly(methyl methacrylate) graft copolymer, but were associated with reductions in the efficiency of grafting. Thiol groups were introduced on the holocellulose by treatment with dilute thioglycollic acid solutions at 29°C. The influence on the level of grafting and on the molecular weight of the grafted polymer by the incorporated thiol groups on the substrate was examined.     

The role of methyl methacrylate on branching and gel formation in the emulsion copolymerization of BA/MMA

The effect of the monomer ratio on the microstructure of BA/MMA emulsion copolymers was investigated. Monomer ratios spanned from pure BA used for adhesives to 50/50 wt/wt BA/MMA copolymers used for coatings. The gel content varied from 55% for pure BA to nil for the 50/50 copolymer. The branching level was reduced from 2.6% for pure BA to 0.3% for a 75/25 BA/MMA copolymer. The mechanisms responsible for the reduction of gel content can be found in the lower reactivity of the MMA terminated chains for hydrogen abstraction, the absence of abstractable hydrogens in the MMA units and the fact that MMA radicals terminate predominantly by disproportionation. The reduction of the level of branches is mainly due to the lower reactivity of MMA for intramolecular transfer and the lower instantaneous conversions that favored propagation over backbiting.     

Graft copolymerization of gelatin with poly(methyl methacrylate) in aqueous medium

The grafting of poly(methyl methacrylate) onto gelatin in aqueous medium has been studied experimentally. The polymerization system is heterogeneous and the temperature and the initial concentration of gelatin charged in the reactor have been found to be extremely important. It is found that the amount of graft polymer increases rapidly and the formation of homopolymers is suppressed for large times. The predominantly graft polymer for the large times is essentially free from homopolymers and needs no separation. A theoretical model has been proposed which accounts for the heterogeneity in the reaction mass. The numerical solution of mass balance equations and its validation against experimental data suggests that graft copolymers react at the waterdroplet interphase at considerably higher rate.     

The stabilization effect of mixed-surfactants in the emulsion polymerization of methyl methacrylate

Summary The emulsion polymerization of methyl methacrylate (MMA) was conducted at 50°C using either anionic or nonionic surfactants, or a mixture of the two at different surfactant concentrations. In the singlesurfactant systems a proportional relationship was observed between the total particle surface area per cm³ of aqueous solution at 90% conversion (TS) and the amount of surfactant used. For mixed-surfactant systems, a relationship close to an additive one was found between the TS value and the amount of each surfactant used. The particle number did not remain constant during the polymerization, while the TS value continuously increased. It was also found that MMA formed a paste easily at higher (M/W) ratios, which could be alleviated by using higher surfactant concentrations.     

Studies on the copolymerization of methyl methacrylate and N-aryl maleimides

This article describes the synthesis and characterization of copolymers of methyl methacrylate (MMA) and N-4-chlorophenyl maleimide (PC)/N-3-chlorophenyl maleimide (MC). The copolymers were synthesized by varying the mole fraction of N-aryl maleimides from 0.1 to 0.5 in the initial feed using azobisisobutyronitrile (AIBN) as an initiator and tetrahydrofuran (THF) as the solvent. The copolymer composition was determined from the ¹H-NMR spectra by taking the ratio of proton resonance signals due to methoxy protons (δ = 3.59 ppm) of MMA and aromatic protons (δ = 7.2–7.4 ppm) of N-aryl maleimides. The reactivity ratios for MMA–PC and MMA–MC copolymers were found to be 0.952 (r₁), 0.029 (r₂) and 0.833 (r₁) and 0.033 (r₂), respectively. Thermal characterization of the copolymers was done using differential scanning calorimetry (DSC) and dynamic thermo-gravimetry. Initial decomposition temperature and glass transition temperature increased with increasing mole fraction of N-aryl maleimide content in the copolymers. © 1996 John Wiley & Sons, Inc.     

Atom transfer radical copolymerization of glycidyl methacrylate and methyl methacrylate

Glycidyl methacrylate (GMA) and methyl methacrylate (MMA) copolymers were synthesized by atom transfer radical polymerization (ATRP). The effect of different molar fractions of GMA, ranging from 0.28 to 1.0, on the polymer polydispersity index (weight‐average molecular weight/number‐average molecular weight) as the indicator of a controlled process was investigated at 70°C, with ethyl 2‐bromoisobutyrate as an initiator and 4,4′‐dinonyl‐2,2′‐bipyridyne (dNbpy)/CuBr as a catalyst system in anisole. The monomer reactivity ratios (r values) were obtained by the application of the conventional linearization Fineman–Ross method (r_GMA = 1.24 ± 0.02 and r_MMA = 0.85 ± 0.03) and by the Mayo–Lewis method (r_GMA = 1.19 ± 0.04 and r_MMA = 0.86 ± 0.03). The molecular weights and polydispersities of the copolymers exhibited a linear increase with GMA content. The copolymer compositions were determined by ¹H‐NMR and showed a domination of syndiotactic structures. The glass‐transition temperatures (T_g) of the copolymers analyzed by differential scanning calorimetry (DSC) decreased in the range 105–65°C with increasing GMA units. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Graft copolymerization of methyl methacrylate upon gelatin initiated by benzoyl peroxide in aqueous medium

The graft copolymerization of methyl methacrylate upon gelatin was studied using benzoyl peroxide as an organic initiator in aqueous medium. The grafting reactions were carried out within the 65–90°C temperature range, and the effect of monomer and initiator concentrations on the graft yield were also investigated. The maximum graft yield was obtained at a benzoyl peroxide concentration of 0.20 × 10⁻² mol/L and the optimum temperature was 80°C. Thermogravimetric analysis showed that the thermal stability of gelatin increased as a result of grafting. Further, such changes in the properties of methyl methacrylate‐grafted gelatin as density, moisture regain, and water uptake were also determined. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1547–1556, 1999     

水性聚氨酯与丙烯酸酯共聚乳液的研究

用乳液聚合的方法 ,制备出了具有核壳结构的水性聚氨酯与丙烯酸酯共聚乳液 (PUA乳液 ) ,对PUA的性能进行了初步的研究。结果表明 ,丙烯酸酯的用量对吸水率、热性能和机械性能产生重要的影响     

Graft copolymerization of methyl methacrylate (MMA) on hydrazine treated oxycellulose in limited aqueous system

Graft copolymerization of methyl methacrylate (MMA) on oxycellulose modified with hydrazine treatment was studied in a limited aqueous system using K₂S₂O₂ as the initiator. Hydrazine modified oxycellulose prepared from oxycellulose corresponding to low degrees of oxidation (copper nos. 2–6) produced the best grafting effects. Grafting parameters under different sets of conditions were studied and compared and the mechanism of graft copolymerization discussed.     

Graft copolymerization of methyl methacrylate and natural rubber

Graft copolymerization of natural rubber and MMA was carried out in the presence of Bz₂O₂ or AIBN as thermal initiator and hydrogen peroxide or benzophenone as photosensitizer. From the overall copolymerization product, the rubber–PMMA graft copolymer fraction was isolated from unreacted rubber and free PMMA fractions and composition characterization of the separated fractions was done by determination of rubber unsaturation. The efficiency of grafting under different conditions has been calculated and compared.