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     

Organization in sol-gel polymerization of methacrylate co-oligomers containing trimethoxysilylpropyl methacrylate

The sol-gel polymerization and resulting structures of organic-inorganic systems based on hybrid methacrylate oligomers have been studied using SEC, DSC, and SAXS. The block and random oligomers with narrow polydipersity were prepared by group transfer polymerization. All the oligomers contain 3-(trimethoxysilyl)propyl methacrylates in the chain and form silsesquioxane (SSQO) clusters by hydrolytic polycondensation, serving as cross-linking domains of the organic-inorganic network. The water miscibility and gelation of synthesized oligomers were evaluated. The systems studied can be divided into two groups—gelling and non-gelling oligomers as a result of the competition between cyclization and intermolecular reaction. The extent of cyclization and intermolecular polycondensation depends on the oligomer structure, i.e. position and number of the functional trimethoxysilyl-monomer units, and on molecular weight of the oligomeric chains. Due to the incompatibility of the SSQO framework and organic chains, microphase separation and structure ordering occur during polymerization.     

Preparation and characterization of copolymers from methyl methacrylate and cardanyl methacrylate

Copolymers of methyl methacrylate (MMA) and cardanyl methacrylate (CMA) were synthesized, characterized and their physico-mechanical properties were investigated. The benzoyl peroxide-initiated copolymerization was carried out by using different mole fractions of CMA (0.02–0.10) in the initial feed at 80°C. Structural characterization of copolymers was done using FTIR and ¹H NMR spectroscopic techniques. The thermal stability of the copolymers was evaluated using dynamic thermogravimetry. Incorporation of CMA in the MMA backbone leads to an improvement in thermal stability.     

乙酰乙酸基甲基丙烯酸乙酯的合成

以甲基丙烯酸羟乙酯(HEMA)和乙酰乙酸乙酯(AAA)为原料,固体酸为催化剂,采用酯交换法合成了乙酰乙酸基甲基丙烯酸乙酯(AAEM)。采用单因素和正交实验的方法对反应条件进行了探究,确定较佳的反应条件为:n(AAA)∶n(HEMA)=3∶1,反应温度130℃,反应时间3 h,催化剂的用量4.5%(HEMA),阻聚剂的用量0.3%(HEMA)。在上述条件下,产品收率93%以上,含量97%,采用FTIR和1H NMR对产品结构进行了表征。     

乙酰乙酸基甲基丙烯酸乙酯的合成

以甲基丙烯酸羟乙酯(HEMA)和乙酰乙酸乙酯(AAA)为原料,固体酸为催化剂,采用酯交换法合成了乙酰乙酸基甲基丙烯酸乙酯(AAEM)。采用单因素和正交实验的方法对反应条件进行了探究,确定较佳的反应条件为:n(AAA)∶n(HEMA)=3∶1,反应温度130℃,反应时间3 h,催化剂的用量4.5%(HEMA),阻聚剂的用量0.3%(HEMA)。在上述条件下,产品收率93%以上,含量97%,采用FTIR和1H NMR对产品结构进行了表征。     

Miscibility of poly(methoxymethyl methacrylate) and poly(methylthiomethyl methacrylate) with poly(methyl methacrylate)

Summary Poly(n-propyl methacrylate) is known to be immiscible with poly(methyl methacrylate) (PMMA). However, we have found that poly(methoxymethyl methacrylate) is miscible with PMMA, indicating the importance of ether oxygen atoms in achieving miscibility. On the other hand, poly(methylthiomethyl methacrylate) is immiscible with PMMA.     

The transport of methyl methacrylate monomer in poly(methyl methacrylate)

The absorption kinetics and equlibria of methyl methacrylate monomer into poly(methyl methacrylate) were studied over a range of penetrant activities. The interval sorption kinetics at elevated activities were determined, compared, and contrasted with the integral sorption experiments in previously unpenetrated film samples. The sorption kinetics in previously unpenetrated films were predominantly case II or relaxation controlled at high activities. A Fickian contribution to the overall kinetics was apparent at lower activities. In contrast, interval sorption, at elevated activities in previously equilibrated and plasticized samples, followed Fickian kinetics rather closely, whereas resorption, over an activity range which involved a traversal of the effective T_g, was characterized by more complicated kinetics involving a super case II mechanism at long times. These composite results reinforce the notion that the kinetics describing penetration of a single penetrant into a single polymer are extremely sensitive to the boundary condition imposed upon the polymeric sorbent.     

Studies on tri-n-butyltin methacrylate (TBTM). IV. Antifouling compositions based on copolymers of tri-n-butyltin methacrylate and methyl methacrylate

Based on reactivity ratios reported earlier, a number of copolymers of methyl methacrylate and tri-n-butyltin methacrylate has been prepared. Release of tri-n-butyltin oxide into seawater from the copolymer films has been determined at 30°C as a function of time. The copolymers behave in a typical manner—an initial increase in leaching rate followed by a steady state which is reached after about 60 days. Pigmented copolymer films behave in a similar manner, even though the overall leaching rate is slightly lower. Release rate data are also presented for a typical antifouling paint formulation.     

Synthesis and characterization of butyl acrylate/methyl methacrylate/glycidyl methacrylate latexes

The butyl acrylate (BA)/methyl methacrylate (MMA), and glycidyl methacrylate (GMA) composite copolymer latex was synthesized by seeded emulsion polymerization technique taking poly(methyl methacrylate) (PMMA) latex as the seed. Four series of experiments were carried out by varying the ratio of BA : MMA (w/w) (i.e. 3.1 : 1, 2.3 : 1, 1.8 : 1, and 1.5 : 1) and in each series GMA content was varied from 1 to 5% (w/w). The structural properties of the copolymer were analyzed by FTIR, ¹H‐, and ¹³C‐NMR. Morphological characterization was carried out using transmission electron microscopy (TEM). In all the experiments, monomer conversion was ～99% and final copolymer composition was similar to that of feed composition. The incorporation of GMA into the copolymer chain was confirmed by ¹³C‐NMR. The glass transition temperature (T_g) of the copolymer latex obtained from the differential scanning calorimetry (DSC) curve was comparable to the values calculated theoretically. With increase in GMA content, particles having core‐shell morphology were obtained, and there was a decrease in the particle size as we go from 2–5% (w/w) of GMA. The adhesive strength of the latexes was found to be dependent on the monomer composition. With increase in BA : MMA ratio, the tackiness of the film increased while with its decrease the hardness of the film increased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Grafting of 2-hydroxyethyl methacrylate and methyl methacrylate onto chrome tanned collagen fibers

Grafting of 2-hydroxyethyl methacrylate and methyl methacrylate onto chrome tanned collagen fibers, initiated by the bisulfite/pesulfate redox system, has been investigated. Using the method of statistical planning of experiments, regression equations have been obtained describing the effects of the monomers concentration and the composition of the initiating system on the monomers conversion, degree of grafting and on physical properties of grafted collagen. The relationship between the polyacrylate content in the composites prepared and their swelling ability, water absorption capacity, and the tensile strength is discussed.     

丙烯酸-3-环己烯基甲酯的合成研究

以丙烯酸甲酯(MA)和3-环己烯-1-甲醇为原料,采用酯交换法合成了丙烯酸-3-环己烯基甲酯,考察了催化剂种类与用量、反应时间、反应物配比、阻聚剂种类以及用量等因素对反应结果的影响。结果表明,采用有机锡类催化剂和吩噻嗪阻聚剂,m(有机锡)∶m(3-环己烯-1-甲醇)=0.04、反应时间7 h、n(MA)∶n(3-环己烯-1-甲醇)=3.5∶1,在此条件下,3-环己烯-1-甲醇的转化率达95%以上,产品收率91%。并采用IR和1H NMR技术对产品的结构进行了表征。     

Stereoregular oligomers of methyl methacrylate

Summary Packed column SFC has been found suitable for the rapid and detailed analysis of the isotactic and syndiotactic oligomers of MMA, when the temperature gradient technique was applied and the modifier was employed. Oligomer components from trimer to 20-mer separated completely. The heptamer fraction collected three times by SFC gave the ¹H NMR spectrum of satisfactorily high S/N ratio; the spectrum agreed well with that of the standard sample. Separation by tacticity as well as by molecular weight was observed for the SFC of a mixture of the isotactic and syndiotactic oligomers. The isotactic oligomers had longer retention time than the syndiotactic oligomers of the corresponding degree of polymerization. Part 3: cf. Ute K. Nishimura T, Hatada K, Polym J (1989) 21: 1027     

丙烯酸-3-环己烯基甲酯的合成研究

以丙烯酸甲酯(MA)和3-环己烯-1-甲醇为原料,采用酯交换法合成了丙烯酸-3-环己烯基甲酯,考察了催化剂种类与用量、反应时间、反应物配比、阻聚剂种类以及用量等因素对反应结果的影响。结果表明,采用有机锡类催化剂和吩噻嗪阻聚剂,m(有机锡)∶m(3-环己烯-1-甲醇)=0.04、反应时间7 h、n(MA)∶n(3-环己烯-1-甲醇)=3.5∶1,在此条件下,3-环己烯-1-甲醇的转化率达95%以上,产品收率>91%。并采用IR和1H NMR技术对产品的结构进行了表征。     

Studies on tributyl tin methacrylate (TBTM). VI. Thermal and tensile behavior of copolymer of tri-n-butyl tin methacrylate and methyl methacrylate

The thermal and tensile properties of polytributyl tin methacrylate (PTBTM) and n-tributyl tin methacrylate–methyl methacrylate (TBTM—MMA) copolymers have been studied. Thermogravimetric study showed that with increasing the TBTM content in the copolymer the thermal stability decreases. The glass transition temperature (T_g) decreases continuously as the TBTM content increases. All the polymers showed multistep decomposition. MS study showed that in addition to monomer formation several other side reactions also take place during degradation, leading to formation of other products. Studies on tensile properties show that the tensile strength decreases with increasing TBTM content, whereas elongation at break increases. © 1992 John Wiley & Sons, Inc.     

Stereoregular oligomers of methyl methacrylate

Summary Isotactic (it-) and syndiotactic (st-) MMA oligomers from 19-mer to 29-mer could be isolated efficiently from it-PMMA ( = 28.6) and st-PMMA ( = 28.6) (sample load: 50 mg) by the SFC using a 10 mm i. d. x 250 mm column packed with silica gel. DP of each isolated oligomer was determined by FD mass spectroscopy, and the values agreed well with those calculated from the relative intensity of ¹H NMR signals due to CH₃O- and the terminal t-C₄H₉-groups. Glass transition temperature (T _g) of the it-28-mer measured by DSC was 34.5°C, which was higher than that of the it-PMMA by 6.5°C. T _g of both the it-and st-oligomers increased linearly with DP in the range of DP=2029. A 1: 1 mixture of the it- and st-27-mers annealed at 140°C showed an endothermic transition at 102.3°C which was attributable to melting of stereocomplex, whereas an annealed 1: 1 mixture of the it- and st-PMMAs had a much broader endotherm around 80140°C.Part 5: Ute K, Miyatake N, Hatada K (1992) J. Macromol. Sci.-Chem., A29, in press