• Macromolecular Research
• /
• v.17 no.4
• /
• pp.240-244
• /
• 2009

High molecular weight(MW), 3-arm star poly(methyl methacrylate)(PMMA) with a narrow MW distribution($M_n$=570,000 g/mol, PDI=1.36) was successfully synthesized by activators regenerated by electron transfer(ARGET) atom transfer radical polymerization(ATRP). The polymerization was carried out with a trifunctional initiator/$CuBr_2$/N,N,N',N",N"-pentamethyldiethy lenetriamine(PMDETA) initiator/catalyst system in the presence of a tin(II) 2-ethylhexanoate [$Sn(EH)_2$] reducing agent at $90^{\circ}C$. The concentration of the copper catalyst was as low as 30 ppm, and a high initiation efficiency of the initiating sites was obtained. The chain-end functionality of the high MW, 3-arm star PMMA was confirmed by a chain extension experiment with styrene via ARGET ATRP, using the same catalyst system.

• Macromolecular Research
• /
• v.15 no.5
• /
• pp.418-423
• /
• 2007

A methacrylate copolymer based on isobornyl methacrylate (IBMA) and methyl methacrylate (MMA) was synthesized in an aqueous suspension via free-radical polymerization. The potential of this copolymer as a heat-resistant optical polymer is also discussed. 1,1,3,3-tetramethylbutyl peroxy-2-ethyl hexanoate and n-octyl mercaptan were used as the initiator and chain transfer agents, respectively. The effect of IBMA on the properties of the copolymer was investigated. The composition of the copolymer was analyzed using $^1H-NMR$, and the heat resistance by measuring the glass transition temperature, which exhibited a linear dependency on the IBMA content in the copolymer. Variation of the chain transfer content used in the synthesis step was effective for the optimization of the copolymer for practical use.

• Macromolecular Research
• /
• v.14 no.5
• /
• pp.559-564
• /
• 2006

The improvement of spatial resolution is a fundamental issue in the two-photon, polymerization-based, laser writing. In this study, a voxel tuning method using a radical quencher was proposed to increase the resolution, and the quenching effect according to the amount of radical quencher was experimentally investigated. Employing the proposed method, the lateral resolution of the line patterns was improved almost to 100 nm. However, a shortcoming of the quenching effect was the low mechanical strength of polymerized structures due to their short chain lengths. Nano-indentation tests were conducted to evaluate quantitatively the relationship between mechanical strength and the mixture ratio of the radical quencher into the resins. The elastic modulus was dramatically reduced from an average value of 3.015 to 2.078 GPa when 5 wt% of radical quencher was mixed into the resin. Three-dimensional woodpile structures were fabricated to compare the strength between the resin containing radical quencher and the original resin.

• Composites Research
• /
• v.32 no.3
• /
• pp.163-169
• /
• 2019

In this paper, we constructed a molecular dynamics (MD) polymer model of PMMA with 95% of conversion by using dynamic polymerization algorithm of a thermoplastic polymer based on free radical polymerization. In this algorithm, we introduced a united-atom level coarse-grained force field that combines the non-bonded terms from the TraPPE-UA force field and the bonded terms from the PCFF force field to alleviate the computation efforts. The molecular weight distribution and the average molecular weight of the polymer were calculated by investigating each chain generated from the free radical polymerization simulation. The molecular weight of the polymer was controlled by the number of initiator radicals presented in the initial state and molecular weight effect to the density, the glass transition temperature, and the mechanical properties were studied.

• 제어로봇시스템학회:학술대회논문집
• /
• 1998.10a
• /
• pp.468-473
• /
• 1998

A mathematical model was developed for a continuous re-actor in which free radical polymerization of methyl methacrylate (MMA) occurred. Elementary reactions considered in this study were initiation, propagation, termination, and chain transfers to monomer and solvent. The reactor model took into account the density change of the reactor contents and the gel effect. A control system was designed for a continuous reactor using extended Kalman filter (EKF) based non-linear model predictive controller (NLMPC) to control the conversion and the weight average molecular weight of the polymer product. Control input variables were the jacket inlet temperature and the feed flow rate. For the purpose of validation of the control strategy, on-line digital control experiments were conducted with densitometer and viscometer for the measurement of the polymer properties. Despite the com-plex and nonlinear features of the polymerization reaction system, the EKF based NLMPC performed quite satisfactorily for the property control of the continuous polymerization reactor.

• Elastomers and Composites
• /
• v.37 no.1
• /
• pp.31-38
• /
• 2002

Polymerization of carboxylated styrene-butadiene latex takes longer time than that of acrylic emulsion due to delocalization of radical in butadiene unit having conjugated double bond. A latex stability is the most important properties owing to use intact without separating polymer from base latex. For reducing polymerization time without decreasing any properties of latex, carbon tetra-chloride which has been used as the most popular chain transfer agent was replaced to combination of tert-dodecylmercaptane and ${\alpha}$-methylstyrene dimer. The replacement yielded reducement or 2 hr in polymerization time. In the increment step, charge amount of acrylic acid was limited to 0.3 part to restrain viscosity enhancement. Just after initial step, addition of 0.1 part acrylamide prevent polymer chain from diffusing between two region followed by giving hardness and final good adhesive force to latex particles.

• Proceedings of the Polymer Society of Korea Conference
• /
• 2006.10a
• /
• pp.322-322
• /
• 2006

Well-defined poly(N-vinylcarbazole), poly(NVC), was synthesized by macromolecular design via interchange of the xanthate (MADIX)/reversible addition-fragmentation chain transfer (RAFT) polymerization in the presence of a suitable xanthate-type chain transfer agent (CTA). Good control of the polymerization was confirmed by the linear first-order kinetic plot, the molecular weight controlled by the monomer/CTA molar ratio, linear increase in the molecular weight with the conversion, and the ability to extend the chains by the second addition of the monomer. Star polymers having various architectures were also synthesized using this technique.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
• /
• 2004.11a
• /
• pp.583-585
• /
• 2004

In this paper, we synthesized a new photo-crosslinkable polyitaconimide containing cinnamoyl moiety by radical polymerization. Also, the NLC alignment capabilities on these photopolymer surfaces were studied. Good LC alignment with W exposure on the polyitaconimide surfaces can be obtained. A homogenous alignment using UV exposure on the polyitaconimide with 1-carbon chain cinnamoyl group and 4-carbon chain cinnamoly group can be obtained. However, the homeotripic alignment using UV exposure was observed on polyitaconimide with 6-carbon chain cinnamoyl. The LC aligning ability on the polyitaconimide depends on the side chain length of photopolymer.

• Journal of Korean Ophthalmic Optics Society
• /
• v.8 no.2
• /
• pp.129-134
• /
• 2003

A wide variety of unsaturated vinyl derivatives can be induced to undergo free-radical chain polymerization. The capability to carry out a thermodynamically feasible polymerization relies on its kinetic feasibility on whether the proceeds at a reasonable rate under a given set of reaction conditions. Initiator or promoter is often required to achieve the kinetic feasibility. Only a few unsaturated monomers including methyl methacrylate(MMA) are known to absorb light between 250 and 500 nm which is the most convenient wavelength range. Also, the polysilanes with unusual optical and electronic properties have been used as ceramic precursors, deep UV photoresists, photoconductors. The hydrosilation has been used to make many interesting types of silicon containing polymers such as copolymer, dendrimers. Bulk polymerization of monomers with different molar radio of hydrosilanes(9:1 through 1:9) were performed. A quartz test tube charged with monomer and hydrosilane was degassed and irradiated with 250 nm UV for 6 hours. The polymer was taken in toluene, precipitated in hexane, filtered off, and dried. It was found that the initiators appeared to competitively and concurrently function as both chain initiation and transfer agents in the polymerization of vinyl monomers.

• Elastomers and Composites
• /
• v.44 no.2
• /
• pp.122-133
• /
• 2009

Rubbers, such as natural rubber, polybutadiene, styrene-butadiene rubber, nitrile-butadiene rubber, chlorinated rubber and EPDM, have been continuously improved in response to a heavy demand and a new property requirement from industry. One of the best ways to realize the improvement is the modification of rubbers through chemical reactions, which produce materials with novel properties. In this review, chemical modification reactions of rubbers that contain carbon-carbon double bond units either in their main backbone or as a side group were briefly summarized. The chemical reactions introduce functional groups or functional polymer chains to polymer backbone, which transform a classical rubber to a highly functional material. Especially, we focused on a controlled/"living" radical polymerization techniques, with which a revolutionary broadening of the spectrum of the materials with well defined molecular weight, molecular weight distribution, chain end-functionality and architectures become possible.