It is attempted to develop flame retardant polyurethane coatings, which have received significant attention in recent years. It is the purpose of this study to synthesize new reactive polyurethane coatings containing halogen. Lactone based modified polyester polyols, using trichlorobenzoic acid as chlorine moiety (TBAOs) were synthesized. These polyesters were cured with isophorone diisocyanate (IPDI)-isocyanurate at room temperature (TBAPUs). Physical properties of these flame retardant coatings were similar with those of non-flame retardant coatings. The flammability of coatings was strongly dependent on the chlorine contents. We found that the increasing chlorine contents showed better flame retarding properties and that, however, they also resulted in more smog generation during combustion. The detailed results of flammability test using various methods indicated 24~26% in LOI and 3.7~5.3 cm char length in 45˚ Meckel burner method.

Methanol and formaldehyde were produced directly by the partial oxidation of methane over mixed oxide catalysts. The catalysts were composed of Mo and Bi with late-transition metals, such as Mn, Fe, and Co. The reaction was carried out at 450℃, 50 bar in a fixed-bed differential reactor. The prepared catalysts were characterized by O2-TPD and BET apparatus. Among the catalysts used, the catalyst composed of 1:1:2.5 molar ratio of Mo:Bi:Mn showed the best methane conversion and methanol selectivity. The change in ratio of methane to oxygen affected at the conversion and selectivity, and the most proper ratio was 10:1.5. Methane conversion, methanol and formaldehyde selectivities increased with the surface areas of the catalysts. From the O2-TPD result, it was found that the oxygen species responsible for this reaction might be the lattice oxygen species desorbed at high temperature around 800℃.

Acrylic adhesives for automobiles protection were prepared by emulsion polymerization. Monomers used were n-butyl acrylate(BA), acrylonitrile (AN), butyl methacrylate(BMA), glycidyl methacrylate(GMA), and acrylic acid (AA). Emulsifiers used were sodium lauryl sulfate and polyoxyethylene lauryl ether, which are an anionic emulsifier and a nonionic emulsifier respectively. Potassium persulfate was used as an initiator and polyvinyl alcohol was used as a stabilizer. Emulsion polymerization was carried out in a semi-batch reactor at 70℃ and agitation speed was kept at 200 rpm. Water resistance, heat resistance, acid resistance, alkali resistance and smoke resistance were examined. As a result, when each 0.03 mole of GMA and AA was introduced, the adhesion properties and various above mentioned resistances of the prepared adhesives were satisfied the standard for automobiles.

The high-solid coatings were prepared by blending the synthesized acrylic resin in the previous paper, and hexamethylene diisocyanate-trimer and curing it at room temperature. The characterization of the films of the prepared coatings was performed. The 60˚ specular gloss, impact resistance, cross-hatch adhesion, and heat resistance of the films proved to be good, and the pencil hardness, drying time, and pot-life proved to be slightly poor. From a viscoelastic measurement using a rigid-body pendulum, curing was accelerated with the Tg value.

In order to obtain the maximum flame retardancy as well as the minimum deterioration of physical properties of PU flame-retardant coatings, chlorine and phosphorus functional groups were introduced into the pre-polymer of modified polyesters. In the first step, the tetramethylene bis(orthophosphate) (TBOP) and neohexanediol dichloroacetate (DCA-adduct) intermediates were synthesized. In the second step, 1,4-butanediol and adipic acid monomers were polymerized with the two kinds of intermediates to obtain copolymers. The modified polyesters containing chlorine and phosphorus (ATBA-10C, -20C, and -30C) were synthesized by adjusting that the content of phosphorus compound was fixed as 2wt% and the contents of chlorine compound (dichloroacetic acid) were varied as 10, 20, and 30wt%. Average molecular weight and polydispersity index of the preparation of ATBAs were decreased with increasing DCA content because of the increase in hydroxyl group that retards reaction.

Acrylic resins (HSCs : EA/EMA/2-HEMA/CLA) which contain 80% solid content were synthesized by the copolymerization of monomers (ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate) and functional monomer (caprolactone acrylate : CLA) which improves the crosslinking density and physical properties of films. The physical properties of the prepared acrylic resins (HSCs) containing CLA, are as follows: viscosity 1440~2630 cps ; Mn 1590~1660 ; and conversions, 81~86%, respectively. From the correlation of Tg values, viscosities, and Mn of the HSCs, it was found thst viscosity and Mn increased with Tg value.

Modified polyesters (TTBA-10C, -20C, -30C) that contain phosphorus and chlorine were synthesized by the condensation polymerization of tetramethylene bis(orthophosphate), neohexanediol trichlorobenzoate, 1,4-butanediol and adipic acid, in which tetramethylene bis(orthophosphate) and neohexanediol trichlorobenzoate were prepared previously in our laboratory. In this study, two-component flame-retardant polyurethane coatings (TTBA-10C/HDI-trimer=TTHD-10C, TTBA-20C/ HDI-trimer= TTHD-20C, TTBA-30C/HDI-trimer= TTHD-30C) were obtained by curing at room temperature with the synthesized TTBAs and hexamethylene diisocyanate (HDI)-trimer as a curing agent. The obtained TTHDs were made into coating samples and used as test samples for various physical properties. The physical properties of the flame-retardant coatings containing chlorine and phosphorus groups were generally inferior to those containing only phosphorus group. Flame retardancy was tested by vertical and horizontal combustion method, and 45˚ Meckel burner method. Since the retardancy of flame-retardant coatings containing chlorine and phosphorus groups was better than that containing only phosphorus group, it could be concluded that the retardancy by the synergism effect of chlorine and phosphorus groups exhibited.

Methanol and formaldehyde were produced directly by the partial oxidation of methane. The catalysts used were mixed oxides of late-transition metals, such as Mn, Fe, Co, Ni and Cu. The reaction was carried out at 450℃, 50 bar in a fixed-bed differential reactor. The prepared catalysts were characterized by XRD, TPD and BET apparatus. Of the catalysts, A-Mn0.2-6, which contains 0.2 mole of Mn and calcined at 600℃, showed the best catalytic activity: 3.7% methane conversion, and 30 and 28% methanol and formaldehyde selectivities, respectively. The catalytic activity was changed with the content of Mn and the calcination temperature. Catalytic activity increased with the specific surface areas of the catalysts. With XRD, it was found that the structure of the catalysts are changed with calcination temperature. Through O2-TPD experiment, it was found that the catalysts showing good catalytic activity showed O2 desorption peak around 800℃.

Solvent-free low foaming scouring agents (LFSC) were prepared by blending of 2-ethylhexylaminoethyl sulfate (2-EHAS), POE(10) octadecylbenzyl- ammonium chloride (POBAC) and Sedlan FF-200 (FF-200). As the results of several tests, 2-EHAS/POBAC/FF-200/water (8g/12g/20g/60g) mixture (LFSC-5) showed good cleaning power, penetrating ability and stability to alkali, and gave less problem in water pollution. The foaming power of LFSC-5 measured by Ross and Miles method was 8mm foam height immediately after foaming, and that measured by Ross and Clark method was less than 300mm foam height at 30℃, and 18mm at 80℃. As a result, LFSC-5 proved a good low foaming scouring agent for fiber.

The aim of this study is to synthesis basic resins for the preparation of PU flame-retardant coatings that contain phosphorus and chlorine. After synthesizing intermediates of tetramethylene bis(orthophophate) (TMBO) and neohexanediol trichlorobenzoate (TBA-adduct), the condensation polymerization was performed with the intermediates, 1,4-butanediol, and adipic acid to obtain four-component copolymers. In the condensation polymerization, the content of phosphorus was fixed to be 2%, and the content of trichlorobenzoic acid (TBA) that provides chlorine component was varied to be 10, 20, and 30wt%, and we designated the prepared modified polyesters containing chlorine and phosphorus as TTBA-10C, TTBA-20C and TTBA-30C. Average molecular weight and polydispersity index of the prepared TTBAs decreased with increasing TBA content because of the increase in the number of hydroxyl groups that retards reaction. We found that the thermal stability of the prepared TTBAs increased with chlorine content at high temperatures.

In the previous study, three kinds of monomers and the functional monomer, acetoacetoxyethyl methacrylate (AAEM), which could improve the film property and cross-linkage, were polymerzied into acrylic resin copolymers (HSA-98-20, HSA-98-0, HSA-98+20) containing 80% solid content. In this study, the high-solid coatings(HSA-98-20C, HSA-98-0C, HSA-98+20C) were prepared by the curing reaction between acrylic resins containing 80% solid content and isocyanate at room temperature. Various properties were examined for the film coated with the prepared high-solid coatings. The introduction of AAEM in the coatings enhanced the abrasion resistance and solvent resistance of coatings, which indicated the possible use of high-solid coatings for top-coating materials of automobile. The curing times measured by viscoelastic measurement were 350, 264, and 212 min for HSA-98-20C, HSA-98-0C, and HSA-98+20C, respectively. This shows that the curing times become shorter with increasing Tg values.

Copolymers (HSA-98-20, HSA-98-0, HSA-98+20) which are acrylic resin containing 80% solid content were synthesized by the reaction of monomers, including methyl methacrylate, n-butyl acrylate, and 2-hydroxyethyl acrylate with a functional monomer, such as acetoacetoxyethyl methacrylate (AAEM), which may improve in cross-linking density and physical properties of films. The physical properties of prepared acrylic resins, containing AAEM, are as follows : viscosity, 1420~5760cps ; number average molecular weight, 2080~2300 ; polydispersity index, 2.07~2.19 ; conversions, 88~93%, respectively. To prepare acryl resins, four kinds of initiators including α,α'-azobisisobutyronitirile (AIBN), di-tert-butyl peroxide (DTBP), t-amylperoxy-2-ethyl hexanoate (APEH), benzoyl peroxide (BPO) were used. The viscosity of the acrylic resins prepared with these initiators was increased in the order of DTBP〉APEH〉AIBN〉BPO. APEH was proved as a suitable initiator in this study. Shear rates of acrylic resins were constant in respect to viscosity. From these results, it would appear that the resins have Newtonian flow characteristics and good workability.

This study was conducted to prepare acrylic removable protective coatings by emulsion polymerization. Monomers used were n-butyl acrylate, acrylonitrile, butyl methacrylate. Emulsifiers used were sodium lauryl sulfate and polyoxyethylene lauryl ether, which are an anionic emulsifier and a nonionic emulsifier respectively. Potassium persulfate was used as an initiator and polyvinyl alcohol was used as a stabilizer. Emulsion polymerization was carried out in a semi-batch reactor at 70℃ and agitation speed was 200 rpm. Tensile strength, extension, peel strength, viscosity, and solid contents of the synthesized coatings were examined. The coatings prepared with BA:AN = 60:20 (in weight ratio) satisfied the standard for automobile in terms of extension and peel strength. When the concentration of BMA was in a range of 18~23 wt%, the prepared coatings satisfied the standard for automobile in terms of peel strength and water resistance.

In order to improve resistant properties of water-borne acrylic pressure sensitive adhesives(PSAs) for automobiles, this study was carried out. Removable PSAs for automobiles were synthesized by emulsion polymerization of monomers, n-butyl acrylate(BA), n-butyl methacrylate(BMA), acrylonitrile(AN), acrylic acid(AA) and 2-hydroxyethyl methacrylate(2-HEMA), and AA and 2-HEMA could act as functional monomers for crosslink. Emulsion polymerization was carried out in a semi-batch type reactor. Water resistance, heat resistance, acid resistance, alkali resistance and smoke resistance were examined. As a result, water resistance increased with the amount of BMA, however, the effect of BMA content on the water resistance was insignificant at a range of over 14 wt%. The water resistance also increased with the amount of functional monomers, AA and 2-HEMA. The prepared PSAs satisfied all the standard for automobiles except heat resistance. However, the heat resistance comes nearly up to the standard. Also, acid resistance, alkali resistance and smoke resistance of the prepared PSAs satisfied with the standard.

To maximize a synergy effect in flame-retardancy of flame-retardant coatings, phosphorus and chlorine were introduced in polymer chains. Two-components PU flame-retardant modified polyesters (ABTTC-10C, -20C, -30C) were prepared by curing, at room temperature, of isocyanate (allophanate-trimer) and prepared modified polyesters which contain phosphorus and chlorine. To examine the film properties of the prepared flame-retardant coatings, film specimens were prepared with the prepared coatings. The film properties of ABTTC, ABTTC-10C and ABTTC-20C, which contain 0, 10 and 20wt%, 2,4-dichlorobenzoic acid (2,4-DCBA), respectively, were proved to be good, whereas the film properties of ABTTC-30C, which contains 30wt% 2,4-DCBA, were proved to be a little bit poor. Two kinds of flame retardancy tests, 45˚Meckel burner method and LOI method, were performed. With the 45˚Meckel burner method, three flame-retardant coatings except ABTTC showed less than 3.4 cm of char length, and showed less than 2 seconds of afterflaming and afterglow. From this result, the prepared flame-retardant coatings were proved to have the 1st grade flame retardancy. With the LOI method, the LOI values of the coatings containing more than 10wt% 2,4-DCBA were higher than 30wt%, which means that the coatings possess good flame-retardancy. From these results, it was found that synergistic effect in flame-retardancy was taken place by the introduced phosphorus and chlorine.

This study was focused on the maximization of flame-retardancy of polyesters by a synergism of simultaneously introduced chlorine and phosphorus into polymer chains of modified polyesters. To prepare modified polyesters, reaction intermediates, TD-adduct (prepared from trimethylolpropane /2,4-dichlorobenzoic acid (2,4-DCBA)) and TMBO (prepared from tetramethlene bis (orthophosphate)), were prepared first, then condensation polymerization of the prepared intermediates, adipic acid, and 1,4-butanediol were carried out. In the condensation polymerization, the content of phosphorus was fixed to be 2wt%, and the content of 2,4-DCBA that provides chlorine component was varied to be 10, 20, and 30wt%, and we designated the prepared modified polyesters containing chlorine and phosphorus as ABTTs. The prepared intermediates and modified polyesters were characterized with FT-IR, NMR, GPC, and TGA analysis. Average molecular weight and polydipersity index of the preparation of ABTTs were decreased with increasing 2,4-DCBA content because of the incease in hydroxyl group that retards reaction. We found that the thermal stability of the prepared ABTTs increased with chlorine content at high temperatures.

Removable protective adhesives for automobiles were synthesized by an emulsion polymerization of monomers such as n-butyl acrylate (BA), n-butyl methacrylate (BMA), acrylonitrile (AN), acrylic acid (AA) and 2-hydroxyethyl methacrylate (2-HEMA), in which AA and 2-HEMA were functional monomers. Potassium persulfate (KPS) was used as an initiator and sodium lauryl sulfate (SLS) was used as an emulsifier, and polyvinyl alcohol (PVA) was used as a stabilizer. Emulsion polymerization was carried out in a semi-batch type reactor. Tensile strength, extension, peel strength, viscosity and solid content of the synthesized adhesives were tested. The optimum physical properties of the removable protective adhesives for automobiles were obtained with the composition of 0.43 mole BA, 0.57 mole AN, 0.21 mole BMA, 0.03 mole AA, and 0.03 mole 2-HEMA.

The natural graphite particles A and heat-treated graphite particles B at 1800 ℃ after pitch-coating were used as the anode base materials for lithium ion secondary battery. In order to improve the performance of anode materials, the base anode materials were treated with various acids. With the acid treatments of 62% HNO3 and 95% H2SO4 aqueous solution, the specific surface area and electrical conductivity of base anode materials were increased, and the initial charge-discharge capacity and cycle performance were improved due to the elimination of structural defects.

Reaction intermediates PCP/BZA (PBI) and tetramethylene bis(orthophosphate)(TBOP) were synthesized from polycaprolactone (PCP) and benzoic acid (BZA) and from pyrophosphoric acid and 1,4-butanediol, respectively. Benzoic acid modified polyesters containing phosphorus (APTB-S, -10, -15) were synthesized by polycondensation of the prepared PBI (containing 5, 10, 15wt% of benzoic acid), TBOP, adipic acid, and 1,4-butanediol. Network structured PU flame-retardant coatings (APHD) were prepared by curing the synthesized benzoic acid modified polyesters containing phosphorus (APT B - 5 , -10, -15) with hexamethylene diisocyanate (HDI)-timer. From the TGA analysis of APTBs, it was found that the afterglow decreased with the amount of BZA content at the high temperatures. With the introduction of BZA, the film viscosity and film hardness of APHD decreased. With the introduction of caprolactone group, the flexibility, impact resistance, accelerated weathering resistance of APTBs increased. Flame retardancy of the coatings was tested. In a vertical burning method, APHD shows 210~313 seconds, which indicates that the coatings are good flame-retardant coatings. Moreover, the amount of afterglow and flame retardancy of the coatings are decreased with increasing BZA content.

Room temperature cure type of acryl-urethane coatings with high solid content were prepared in this study. Acrylic resins with 80% solid content were cured with hexamethylene diisocyanate (Desmodure N-3600). The cure time of prepared coatings BEHCC-84 (BEHC-84 : Tg=0℃) and BEHCC-87 (BEHC-87 : Tg=30℃), measured by rigid-body pendulum method, was recorded 8.3 hours and 3.8 hours, respectively. Dynamic viscoelastic experiment also revealed the glass transition temperature of BEHCC-84 and BEHCC-87 to be Tg=40.3℃ and Tg=43.3℃, respectively. It was found that the adhesion and flexural properties among various propeties of coatings were enhanced by the incorporation of caprolactone acrylate monomer into the acrylic resins.