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.
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.
Na2CO3. Sodium orthosilicate (Na-OSi), Tetronix T-701 (T-701), Na-dioctyl sulfosuccinate (303C), Newpol PE-68 (PE-68), MJU-100A, and tetrasodium pyrophosphate were blended to prepare high performance alkaline cleaning agents (ACASs). The results of cleaning test with steel specimen showed that ACAS-6 (Na2CO3 50g/Na-OSi 35g/T-701 20g/303C 18g/PE-68 17g/MJU-100A 10g/TSPP 20g/ water 180g mixture) had a good cleaning power. The cleaning power for press-rust preventing oil was 98% and 99% degreasing at 4wt%, 70℃ and 90℃, respectively ; for quenching oil, the cleaning power of ACAS-6 was 91% degreasing at 4wt% and 70℃. The foam heights measured immediately after foaming by Ross & Miles method and Ross & Clark method at 6wt%, 60℃ were 18mm and 65mm, respectively. It was concluded that ACAS-6 had a good low foaming cleaning agent.
High-solid coatings were prepared by blending of previosly synthesized acrylic resins and hexamethylene diisocyanate-trimer and curing it at room temperature. The characterization of the films of the prepared coatings was performed. The impact resistance, cross-hatch adhesion, 60˚specular gloss, and heat resistance of the films proved to be good, and the pencil hardness and drying time proved to be slightly poor. Especially, there was a remarkable improvement in the heat resistance. This improvement may stem from the regular arrangement of ethyl groups introduced into the acrylic resin. As a result of Rigid-body pendulum visco-elasticity measurement, dynamic Tg values of cured films increased with dynamic Tg values.
Acrylic resins (HSCs : EA/EMA/2-HEMA/CLA) which contain 70% solid content were synthesized by the copolymerization of monomers (2-hydroxyethyl methacrylate, ethyl acrylate, and ethyl 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 245~515 cps ; Mn 2670~2840 ; and conversions, 83~91%, respectively. From the correlation of Tg values, viscosities, and Mn of the HSCs, it was found that viscosity and Mn increased with Tg value.
An emulsion of octadecamidoethylaminoethyl dodecate (which provides softness) and an emulsion silicone oil KF-96 (which provides lubricity) were separately synthesized. Then PP finishing softeners (SSA-7) was prepared by blending of the synthesized emulsions with beef tallow hardened oil (a softness improving agent). PP finishing treatment was carried out with the prepared SSA-7 and PP finishing resin by a one bath method, and several physical properties were tested. As a result, crease recovery, tear strength, softness, lubricity, and bending resistance were all good, indicating that the prepared SSA-7 is a good PP finishing softener.
PU flame-retardant coatings (APHD) containing phosphorous were prepared by blending of hexamethylene diisocyanate-trimer, white pigment, dispersing agent, flowing agent, and previously prepared benzoic acid modified polyester (APTB) that contains phosphorous. Physical properties of the prepared APHD were examined. With the introduction of BZA (contained in APTB), 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, and in a 45˚ Meckel burner method, shows 1.3~4.0cm2 of char length, 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.
Reaction intermediates PCP/BZA (PBI) and tetramethylene bis(orthophosphate) (TBOP) wer synthesized from polycaprolactone (PCP) and benzoic acid (BZA) and from pyrophosphoric acid and 1,4-butanediol, respectively. Benzoic acid modified polyesters containing phosphorus (APTB-5, -10, -15) were synthesized by polycondensation of the prepared PBI (containing 5, 10, 15wt% of benzoic acid), TBOP, adipic acid, and 1,4-butanediol. The structure and characteristics of APTBs were examined using FT-IR, NMR, GPC, and TGA analysis. The increase of the amount of BZA in the synthesis of APTBs resulted in decrease in average molecular weight and kinematic viscosity. From the TGA analysis of APTBs, it was found that the afterglow decreased with the amount of BZA content at the high temperatures.
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 impact resistance, 60℃ specular gloss, cross-hatch adhension, and heat resistance of the films proved to be good, and the pencil hardness and drying time proved to be slightly poor. Especially, there was a remarkable improvement in the heat resistance. This improvement may stem from the regular arrangement of ethyl groups introduced into the acrylic resin. From a viscoelastic measurement using a rigid-body pendulum, curing was accelerated with the Tg value. With the increase in Tg, log damp value was lowered and dynamic viscoelasic Tg of a cured film was increased.
A copolymer 〈HSAs : EA/EMA/2-HEMA/AAEM) which is an acrylic resin containing 70% solid content was synthesized by the reaction of monomers, including ethyl acrylate, ethyl methacrylate, and 2-hydroxyethyl methacrylate with a functional monomer, such as acetoacetoxyethyl methacrylate, which may give improvements in cross-linking density and physical properties of films. The physical properties of prepared acrylic resins, HSA containing AAEM, are as follows : viscosity, 203~550cps ; Mn, 2590~2850 ; and conversion, 82~89%, respectively. It was found from the plotting of Tg versus viscosity and Tg versus molecular weight that viscosity increased with Tg while number averaged molecular weight decreased with increasing Tg.