CAJ | 학술논문

以苯基磷酰二氯和乙二醇为原料合成了苯基磷酸二(乙二醇)酯(BHEPP),将其与1,2-丙二醇、顺丁烯二酸酐和邻苯二甲酸酐共聚,得到了反应型含磷阻燃不饱和聚酯(P-UPR).当P-UPR固化物中磷的质量分数为2.66%时,固化产物的极限氧指数为29,阻燃效果达到UL94 V-0级.热重分析结果表明,当反应单体中BHEPP的质量分数由0增至35%时,固化后的P-UPR在氮气和空气气氛中的起始分解温度分别下降了32.2 ℃和63.9 ℃,最大热分解温度分别下降了52.3 ℃和54.0 ℃.用示差扫描量热分析仪测试了P-UPR的非等温固化过程,根据Kamal模型计算转化率(α)和时间的关系曲线,当0.1<α<0.8时,固化反应由动力学控制;当α>0.8时,固化反应由扩散效应控制,在固化过程初期,无固化延迟效应.
이분기린선이록화을이순위원료합성료분기린산이(을이순)지(BHEPP),장기여1,2-병이순、순정희이산항화린분이갑산항공취,득도료반응형함린조연불포화취지(P-UPR).당P-UPR고화물중린적질량분수위2.66%시,고화산물적겁한양지수위29,조연효과체도UL94 V-0급.열중분석결과표명,당반응단체중BHEPP적질량분수유0증지35%시,고화후적P-UPR재담기화공기기분중적기시분해온도분별하강료32.2 ℃화63.9 ℃,최대열분해온도분별하강료52.3 ℃화54.0 ℃.용시차소묘량열분석의측시료P-UPR적비등온고화과정,근거Kamal모형계산전화솔(α)화시간적관계곡선,당0.1<α<0.8시,고화반응유동역학공제;당α>0.8시,고화반응유확산효응공제,재고화과정초기,무고화연지효응.
A reactive flame-retardant phosphorus-containing unsaturated polyester resin(P-UPR) was prepared by polycondensation of maleic anhydride, phthalic anhydride, propylene glycol and bis(hydroxyethyl)phenylphosphonate(BHEPP). The latter was synthesized from phenyl phosphonic dichloride and ethylene glycol. The specifications of UL94 V-0 rating and limiting oxygen index of 29 were achieved when mass fraction of phophorus was 2.66% (based on the P-UPR mass) in the cured P-UPR. The TGA results showed that with the increase of BHEPP mass fraction(based on total mass of monomers) from 0 to 35%, the initial decomposition temperature of cured P-UPR lowered by 32.2 ℃ in N2 and 63.9 ℃ in air, and the maximum decomposition temperature lowered by 52.3 ℃ in N2 and 54.0 ℃ in air. The non-isothermal curing behavior of P-UPR was studied by DSC. According to the plot of conversion (α) versus time calculated by Kamal's equation, the curing process of UPR was controlled by kinetics with 0.1<α<0.8 and by diffusion with α> 0.8. No delay effect appeared in the initial curing stage.