双酚 A(BPA)作为一种典型的环境内分泌干扰物,因其实现雌激素活性、毒理学效应以及严重的污染情况,在许多国家的众多领域中被限制使用。因此,很多商家纷纷寻找 BPA 的替代品。双酚 S (BPS) 是通过将 BPA 分子结构中的丙烷基替换为砜基而得到的一种衍生物。近年,BPS 作为生产聚碳酸酯、聚酯树脂、聚砜和聚醚酯树脂以及环氧树脂的工业原料,在禁止或限制使用 BPA 的日常用品制造中得到了广泛应用,如食品包装材料、食品罐内衬、奶瓶和纸制品。
毒理学目前,关于双酚 S(BPS)毒理学的研究主要围绕基因毒性、生殖发育毒性以及内分泌干扰效应展开。大量基于不同受体模型的体外试验已经证实 BPS 具有雌激素效应及抗雄性激素效应,其激素效应分别为 BPA 的 32%±28% 和 25%,对淋巴细胞的增值作用也有报道。BPS 在某些毒理效应上甚至比 BPA 更强。Kyunghee 等人的研究表明,将雄性和雌性斑马鱼暴露在 0.5-50ug/L 的 BPS 水样中 21 天后,雌性和雄性斑马鱼血浆中的雌二醇含量显著升高,而雄性斑马鱼血浆中的睾酮含量则显著降低。引起同样的效应,需要将鲤鱼暴露在 1000ug/L 的 BPA 水样中 14 天、幼比目鱼在 59ug/L 的 BPA 水样中暴露 21 天以及热水管接头中的双酚 S。
制备方法(1)双酚S粗品的制备:将苯酚和均三甲苯投入烧瓶内,开启搅拌并升温至100℃。滴加98%浓硫酸,滴完后继续升温回流分水,保温在165℃反应5小时,得双酚S粗品,并回收均三甲苯。
(2)双酚S的精制:向双酚S粗品中依次加入有机溶剂和活性炭,在65℃下脱色1小时。趁热过滤,滤液转入瓶中,再缓慢降温至有晶体析出时降至室温,最后过滤固体,并用少量有机溶液冲洗固体并烘干得产品。
化学性质双酚S是一种白色针状结晶物,熔点为240-241℃。易溶于脂肪烃,溶于醇和醚,微溶于芳烃,难溶于水。该品分子中含两个羟基和一个吸电子很强的砜基,故酸性比其他酚类强。
用途双酚S主要用作固色剂,并可用作镀液添加剂、皮革鞣剂、分散染料高温染色的分散剂、酚醛树脂硬化促进剂,树脂阻燃剂等。也是农药、染料、助剂的中间体,作为 BPA 的代用品,可作为聚碳酸酯、环氧树脂、聚酯、酚醛树脂的原料以及聚砜和聚醚酸树脂的原料。此外,还可用于制造彩色摄影材料、照相反差增强剂、热敏记录材料(显色剂)、日用表面活性剂和高效除臭剂等。
生产方法双酚 S 由苯酚与硫酸反应而得。
中文名称 | 英文名称 | CAS号 | 化学式 | 分子量 |
---|---|---|---|---|
—— | bis(p-anisyl)sulfone | 3112-80-9 | C14H14O4S | 278.329 |
4,4’-二羟基二苯亚砜 | bis(4-hydroxyphenyl) sulfoxide | 1774-34-1 | C12H10O3S | 234.276 |
—— | bis-(4-ethoxy-phenyl)-sulfone | 66294-58-4 | C16H18O4S | 306.383 |
4,4'-二甲氧基二苯基氧化硫 | bis(4-methoxyphenyl) sulfoxide | 1774-36-3 | C14H14O3S | 262.329 |
4,4'-磺酰基二(苯酚)二乙酸酯 | 4,4'-diacetoxydiphenylsulfone | 5456-51-9 | C16H14O6S | 334.35 |
2,4-二羟基二苯砜 | 2,4'-dihydroxydiphenyl sulfone | 5397-34-2 | C12H10O4S | 250.275 |
—— | bis-(4-ethoxy-phenyl)-sulfoxide | —— | C16H18O3S | 290.383 |
4,4'-二氟二苯砜 | 4-fluorophenyl sulfone | 383-29-9 | C12H8F2O2S | 254.257 |
4,4'-二氯二苯砜 | 4,4'-dichlorodiphenyl sulphone | 80-07-9 | C12H8Cl2O2S | 287.166 |
氨苯砜 | dapsone | 80-08-0 | C12H12N2O2S | 248.305 |
4,4-磺酰二(2-甲基苯酚) | bis[3-methyl-4-hydroxyphenyl]sulfone | 16346-97-7 | C14H14O4S | 278.329 |
—— | sulfinylbis(4,1-phenylene) diacetate | 47225-87-6 | C16H14O5S | 318.35 |
4,4'-二羟基二苯硫醚 | 4,4'-Thiodiphenol | 2664-63-3 | C12H10O2S | 218.276 |
—— | 4,4'-sulfonyl-di-benzoic acid diamide | 14052-63-2 | C14H12N2O4S | 304.326 |
—— | 4,4′-sulfonyldibenzoyldichloride | 4462-61-7 | C14H8Cl2O4S | 343.187 |
中文名称 | 英文名称 | CAS号 | 化学式 | 分子量 |
---|---|---|---|---|
—— | bis(p-anisyl)sulfone | 3112-80-9 | C14H14O4S | 278.329 |
—— | 4-((4′-methoxyphenyl)sulfonyl)phenol | 98116-80-4 | C13H12O4S | 264.302 |
—— | bis-(4-ethoxy-phenyl)-sulfone | 66294-58-4 | C16H18O4S | 306.383 |
二[4-(2-羟基乙氧基)苯基]砜 | bis[4-(2-hydroxyethoxy)phenyl]sulfone | 27205-03-4 | C16H18O6S | 338.381 |
—— | bis-(4-propoxy-phenyl)-sulfone | 97042-12-1 | C18H22O4S | 334.436 |
二苯砜 | Diphenyl sulfone | 127-63-9 | C12H10O2S | 218.276 |
4-羟基-4'-异丙氧基二苯砜 | 4-hydroxy-4'-isopropoxydiphenylsulfone | 95235-30-6 | C15H16O4S | 292.356 |
1,1'-砜基双[4-(2-丙烯)氧基苯] | 4,4'-diallyloxydiphenyl sulfone | 41481-63-4 | C18H18O4S | 330.405 |
4-((4-(烯丙氧基)苯基)磺酰基)苯酚 | 4-allyloxy-4'-hydroxydiphenyl-sulfone | 97042-18-7 | C15H14O4S | 290.34 |
—— | 4,4'-Di-(trimethylsilylhydroxy)-diphenylsulfon | 71918-64-4 | C18H26O4SSi2 | 394.639 |
—— | bis-(4-butoxy-phenyl)-sulfone | 95210-59-6 | C20H26O4S | 362.49 |
—— | bis-(4-pentyloxy-phenyl)-sulfone | 95210-60-9 | C22H30O4S | 390.544 |
4,4'-磺酰基二(苯酚)二乙酸酯 | 4,4'-diacetoxydiphenylsulfone | 5456-51-9 | C16H14O6S | 334.35 |
—— | bis-(4-isopentyloxy-phenyl)-sulfone | 97042-13-2 | C22H30O4S | 390.544 |
—— | 4-(4-acetoxy-benzenesulfonyl)-phenol | 114433-13-5 | C14H12O5S | 292.312 |
1H-吲哚,1-[(4,5-二氢-1H-咪唑-2-基)甲基]-3-甲基- | 1,1'-[((sulfonylbis(4,1-phenylene))bis(oxy))bispropan-2-ol] | 50326-38-0 | C18H22O6S | 366.435 |
—— | 4-[[4-(2-Hydroxypropoxy)phenyl]sulfonyl]phenol | 97042-19-8 | C15H16O5S | 308.4 |
—— | 2,2'-bis[4-(4-hydroxyphenylsulfonyl)phenyloxy]diethylether | 29239-85-8 | C28H26O9S2 | 570.641 |
—— | 2,2'-(4,4'-sulfonylbis(4,1-phenylene)bis(oxy))bis(N,N-dimethylethanamine) | 1429763-74-5 | C20H28N2O4S | 392.519 |
—— | 1-Hexoxy-4-(4-hexoxyphenyl)sulfonylbenzene | —— | C24H34O4S | 418.6 |
4,4'-双(4-氨基苯氧基)二苯砜 | bis[4-(4-aminophenoxy)phenyl]sulfone | 13080-89-2 | C24H20N2O4S | 432.5 |
—— | bis-(4-carboxymethoxy-phenyl)-sulfone | 30596-06-6 | C16H14O8S | 366.348 |
—— | 1-Heptoxy-4-(4-heptoxyphenyl)sulfonylbenzene | —— | C26H38O4S | 446.6 |
—— | 2-[4-[4-(2-Chloro-2-oxoethoxy)phenyl]sulfonylphenoxy]acetyl chloride | 30625-15-1 | C16H12Cl2O6S | 403.24 |
—— | 1-Decoxy-4-(4-decoxyphenyl)sulfonylbenzene | —— | C32H50O4S | 530.8 |
—— | [4-(4-Phenoxycarbonyloxyphenyl)sulfonylphenyl] phenyl carbonate | 90745-50-9 | C26H18O8S | 490.49 |
2,4-二羟基二苯砜 | 2,4'-dihydroxydiphenyl sulfone | 5397-34-2 | C12H10O4S | 250.275 |
—— | 4,4'-sulfonylbis(4,1-phenylene) disulfofluoridate | 42158-98-5 | C12H8F2O8S3 | 414.386 |
—— | methyl 4-(4-hydroxyphenylsulfonyl)phenoxyacetate | 688317-01-3 | C15H14O6S | 322.339 |
—— | 4-(4-hydroxyphenyl)-4'-hydroxydiphenyl sulfone | 157689-62-8 | C18H14O4S | 326.373 |
—— | 4,4'-sulfonyldiphenyl dipropiolate | 117583-47-8 | C18H10O6S | 354.34 |
双(3-氨基-4-羟苯基)砜 | bis(3-amino-4-hydroxyphenyl)sulfone | 7545-50-8 | C12H12N2O4S | 280.304 |
—— | bis-[4-(2,3-epoxy-propoxy)-phenyl]-sulfone | 3878-43-1 | C18H18O6S | 362.403 |
—— | 4,4'-bis-(3-bromophenoxy)diphenyl sulfone | 79915-96-1 | C24H16Br2O4S | 560.263 |
4,4'-二氟二苯砜 | 4-fluorophenyl sulfone | 383-29-9 | C12H8F2O2S | 254.257 |
—— | p,p'-bis(hydrazinocarbonylmethoxy)diphenyl sulphone | 65328-81-6 | C16H18N4O6S | 394.408 |
4-氯二苯砜 | 4-Chlorophenyl phenyl sulfone | 80-00-2 | C12H9ClO2S | 252.721 |
4,4'-二氯二苯砜 | 4,4'-dichlorodiphenyl sulphone | 80-07-9 | C12H8Cl2O2S | 287.166 |
二(4-苄基氧基苯基)砜 | 4,4'-sulfonylbis((benzyloxy)benzene) | 71338-01-7 | C26H22O4S | 430.524 |
4-羟基-4'-苄氧基二苯砜 | 4-benzyloxyphenyl-4-hydroxyphenyl sulfone | 63134-33-8 | C19H16O4S | 340.4 |
氨苯砜 | dapsone | 80-08-0 | C12H12N2O2S | 248.305 |
4-(苯基磺酰基)苯胺 | 4-(phenylsulfonyl)aniline | 7019-01-4 | C12H11NO2S | 233.291 |
—— | diethyl 2,2'-(sulfonylbis(4,1-phenylene)bis(oxy))diacetate | 38775-52-9 | C20H22O8S | 422.456 |
二(3-氯-4-羟基苯基)砜 | bis(4-hydroxy-3-chlorophenyl)sulfone | 46947-87-9 | C12H8Cl2O4S | 319.165 |
—— | 1,1'-(2,2'-(4,4'-sulfonylbis(1,4-phenylene)bis(oxy))bis(ethane-1,2-diyl))-dipiperidine | 120639-07-8 | C26H36N2O4S | 472.649 |
—— | bis-(4-allyloxycarbonyloxy-phenyl)-sulfone | 129080-27-9 | C20H18O8S | 418.424 |
—— | bis(p-(3-butoxy-2-hydroxypropyloxy)phenyl)sulphone | 77246-71-0 | C26H38O8S | 510.649 |
四溴双酚S | tetrabromobisphenol S | 39635-79-5 | C12H6Br4O4S | 565.859 |
—— | (4,4'-sulfonylbis(4,1-phenylene)bis(oxy))bis(tert-butyldimethylsilane) | 154116-76-4 | C24H38O4SSi2 | 478.8 |
—— | Bis(4-propargyloxycarbonyloxyphenyl)sulfone | 139226-78-1 | C20H14O8S | 414.392 |
四氯双酚S | Bis-<3.5-dichlor-4-hydroxy-phenyl>-sulfon, 2.6.2'.6'-Tetrachlor-4.4'-sulfonyl-di-phenol | 30609-79-1 | C12H6Cl4O4S | 388.055 |
—— | 4-(4-hydroxyphenylsulfonyl)phenoxyacetic acid diethylamide | 688317-09-1 | C18H21NO5S | 363.434 |
—— | bis[4-(tert-butoxycarbonyloxy)phenyl]sulfone | 129104-70-7 | C22H26O8S | 450.51 |
—— | 5-[4-[4-(4-Carboxy-4-methylpentoxy)phenyl]sulfonylphenoxy]-2,2-dimethylpentanoic acid | 85629-87-4 | C26H34O8S | 506.617 |
—— | Benzene, 1,1'-sulfonylbis[4-(4-nitrophenoxy)- | 27594-94-1 | C24H16N2O8S | 492.466 |
—— | bis-4-trifluoromethanesulfonyloxyphenylsulfone | 17763-90-5 | C14H8F6O8S3 | 514.401 |
—— | 4-(4-hydroxyphenylsulfonyl)phenyl trifluoromethanesulfonate | 1349856-56-9 | C13H9F3O6S2 | 382.338 |
—— | 3,3'-Dichlor-4,4'-dimethoxy-diphenylsulfon | 66294-54-0 | C14H12Cl2O4S | 347.219 |
—— | 4,4''-sulfonyldi-1,1'-biphenyl | 19942-80-4 | C24H18O2S | 370.472 |
—— | 4-(4-(2-hydroxyethyloxy)phenyl)-4'-(2-hydroxyethyloxy)diphenyl sulfone | —— | C22H22O6S | 414.479 |
—— | bis-(4-benzenesulfonyloxy-phenyl)-sulfone | 59707-18-5 | C24H18O8S3 | 530.6 |
—— | 4-(4-benzenesulfonyloxy-benzenesulfonyl)-phenol | 98281-81-3 | C18H14O6S2 | 390.438 |
—— | 4,4'-Dihydroxy-3,3'-dihydroxymethyl-diphenyl-sulfon | 2761-12-8 | C14H14O6S | 310.328 |
—— | 6-methoxy-2,4-di[4-(4-hydroxy-phenylsulfonyl)phenoxy]-1,3,5-triazine | —— | C28H21N3O9S2 | 607.621 |
—— | 4-(4-benzoyloxy-benzenesulfonyl)-phenol | 33123-51-2 | C19H14O5S | 354.383 |
—— | bis-(4-benzoyloxy-phenyl)-sulfone | 58849-83-5 | C26H18O6S | 458.491 |
—— | 4-(4-(2-hydroxyethylthio)phenyl)-4'-(2-hydroxyethyloxy)diphenyl sulfone | 1360864-23-8 | C22H22O5S2 | 430.546 |
—— | 4,4'-dihydroxydiphenylsulfonebis(4-carbomethoxybenzyl) ether | 64965-81-7 | C30H26O8S | 546.598 |
—— | bis-(4-trans-cinnamoyloxy-phenyl)-sulfone | 121600-58-6 | C30H22O6S | 510.567 |
N-[4-(4-乙酰氨基苯基)磺酰基苯基]乙酰胺 | acedapsone | 77-46-3 | C16H16N2O4S | 332.38 |
—— | 4,4'-Bis-(3,4-dicyanophenoxy)diphenylsulfon | 38791-70-7 | C28H14N4O4S | 502.51 |
—— | [4-[4-(Pyridine-4-carbonyloxy)phenyl]sulfonylphenyl] pyridine-4-carboxylate | —— | C24H16N2O6S | 460.467 |