新型不饱和橡胶氯化剂的合成与表征

以次氯酸钠、叔丁醇和冰乙酸为原料合成了次氯酸叔丁酯。考察了反应温度、反应物配比、投料方式对产物的收率及纯度的影响以及放置时间对贮存稳定性的影响,确定了次氯酸叔丁酯合成的工艺条件,并用色谱-质谱对其纯度、杂质含量及产物结构进行了表征。结果表明,产物中次氯酸叔丁酯的质量分数可达92％,其纯度随放置时间的延长降低,杂质叔丁醇含量增加。将氯化试剂用于镍系顺丁橡胶的氯化反应,氯化反应为加成反应,氯化程度可控而且氯化顺丁橡胶的凝胶质量分数可控制在5％以下。     

氯酯化顺丁橡胶及其并用胶的性能研究

将BR原胶液经甲苯稀释后与次氯酸叔丁酯和苯甲酸进行氯化反应,制备氯酯化顺丁橡胶(CEBR),研究不同硫化体系对CEBR性能的影响以及CEBR/BR和CEBR/SSBR并用胶的物理性能.结果表明,促进剂CZ可有效促进CEBR的硫化;CEBR/BR并用比为50/50时,硫化胶综合物理性能较好;当并用胶中CEBR用量相同时,CEBR/SSBR并用胶与CEBR/BR并用胶相比,t90缩短.拉伸强度增大.     

氯化顺丁橡胶基本性能的研究

试验考察新型改性橡胶氯化顺丁橡胶(CBR)的基本性能。CBR的门尼粘度和玻璃化温度随氯含量的增大而升高;CBR的混炼性能优于BR和CR,硫化速度低于BR但高于CR,焦烧时间长于BR和CR,且随氯含量的增大而延长;CBR硫化胶的物理性能和耐热空气老化性能均明显优于BR,且氯含量越大,改善越明显;CBR的耐油性能不如CR和NBR,但比BR明显提高,可以在耐油要求不太苛刻的制品中使用;CBR的阻燃性能虽不如CR,但氯质量分数为0 35的CBR已属于难燃聚合物,可用于阻燃制品。     

氯酯化顺T橡胶的基本性能

将顺丁橡胶胶液与次氯酸叔丁酯及甲酸反应,制得了舍氯和酯侧基的氯酯化顺丁橡胶(CEBR).研究了CEBR生胶的热稳定性能、玻璃化转变温度及门尼黏度,并测定了其硫化胶的力学性能.结果表明,随着结合氯质量分数的提高,CEBR的热稳定性逐渐降低,门尼黏度和玻璃化转变温度上升;CEBR的硫化速率低于顺丁橡胶,且结合氯质量分数越高,硫化速率就越小.必须使用超速硫化促进剂;氯和酯侧基的引入提高了分子的极性,破坏了分子链的规整性,CEBR为非结晶性橡胶;随着结合氯质量分数的增加,CEBR硫化胶的拉伸强度和耐油性提高,且用20份和50份炭黑增强CEBR.当氯的质量分数为3%时,CEBR硫化胶的扯断伸长率可达200%以上.     

氯乙酸尾气的治理与利用

在醋酸氯化法生产氯乙酸的过程中,每生产一吨氯乙酸(以100％计)就有386公斤的氯化氢气体生成。如直接排入大气,势必造成坏境污染。氯乙酸尾气除含有80—90％的HC1气体外,还含有氯化硫、乙酰氯、醋酸和游离氯     

氯丙烯的衍生物及其应用

氯丙烯是一种重要的化工中间体,主要用于树脂、药物、甘油和精细化工的生产。氯丙烯由于双键和氯原子的存在而变得很活泼,氯丙烯通过双键加成和氯原子上的反应可以得到各种衍生物。本文介绍氯丙烯及其衍生物在化工中的应用。     

ATRP法合成大分子单体及其在微球制备中的应用

以α-溴代丙酸乙酯(EPN-Br)为引发剂,氯化亚铜(CuCl)与N,N,N′,N″,N″-五甲基二亚乙基三胺(PMDETA)组成的混合体系为催化剂,使甲基丙烯酸叔丁酯(tBMA)进行原子转移自由基聚合(ATRP),得到了端基为溴原子的聚甲基丙烯酸叔丁酯大分子中间体PtBMA-Br。使其末端的Br与甲基丙烯酸发生亲核取代反应,得到甲基丙烯酸封端的大分子单体。FTIR和1H-NMR的分析表明大分子单体结构明确,双键导入率高;再用该大分子单体与苯乙烯分散共聚制得形态规整的高分子微球。     

硝苯柳胺合成方法的研究

研究了硝苯柳胺的三种合成方法 ,分析了其影响因素 ,比较了其优缺点并提出了各自的适用范围。其中氯气氯代法可在一个反应器内进行 ,不需分离中间体 ,收率可达 90 % ;次氯酸叔丁酯对水杨酸的氯代有很强的区域专一性反应特性 ,用其作为氯代剂合成硝苯柳胺收率为 81% ,产品纯度 97 9% ;用对硝基苯胺与二氯亚矾在吡啶存在下生成亚硫酰胺 ,再与 5 氯水杨酸反应合成硝苯柳胺 ,收率为 78% ,纯度可达 99%     

氯化聚乙烯应用一例

氯化聚乙烯故名思意就是让氯原子取代了聚乙烯分子中氢原子,而且使氯原子的含量达到25％～46％（通常为35％左右）时,就会由典型PE塑料变成高弹性体CM了。     

催化体系对稀土顺丁橡胶聚合反应和胶料性能的影响

研究催化体系对稀土(钕系)顺丁橡胶(Nd BR)聚合反应和胶料性能的影响。催化体系的优化组成为:新癸酸钕(NdV_3)作主催化剂,二异丁基氢化铝(简称铝剂)作还原剂,氯化二异丁基铝(简称氯剂)作路易斯酸;优化配制工艺为:在NdV_3中先加铝剂再加氯剂,聚合反应时丁二烯和催化体系3个组分陈化液一起加入;优化配合为:在100g丁二烯中n(NdV_3)为(1.36~1.58)×10^(-4)mol,n(NdV_3)/n(铝剂)/n(氯剂)为1/22/(1.71~2);适合的陈化时间为4~64 h。采用优化催化体系聚合的产品收率大于98%,制备的Nd BR顺式-1,4-结构质量分数大于0.98,生胶门尼粘度[ML(1+4)100℃]为45±5,胶料加工性能和物理性能与朗盛NdBR胶料相当,优于BR9000胶料。     

甲苯选择性氯化合成对氯甲苯

综述了国内外甲苯选择性氯化合成对氯甲苯的研究情况，介绍了用氯气、含氯有机化合物和无机氯化物作氯化剂氯化的各种氯化方法，重点介绍了路易斯酸催化剂和含硫助催化剂的催化体系和沸石分子筛催化剂体系，并评价了有关的方法。     

Oxidation and halogenation of jojoba wax

The oxidation with hydrogen peroxide and permanganate and the allylic bromination, chlorination and chloro-etherification of the olefinic bonds of the liquid wax extracted from beans of jojoba (Simmondsia chinensis) were studied. Hydrolytic splitting of the wax into its carboxylic and alcoholic components competed with most reactions carried out in aqueous systems. The use of a suitable phase-transfer catalyst enabled the oxidation of the double bonds to carboxyls using permanganate in aqueous systems. Reaction of the wax with hydrogen peroxide in formic acid yielded formates, which were then hydrolyzed to vicinal glycols. The diglycols obtained by hydrogen peroxide oxidation were benzoylated. Allylic chlorination of jojoba wax with t-butyl hypochlorite in organic solvents was carried out. Conditions were found for the allylic bromination of the wax, yielding mono-, di-, tetra-, or octabromo derivatives.     

甲苯选择性氯化合成对氯甲苯

综述了国内外甲苯选择性氯化合成对氯甲苯的研究情况,介绍了用氯气、含氯有机化合物和无机氯化物作氯化剂氯化的各种氯化方法,重点介绍了路易斯酸催化剂和含硫助催化剂的催化体系和沸石分子筛催化剂体系,并评价了有关的方法。     

对甲苯磺酰氯的合成研究

以甲苯为原料合成了对甲苯磺酰氯。在磺化反应中,采用共沸除水硫酸磺化法。在氯化反应中,以四氯化碳为溶剂,氯气为氯化剂。该工艺硫酸利用率高,生产成本低。     

氯乙酰氯的开发与应用

介绍了氯乙酰按的应用及以氯乙酸为原料，用氯气，一氯化硫进行氯化反应，经萃取，精馏制取高纯氯乙酰氯的生产技术。     

Soy fatty acid oxidation with sodium hypochlorite monitored by nuclear magnetic resonance spectroscopy

The oxidation process of soy fatty acids by sodium hypochlorite with ruthenium trichloride catalyst was examined at different temperatures and active chlorine:fatty acid molar ratios. ¹H and ¹³C distortionless enhancement by polarized transfer nuclear magnetic resonance (NMR) spectroscopy techniques were used to monitor oxidation of the double bonds in unsaturated lipids by measuring the peak integration ratio of double-bond peaks:methylene-methyl peaks. This NMR monitoring technique proved to be an excellent means to quantify double-bond reactions. Gas chromatography-mass spectrometry was used to identify mono- and diacid products, separated by hexane/methylene chloride extraction, as well as other oxidation products. While the presence of ruthenium catalyst increased the initial rate of oxidation, it also catalyzed the decomposition of hypochlorite, decreasing the available reactive chlorine, resulting in a delay in complete oxidation. A 9:1 molar ratio of active chlorine to fatty acids completely oxidized all double bonds of soy fatty acids. However, the yield of low-molecular-weight monoacid oxidation products was only 17%, indicating the probable formation of hydroxy fatty acids.     

3,5-二氯-2-戊酮的合成

α-乙酰基-α-氯-γ-丁内酯在热的盐酸介质中经开环脱羧和亲核氯代反应合成了3,5-二氯-2-戊酮。用无水三氯化铝作催化剂,浓盐酸作氯代剂,正庚烷作氯代反应的带水剂,反应温度95~100℃,反应时间4 h,用一锅法完成了目标物的制备,工艺简单,且显著提高了伯醇氯代反应的收率,总收率达到58.8%。用气质联用和红外光谱对产品结构进行了表征。     

Water-based chlorination treatment of SBS rubber soles to improve their adhesion to waterborne polyurethane adhesives in the footwear industry

Solutions of trichloroisocyanuric acid (TCI) in different organic solvents are commonly employed in the footwear industry to improve the adhesion of SBS (styrene-butadiene-styrene) rubber soles to polyurethane adhesive. To avoid the use of organic solvents in the chlorinating solutions, several water-based chlorinating treatments were investigated in this study: (i) inorganic chlorine compounds (HCl-acidified sodium hypochlorite solution; free active chlorine (FAC) = 47.8 g/l); (ii) organic chlorine donors (aqueous solution of 3 wt% TCI/H₂O, and ethanol solutions of 3 wt% HD (1,3-dichloro-5,5-dimethylhydantoine), or NCS (N-chlorosuccinimide); (iii) organic chlorine donor salts (aqueous solutions containing 3 wt% DCI (sodium dichloro isocyanurate), CB (chloramine B, N-chloro-sodium-phenylsulphenamide), or CT (chloramine T, N-chloro-sodium-p-toluenesulphenamide). The surface modifications produced by treatment of SBS rubber with the aqueous chlorinating agents were compared with those obtained by using the current solvent-based chlorinating treatment (3 wt% TCI/MEK). The FAC concentration and the chlorine stability in the solutions were determined by iodine titration, and the SBS rubber surface pH was determined with a flat pH probe. The surface modifications on the SBS rubber were analyzed by ATR-IR spectroscopy, XPS, contact-angle measurements and SEM. The adhesion properties were evaluated by T-peel strength tests on treated SBS rubber/waterborne polyurethane adhesive/roughened leather joints. The failed surfaces obtained after peel tests were analyzed by ATR-IR spectroscopy to precisely assess the locus of failure of the adhesive joints. The nature of the modifications produced on the SBS rubber surface depended on the chlorinating system used, the SBS rubber surface pH value, and the free active chlorine concentration of the chlorinating solution. The most effective chlorinating agents were TCI/H₂O and HD/EtOH, but they were not stable over time due to quick chlorine evolution. Treatment with NaClO/HCl and DCI/H₂O provided acceptable adhesive strength values although there was fast chlorine evolution in the NaClO/HCl solution; the free active chlorine concentration in the DCI/H₂O solution was stable for at least 4 days after preparation. Finally, the treatment with NCS/EtOH, CB/H₂O and CT/H₂O did not chemically modify the SBS rubber surface, so the adhesion to polyurethane adhesive was not improved.     

PAN/AN-co-ADMH共混纤维的氯化漂洗处理

采用聚丙烯腈(PAN)与丙烯腈(AN)/3-烯丙基-5,5-二甲基乙内酰脲(ADMH)共聚物共混湿法纺丝制备了PAN/AN-co-ADMH共混纤维,用质量分数1%的次氯酸钠溶液对共混纤维进行了漂洗处理,探讨了氯漂条件对共混纤维氯含量的影响,考察了氯漂处理后的共混纤维的耐洗涤性及再生性。结果表明:随漂洗液温度升高和氯化漂洗时间增加,共混纤维中氯含量增加;漂洗时间继续增加,纤维氯含量增势变缓;纤维氯含量随洗涤次数或漂洗次数增加均减少。     

氯乙酸的合成工艺

实验以二氯亚砜为催化剂,同时通氯气和氧气氯化乙酸得到氯乙酸。研究了催化剂种类及用量、反应温度、氯化深度以及助催化剂用量等因素对收率的影响,结果表明该反应最优工艺条件为:反应温度在110℃;乙酸与二氯亚砜摩尔比为10:1;氯气与氧气通速比为2:1,按此工艺反应主产物含量99.5%,经处理后产率96.5%。