16单元丁苯橡胶.ppt

1、UNITUNIT 1616 Styrene-Styrene-Butadiene CopolymerButadiene Copolymer丁二烯-苯乙烯共聚物组员：夏毓霜，武文美，王晶晶简介简介丁苯橡胶（ Styrene-Butadiene Copolymer ），简称SBR.最早工业化的合成橡胶之一由丁二烯和苯乙烯两种单体共聚而得到的弹性体为浅黄褐色弹性固体一种综合性能较好的通用型合成橡胶合成橡胶中产量最大的一个品种，约占整个合成橡胶产量的60%发展史发展史发展史高温丁苯橡胶20世纪50年代生产了5摄氏度下聚合的低温丁苯橡胶20世纪60年代初以烷基锂为引发剂用溶液聚合法制备1933年德国首先用

2、乙炔为原料制得丁苯橡胶1942年美国以石油为原料生产丁苯橡胶分类分类应用应用主要用于制作轮胎Words and ExpressionsWords and Expressionstread tred n.;v 踩，踏Recipe respi n. 配方N-dodecyl mercaptan 正十二烷基硫醇Potassium peroxydisulfate 过硫酸钾Flake flek n. 薄片Short-stop n. 终止剂Hydroquinone hadrkwnn n. 对苯二酚Quench kwent v. 熄灭，抑制Flash distillation n. 闪蒸Antioxidant

3、 ntiksdn n.抗氧剂 Phenyl fenl n.苯基Naphthylamine nflemn n.萘胺Latex leteks n.胶乳，乳液Coagulate kgjulet v. 凝聚Brine bran n.盐水Sulfuric acid n. 硫酸Crumb krm n. 碎屑，团粒Bale bel v. 打包Abnormal bn:ml a.反常的Extender kstend n. 添加物剂，增量剂sacrifice skrfas v.牺牲，损失 lighter-colored 浅色的 dithiocarbamate daaok:bmet n. 二硫代氨基甲酸盐 Chai

4、n-transfer agent 链转移剂 Objectionable a. 反对的，使人不愉快的 Dimethydithiocarbamate n. 二甲基二硫代氨基甲酸盐 Sodium sodim n. 钠 Tert-dodecyl mercaptan n. 特十二烷基硫醇 Diisopropylbenzene n. 二异丙苯 Ferrous sulfate heptahydrate n. 硫酸亚铁七水合物 Pyrophosphate parfsfet n.焦磷酸盐 Aluminum sulfate n.硫酸铝 Ethylenediaminetetraacetate n.乙二胺四乙酸盐 D

5、ece- 构十 Tetra- 构四 Formaldehyde f:rmldhad n.甲醛 Sulfoxylate slfkslet n.次硫酸盐 Rosin acid n.松香酸 Dissociation dsosien n.分裂、分离、离解 Persulfate pslfet n.过硫酸盐 Menthane menen n.薄荷烷 Redox ridks n.氧化还原作用The synthetic rubber industry, based on the free-The synthetic rubber industry, based on the free-radical emuls

6、ion process, was created radical emulsion process, was created almostovernight during World War II.almostovernight during World War II. Styrene-Styrene-butadiene (GR-S) rubber crated at that time gives butadiene (GR-S) rubber crated at that time gives such good tire such good tire treads treads that

7、 natural rubber has never that natural rubber has never regained this marketregained this market. . 合成橡胶工业，以自由基乳液过程为基础，在第二次世界大战期间几乎很快地形成。那时，丁苯橡胶制造的轮胎性能相当优越，使天然橡胶在市场黯然失色。 混合物在搅拌下50加热，每小时转化5%6%，在转化率达70%75%时通过加入“终止剂”聚合反应终止，例如对苯二酚（大约0.1的重量百分含量），抑制自由基并避免过量支化和微凝胶形成。This mixture is heated with stirring and

8、 at 50This mixture is heated with stirring and at 50 gives gives conversions of 5%conversions of 5%6% per hour .Polymerization is 6% per hour .Polymerization is terminated at 70%75% conversion by addition of “terminated at 70%75% conversion by addition of “short-short-stopstop”, such as ”, such as h

9、ydroquinonehydroquinone (approximately 0.1 part),to (approximately 0.1 part),to quenchquench radicals and radicals and preventprevent excessive branching and excessive branching and microgel formation.microgel formation.Unreacted butadiene is removed Unreacted butadiene is removed by by flashflash d

10、istillationdistillation, and syrene by steam-stripping in a , and syrene by steam-stripping in a column. After addition of an column. After addition of an antioxidantantioxidant, such as , such as N-N-phenylphenyl-naphthylaminenaphthylamine (PBNA) (1.25 parts), the (PBNA) (1.25 parts), the latex is

11、coagulated by the addition of latex is coagulated by the addition of brinebrine, , followed by followed by dilute dilute sulfuric acidsulfuric acid or aluminum or aluminum sulfate. The coagulated sulfate. The coagulated crumbcrumb is washed, dried, and is washed, dried, and baledbaled for shipment.

12、for shipment.未反应的丁二烯通过闪蒸去除，苯乙烯在萃取塔中通过蒸汽萃取（剥离）。在加入抗氧剂后，例如N-甲基-萘胺（1.25的重量百分含量），加入盐水，其次加入稀释的硫酸或硫酸铝后乳液凝胶。凝胶碎片被洗涤、干 燥 并 包 装 装 运。今天这种生产过程仍是胶体聚合反应的基础。如图16.1所示一个重要的进步是连续操作；也采用计算机模型描述。This procedure is still This procedure is still the basis for the basis for emulsion emulsion polymerization today .An import

13、ant polymerization today .An important improvementimprovement is is continuous processing illustrated in Fig.16.1;computer continuous processing illustrated in Fig.16.1;computer modeling has also been described.modeling has also been described. InIn thethe continuouscontinuous processprocess, , styr

14、ene,styrene, butadiene,butadiene, soap,soap, i in-itiatorn-itiator, , andand activatoractivator (an(an auxiliaryauxiliary initiatinginitiating agentagent) ) areare pumpedpumped continuouslycontinuously formform storagestorage tankstanks throthrou-ghu-gh a a seriesseries ofof agitatedagitated reactor

15、sreactors atat suchsuch a a rate rate that that the desired degree of conversion is reached at the the desired degree of conversion is reached at the last last reactor. reactor. Shortstop is added, the latex warmed Shortstop is added, the latex warmed with steam, and the with steam, and the unreacte

16、d butadiene unreacted butadiene flashed offflashed off. . Excess styrene Excess styrene is steam-strippedis steam-stripped, and the latex , and the latex finished finished as shown in Fig. 16.1.as shown in Fig. 16.1.在连续操作中，苯乙烯、丁二烯、肥皂、引发剂和活化剂（一种助引发剂）用泵从储罐通过一系列的混合反应器，泵送流率根据末釜的转化率控制。加入终止剂，乳液用蒸气加热，未反应的丁

17、二烯被闪蒸。剩余的苯乙烯被蒸气剥离，如图14.1表示乳液完成。 SBR prepared from the original GR-S SBR prepared from the original GR-S reciperecipe is is often called hot rubber; cold rubber is made at 5 often called hot rubber; cold rubber is made at 5 by using by using a more active initiator system. a more active initiator sys

18、tem. Typical Typical recipes are given in Table 14.1 At 5 ,60% recipes are given in Table 14.1 At 5 ,60% conversion to polymer occurs in 1215h.conversion to polymer occurs in 1215h.由常规丁苯制法制备的丁苯胶常称作热胶；冷胶通过使用一种更高活性的引发体系在5制成。典型的配方在表14.1中给出。5、60%转化率、1215 h聚合物形成。丁二烯苯乙烯特十二烷基硫醇过氧化二异丙苯过氧化薄荷烷硫酸亚铁七水合物焦磷酸钾磷酸钠十

19、水合物 乙二胺四乙酸钠甲醛次硫酸钠松香酸ColdCold SBRSBR tiretire treadstreads areare superiorsuperior toto thosethose ofof hothot SBR.SBR. P Polymersolymers withwith abnormallyabnormally highhigh molecularmolecular weightweight (and(and consequentlyconsequently tootoo toughtough toto processprocess byby ordinaryordinar

20、y factoryfactory equipment)equipment) cancan bebe processedprocessed afterafter thethe additionaddition ofof upup to to 5050 partsparts ofof petroleum-basepetroleum-base oilsoils perper hundredhundred partsparts ofof rubberrubber (phr).(phr).冷丁苯橡胶轮胎优于那些热丁苯胶。具有异常高的分子量的聚合物（因此采用常规的工厂设备由于太粘稠而难以加工）在每一百份的

21、橡胶中加入大于50份的石油基础油后能够加工。These oil These oil extendersextenders make the rubbers more make the rubbers more processible at lower cost and with little sacrifice processible at lower cost and with little sacrifice in properties; they are usually emulsified and in properties; they are usually emulsified a

22、nd blended with the latex before coagulation.blended with the latex before coagulation.这些油添加剂使橡胶更易加工体现在低成本和性能方面低损耗；他们在凝胶之前通常乳化并与胶乳混合。Recent trends have been toward products designed Recent trends have been toward products designed for specific uses. The color of SBR, which is for specific uses. The

23、color of SBR, which is important in many nontire uses, has been improved important in many nontire uses, has been improved by the use of by the use of lighter-coloredlighter-colored soaps, shortstops, soaps, shortstops, antioxidants, and extending oils. For example, antioxidants, and extending oils.

24、 For example, dithiocarbamates dithiocarbamates are substituted for are substituted for hydroquinone hydroquinone as shortstop; the latter is used on hot SBR where as shortstop; the latter is used on hot SBR where dark color is not dark color is not objectionableobjectionable. .最近倾向于设计特殊用途的产品。丁苯橡胶的颜

25、色，在许多非轮胎使用中十分重要，通过使用浅色的肥皂、终止剂、抗氧剂和扩展油加以改进。例如，二硫化氨基甲酸盐替代对苯二酚作为终止剂；后者适用于不被人反对的黑色丁苯橡胶。A shortstop such as A shortstop such as sodium sodium dimethyldithiocarbamate dimethyldithiocarbamate is more effective in is more effective in terminating radicals and terminating radicals and destroying peroxides at

26、 the lower temperatures destroying peroxides at the lower temperatures employed for the cold rubbers.employed for the cold rubbers.在冷胶的制备中如二硫化氨基甲酸钠的终止剂在低温情况下对终止自由基和消灭过氧化物更有效。Free-radical dissociative initiators that function Free-radical dissociative initiators that function by by dissociationdissoc

27、iation of a molecule or ion into two of a molecule or ion into two radical species radical species are normally limited to are normally limited to inorganic inorganic persulfatespersulfates in the case of butadiene polymerization. in the case of butadiene polymerization.在丁二烯聚合反应过程中自由基分解的引发剂即一分子分解或离子成两个自由基物种的引发剂通常限制于过硫酸盐。The other important The other important classclass of free-radic