CN102786618A - 一种溴氯化丁基橡胶的制备方法 - Google Patents
一种溴氯化丁基橡胶的制备方法 Download PDFInfo
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Abstract
本发明涉及一种溴氯化丁基橡胶的制备方法,是在反应挤出装置中进行丁基橡胶固相氯化,在反应挤出中完成对丁基橡胶的氯化、中和和脱挥,得到氯化丁基橡胶,再用溶液法对氯化丁基橡胶进行溴化,制备了溴氯化丁基橡胶。该方法采用先氯化再溴化的制备过程,提供了一种新的制备溴氯化丁基橡胶的工艺,该方法卤化效率高,卤素含量可控。
Description
技术领域
本发明涉及卤化聚合物的制备,特别涉及一种卤素含量可控的溴氯化丁基橡胶的制备方法。
背景技术
丁基橡胶因其优异的气密性而已广泛用作轮胎的基础材料。丁基橡胶经卤化(氯化或溴化)后可大大改善丁基橡胶与天然橡胶和其它不饱和橡胶的共硫化特性、黏结特性和耐热性,可以在非硫磺硫化体系中硫化,在子午线轮胎和无内胎轮胎以及医用瓶塞中得到应用。溴化丁基橡胶在加工性和硫化胶性能上优于氯化丁基橡胶,但氯化丁基橡胶的制备条件和生产设备没有溴化丁基橡胶要求苛刻,且氯化丁基橡胶的生产成本相对较低。氯化丁基橡胶在加工中的可控性高于溴化丁基橡胶。因此,将氯化丁基橡胶和溴化丁基橡胶两者的优点结合起来制备一类新的改性丁基橡胶,即溴氯化丁基橡胶,兼具氯化丁基橡胶和溴化丁基橡胶的优点,丁基橡胶卤化中引入溴可容易达到丁基橡胶中卤素含量,具有优异的加工性能,又可提高卤化丁基橡胶的热稳定性。
中国专利200510038032公开了一种氯化丁基橡胶的制备方法,通过丁基橡胶的溶解、氯化、中和、加助剂制得了氯化丁基橡胶。该法采用了传统的溶液法工艺制备,存在溶剂回收能耗高和环境保护问题。中国专利200810059405公开了一种溴化丁基橡胶的生产方法,将丁基橡胶溶解于溶剂中形成胶液,然后进行溴化反应,经中和、水反复洗涤、加入分散剂和抗热剂后,回收胶液中的溶剂,获得溴化丁基橡胶胶粒。中国专利200610109248公开了一种制造卤化橡胶状聚合物的方法,橡胶的卤化反应是在螺旋和螺杆挤出反应器封闭的干燥***中经塑化、脱气、软化、多级卤化、稳定、脱挥、出料切块制造出卤化橡胶状聚合物产品,卤素含量可控制。
英国专利1483063公开了聚丁二烯或丁二烯与异戊二烯共聚物的溴氯化方法,将聚合物溶解在溶剂中配成5%的溶液,滴入液态的氯化溴进行反应制备了阻燃和热稳定优异的溴氯化聚丁二烯。英国专利1483064公开了一种聚异戊二烯的溴氯化的方法,将聚异戊二烯溶解在溶剂中配成5%的聚异戊二烯溶液,滴入氯化溴溶液反应,或氯气和溴素同时通入聚异戊二烯溶液反应,或先加入氯气的四氯化碳溶液再导入液溴,可制备具有热稳定性和阻燃性的溴氯化聚异戊二烯。但上述专利中都需对聚合物先进行化学降解后再溴氯化,且室温下化学降解需2周以上时间。中国专利200910181102提供了一种用多段式双螺杆挤出机实现1-聚烯烃卤化的方法,提供了一种在反应挤出装置中通过丁基橡胶与氯化溴气体反应挤出得到溴氯化丁基橡胶的制备技术。但该方法对溴氯化丁基橡胶中卤素含量的控制没有具体的说明。本发明在此基础上,实现溴氯化丁基橡胶中卤素含量的可控。丁基橡胶是异丁烯和异戊二烯经阳离子聚合而得到的共聚物,其中异戊二烯的质量分数为1~5%。通过氯化反应挤出制备一定氯含量的氯化丁基橡胶,控制异戊二烯氯化程度,丁基橡胶中未氯化的异戊二烯链段可进一步与溴反应,通过溴化反应生成溴氯化丁基橡胶。
美国专利4563506公开了一种丁基橡胶连续溴化的工艺,并对卤化丁基橡胶的各种构型详细进行了论述,为卤化丁基橡胶的结构进行仪器分析,尤其是用核磁共振技术(NMR)研究卤化丁基橡胶的结构提供了依据。本发明中对溴氯化丁基橡胶的结构测定采用氢核磁共振技术。
测定聚合物中氯含量常用的方法有:紫外分析法、元素分析法、氧瓶燃烧-NaOH滴定法、氧瓶燃烧-电位滴定法、氧瓶燃烧-离子色谱法等核磁分析法。本发明中所涉及的溴氯化丁基橡胶制备中,聚合物的氯含量和溴含量的测定采用氧瓶燃烧-滴定法。
发明内容
本发明提供一种溴氯化丁橡胶的制备方法,依次包括下列步骤:
(1)氯化过程
①预处理:将干燥好的丁基橡胶喂入双螺杆挤出机反应器装置中的喂料机中,进行预软化,塑化。
②氯化反应:将步骤①处理过的物料以饥饿加料法定量进入双螺杆挤出机的反应段,在反应段通入用一定比例氮气稀释的氯气,控制反应段温度在90-120℃,同时在反应段末端注入适量稳定助剂。此反应区中氯气与丁基橡胶充分混合,均匀接触并发生反应生成氯化丁基橡胶。通过控制氯气的导入量可控制氯化丁基橡胶中氯含量,氯化丁基橡胶中氯的质量分数为0.1-1.0%。
③后处理:氯化丁基橡胶经稳定后进入挤出机的脱挥段,在脱挥段注入助脱挥剂,脱出氯化氢、氮气、少量卤素及低沸点物。控制温度在100-130℃,排出气体回收。产物在挤出机末端降温后进行造粒。
(2)溴化过程
①溶解:将氯化丁基橡胶放入溶剂中溶解制得胶液,氯化丁基橡胶在溶剂中的溶解度为5~20%。溶解丁基橡胶所用的有机溶剂为正己烷、环己烷、氯仿、四氯化碳、1,2-二氯乙烷和4-氯乙烯中的一种或一种以上混合溶剂。溶解温度为25~45℃,溶解时间为8~12小时。
②溴化:将液溴稀释溶解在溶剂中,剧烈搅拌下快速加入到氯化丁基橡胶胶液中溴化,溴化中反应温度为60~90℃,反应时间为3~10分钟。通过溴液加入量可实现溴氯化丁基橡胶中溴的质量分数在0.1~1.0%范围的调控。
③中和:将溴化后胶液用质量分数为2%的稀氢氧化钠碱液中和至pH为7.0~9.0,再用去离子水洗涤至pH为中性,分离去除水。
④加助剂制得产品:经中和处理得到的胶液中加入分散剂和热稳定剂。稳定剂为环氧大豆油,其用量为溴氯化丁基橡胶胶液质量分数的1~3%。分散剂是滑石粉或硬脂酸钙,其用量为溴氯化丁基橡胶胶液质量分数的0.1~2%。加入助剂后的溴氯化丁基橡胶胶液用旋转蒸馏除去溶剂,真空干燥得溴氯化丁基橡胶产品。
本发明工艺可操作,安全稳定,卤化效率高且卤素含量可控,溴氯化丁基橡胶可作为一种新型卤化丁基橡胶应用。
附图说明
图1为反应挤出制备1-聚烯烃卤化工艺流程示意图,图示说明如下:
1-聚烯烃固体颗粒或碎块原料加料线1,低压氮气管线2,双螺旋破碎塑化喂料机3,密封氮气4,液态原料进料管5,液态原料罐6,回收烃蒸汽60和61,排气机62,缓冲分离罐63,反应器塑化/混合段7,回收烃蒸汽8,反应器脱气段9,中压纯氮管线64,高沸点增塑剂管10,低沸点软化剂管11,搅拌均化釜12,计量加料泵13,反应器软化段14,惰性气体15,卤素气体16,混合缓冲器17,增压机18,前卤化反应段19,调节剂管线20,液态卤素管线21,渗混釜22,计量加料泵23,中卤化反应段24,后卤化反应段25,溶剂管线26,稳定剂27,混合釜28,计量加料泵29,反应器稳定段30和31,反应器脱挥段32、33,助脱挥剂管34、35,干卤化氢回收线36,冷却冷凝器37,冷凝液罐38,回收低沸点物管39,蒸汽冷却器40、41,真空排气机42,反应器出料计量段43,产品切片(粒)机44,卤化1-聚烯烃产品45,超声波发生器Us-46和Us-47,反应器温度监控点T-48~T-57,压力监控点P-58~P-59。
具体实施方式
下面结合实例对本发明作进一步说明,但本发明的保护范围并不限于下列实施例。
实例1
本实施例用于制备氯化丁基橡胶的设备装置示意图见说明书附图。丁基橡胶氯化的的主设备为一反向双螺杆挤出机组(反应器),螺杆直径φ36mm,长径比L/D=60,除计量出料段是啮合外,其余各段均为非啮合。简体为分段式控温,筒体内冷介质为0℃白油,外筒用电热铜瓦加热套加热。采用切碎的固体丁基橡胶碎块或长条,其最大轮廓外形尺寸或截面<20mm。加入喂料机-螺旋破碎塑化机③的料斗,重量为6kg,其规格为不饱和度2%,门尼34的市售通用丁基橡胶。在料斗下部不停通入0.01MPa压力氮气,流率约0.2NM3/h。螺旋破碎塑化机③的温度控制在50~80℃,将橡胶撕碎并挤压成多孔软化不粘性絮状物,送入下游反应***。在进料通道上,逆物料方向,通入密封氮气。在反应器的塑化(混合)段⑦,错列排列螺梭带切割混合功能的双螺杆,对已软化原料进行塑化,并同时通入氮气与物料混合,塑化段温度,可以控制在90℃左右。在反应脱气段⑨排气口,物料被降压,氮气夹带空气、潮气和可能的不饱和单体或低沸点烃,被排气机抽出,控制缓冲分离罐的压力和中压氮气量,以保证脱气后原料达到要求。脱气后进入反应器软化段在搅拌均化釜加入0.2倍橡胶重量的环己烷和0.1倍橡胶重量的环烷烃油,0.01倍橡胶重量的己二酸酯的软化剂,三种软化剂用前均进行脱去微量水和氧的处理,平均在20ppm以下。上述按比例混均匀后的混合软化剂,用计量加料泵增压加入软化段,料温将降低到60~70℃,并附以超声波降粘。在反应区,以0.1Kg氯气纯氮稀释混合气体(按体积比1/10配成卤化剂),按50%、30%、20%比例,按次加入前、中、后卤化反应段,反应属低放热过程,温度易控,前卤化反应温度50~70℃,中卤化反应温度70~100℃,后卤化反应温度90~130℃。卤化反应段占据了螺杆挤出反应器40%空间,保证了卤化反应足够时间和卤化剂近99%以上利用率。在两个脱气段、分别通入橡胶量5~10%的纯氮,第一脱挥口温度120~130℃,压力50KPa。第二脱挥口温度140~150℃,压力20KPa。排除的含氯化氢、氮、少量氯气和低沸点溶剂,经冷却器、降温后,用排气机增压,再经冷凝器回收溶剂后,纯干氯化氢气体回收利用。
脱去副产卤化氢的氯化丁基橡胶,经计量段,稳流降温升压送入出口模板,辅以超声降粘装置,在此经模面切条机切块并闪蒸降温,得到含氯质量分数为0.9%的氯化丁基橡胶,产品门尼粘度38,含有环烷油4.3%(wt)。
实例2
采用实施例1制备的氯化丁基橡胶在开炼机上破胶,压成薄片,裁成0.5cm×0.5cm×0.5cm的小颗粒。将10克干燥好的氯化丁基橡胶放入装有120mL正己烷的反应釜中溶胀,室温下搅拌使其充分溶解,12小时后形成胶液。
将0.3mL液溴在适量的正己烷中稀释,黑暗的条件下迅速将其滴加入到氯化丁基橡胶胶液中,剧烈搅拌。然后控制反应温度在68℃反应时间5min,冷却至室温。迅速加入质量分数2%的氢氧化钠溶液调节pH值至中性,中和15分钟后用去离子水充分洗涤,分离的油状液继续用去离子水洗涤3次后,分离得到溴氯化丁基橡胶的胶液。搅拌下加入质量分数为溴氯化丁基橡胶胶液1.5%的环氧大豆油和质量分数为溴氯化丁基橡胶胶液0.9%的硬脂酸钙。充分搅拌后,经旋转蒸馏除去溶剂、真空干燥后,在100℃的开炼机上开炼2min,去除水分,得到浅黄色的溴氯化丁基橡胶。用氧瓶燃烧-滴定法测得溴氯化丁基橡胶中氯的质量分数为0.8%,溴的质量分数为0.4%。
实施例3
采用实施例1制备的氯化丁基橡胶在开炼机上破胶,压成薄片,裁成0.5cm×0.5cm×0.5cm的小颗粒。将10克干燥好的氯化丁基橡胶放入装有120mL正己烷的反应釜中溶胀,室温下搅拌使其充分溶解,12小时后形成胶液。
将0.7mL液溴在适量的正己烷中稀释,黑暗的条件下迅速将其滴加入到氯化丁基橡胶胶液中,剧烈搅拌。然后控制反应温度在68℃反应时间5min,冷却至室温。迅速加入质量分数2%的氢氧化钠溶液调节pH值至中性,中和15分钟后用去离子水充分洗涤,分离的油状液继续用去离子水洗涤3次后,分离得到溴氯化丁基橡胶的胶液。搅拌下加入质量分数为溴氯化丁基橡胶胶液1.5%的环氧大豆油和质量分数为溴氯化丁基橡胶胶液0.9%的硬脂酸钙。充分搅拌后,经旋转蒸馏除去溶剂、真空干燥后,在100℃的开炼机上开炼2min,去除水分,得到浅黄色的溴氯化丁基橡胶。用氧瓶燃烧-滴定法测得溴氯化丁基橡胶中氯的质量分数为0.8%,溴的质量分数为0.8%。
本方法中的溴化过程还可以放大到工业生产,从而成为一种可行的工业生产溴氯化丁基橡胶的方法。
实施例4
采用实施例1制备的氯化丁基橡胶在开炼机上破胶,压成薄片,裁成0.5cm×0.5cm×0.5cm的小颗粒。将10克干燥好的氯化丁基橡胶放入装有120mL 1,2-二氯乙烷的反应釜中溶胀,室温下搅拌使其充分溶解,12小时后形成胶液。
将0.6mL液溴在适量的1,2-二氯乙烷中稀释,黑暗的条件下迅速将其滴加入到氯化丁基橡胶胶液中,剧烈搅拌。然后控制反应温度在80℃反应时间5min,冷却至室温。迅速加入质量分数2%的氢氧化钠溶液调节pH值至中性,中和15分钟后用去离子水充分洗涤,分离的油状液继续用去离子水洗涤3次后,分离得到溴氯化丁基橡胶的胶液。搅拌下加入质量分数为溴氯化丁基橡胶胶液1.5%的环氧大豆油和质量分数为溴氯化丁基橡胶胶液0.9%的硬脂酸钙。充分搅拌后,经旋转蒸馏除去溶剂、真空干燥后,在100℃的开炼机上开炼2min,去除水分,得到浅黄色的溴氯化丁基橡胶。用氧瓶燃烧-滴定法测得溴氯化丁基橡胶中氯的质量分数为0.9%,溴的质量分数为0.8%。
本方法中的溴化过程还可以放大到工业生产,从而成为一种可行的工业生产溴氯化丁基橡胶的方法。
Claims (10)
1.一种溴氯化丁基橡胶的制备方法,其特征在于先在反应挤出装置中实现丁基橡胶的氯化,氯化丁基橡胶再用溶液法完成溴化过程,经后处理制备出溴氯化丁基橡胶。
2.根据权利要求1所述的溴氯化丁橡胶的制备方法,其特征在于丁基橡胶的固相氯化是在双螺杆反应挤出装置中进行丁基橡胶的塑化、气固相氯化、稳定脱挥和挤出造粒而得到氯化丁基橡胶。
3.根据权利要求1所述的溴氯化丁橡胶的制备方法,其特征在于氯化丁基橡胶的溴化是在溶液中加入溴素进行的,溴化一定时间可得到一定溴含量的溴氯化丁基橡胶。
4.根据权利要求1所述的溴氯化丁橡胶的制备方法,其特征在于在反应挤出装置中进行丁基橡胶氯化挤出得到的氯化丁基橡胶中氯质量分数为0.1-1.0%。
5.根据权利要求1所述的溴氯化丁橡胶的制备方法,其特征在于氯化丁基橡胶用溶液法完成溴化,是将氯化丁基橡胶先溶解于有机溶剂中形成溶液,氯化丁基橡胶在溶液中的质量分数为5~20%。
6.根据权利要求1所述的溴氯化丁橡胶的制备方法,其特征在于氯化丁基橡胶在溶液中滴入液溴后,在一定条件下溴化反应,得到的溴氯化丁基橡胶中溴质量分数为0.1-1.0%。
7.根据权利要求5所述的氯化丁橡胶溶液的制备方法,其特征在于溶解丁基橡胶所用的有机溶剂为正己烷、环己烷、氯仿、四氯化碳、1,2-二氯乙烷和4-氯乙烯中的一种或一种以上混合溶剂,溶解温度为25~45℃,溶解时间为8~12小时。
8.根据权利要求1所述的溴氯化丁橡胶的制备方法,其特征在于氯化丁基橡胶用溶液法完成溴化过程,溴液滴入氯化丁基橡胶的胶液中,溴化中反应温度为60~90℃,反应时间为3~10分钟。
9.根据权利要求1所述的溴氯化丁橡胶的制备方法,其特征在于氯化丁基橡胶用溶液法完成溴化后,后处理是将氢氧化钠溶液中和胶液至pH为7.0~9.0,再用去离子水洗涤胶液至pH为中性,分离去除水,将胶液旋转蒸馏除去溶剂,真空干燥得产品。
10.根据权利要求1所述的溴氯化丁橡胶的制备方法,其特征在于氯化丁基橡胶用溶液法完成溴化后,在后处理之前在胶液中加入分散剂滑石粉或硬脂酸钙和热稳定剂环氧大豆油,分散剂的用量为胶液质量分数的0.1~2%,热稳定剂的用量为胶液质量分数的1~3%。
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CN105820281A (zh) * | 2015-01-09 | 2016-08-03 | 中国石油化工股份有限公司 | 一种卤化聚合物的制备方法 |
CN111944076A (zh) * | 2020-09-04 | 2020-11-17 | 浙江信汇新材料股份有限公司 | 一种卤化丁基橡胶的水洗工艺 |
CN112661878A (zh) * | 2020-12-17 | 2021-04-16 | 宁波普力通化学有限公司 | 一种用于单涂型橡胶金属粘合剂的高活性合成橡胶及制备 |
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CN105820281A (zh) * | 2015-01-09 | 2016-08-03 | 中国石油化工股份有限公司 | 一种卤化聚合物的制备方法 |
CN105820281B (zh) * | 2015-01-09 | 2018-03-02 | 中国石油化工股份有限公司 | 一种卤化聚合物的制备方法 |
CN105111347A (zh) * | 2015-09-15 | 2015-12-02 | 黄河三角洲京博化工研究院有限公司 | 一种溴化丁基橡胶的生产方法 |
CN111944076A (zh) * | 2020-09-04 | 2020-11-17 | 浙江信汇新材料股份有限公司 | 一种卤化丁基橡胶的水洗工艺 |
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