CN110511300A - 一种卤化的反式丁二烯-异戊二烯共聚橡胶及其制备方法和用途 - Google Patents
一种卤化的反式丁二烯-异戊二烯共聚橡胶及其制备方法和用途 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/12—Incorporating halogen atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/12—Incorporating halogen atoms into the molecule
- C08C19/14—Incorporating halogen atoms into the molecule by reaction with halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/12—Incorporating halogen atoms into the molecule
- C08C19/18—Incorporating halogen atoms into the molecule by reaction with hydrocarbons substituted by halogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明涉及一种卤化的反式丁二烯‑异戊二烯共聚橡胶,尤其涉及一种反式丁二烯‑异戊二烯共聚橡胶的卤化及其制备方法和用途。该卤化的反式丁二烯‑异戊二烯共聚橡胶的卤含量为0.1wt%~82.5wt%,玻璃化温度‑72℃~50℃,熔点25℃~85℃。将反式丁二烯‑异戊二烯共聚橡胶在溶剂中溶解,然后加入卤化试剂在适宜的温度下反应一定时间,加入乙醇析出后得到卤化的反式丁二烯‑异戊二烯共聚橡胶。该卤化的反式丁二烯‑异戊二烯共聚橡胶可应用于轮胎或传送带的帘线层用胶中,其帘线抽出力较未添加卤化的反式丁二烯‑异戊二烯共聚橡胶的帘线抽出力提高15~50%。
Description
技术领域
本发明涉及一种卤化橡胶,特别是卤化的反式丁二烯-异戊二烯共聚橡胶及其制备方法和用途。属于卤化橡胶技术领域,及橡胶配方和加工工艺。
背景技术
卤化橡胶是天然或合成橡胶经卤化改性后的橡胶品,通过在橡胶分子链上引入卤原子或基团,使分子链带有极性,赋予橡胶优良的粘附性、防透水性与难燃性,可以在非极性橡胶与极性材料的粘合等领域得到应用。卤化橡胶有卤化天然橡胶、卤化丁基胶、卤化聚丁二烯橡胶、卤化乙丙胶和卤化SBS等。
橡胶的卤化可以采用固相、乳液、溶液和水相悬浮法,其中最常用的方法是溶液法,其工艺成熟,产品优良。中国发明专利200510038032、200810059405、201210185505等公开了溶液法进行丁基橡胶的氯化和溴化的生产方法,美国专利4254240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。中国发明专利CN201410265217公开了抗氧剂作用下的调节氯化位点的溶液法卤化丁基橡胶。以上报道的卤化橡胶的卤含量均不超过6%。为了获得较高的卤含量,中国发明专利CN01121783报道了一种在有氯气存在的情况下,采用紫外光辐照水相悬浮法氯化天然胶乳的方法得到氯含量60~70%的氯化天然橡胶,其工艺是先氯化后升温降解。但这种工艺对聚合釜要求比较苛刻,需要加装紫外光源,不太适合工业化生产,同时生产中产生大量的废水,不利于环保。乳液法卤化天然橡胶时,由于橡胶分子量大,需要降解后才能进行。但固相、乳液和水相悬浮法进行卤化改性,无法实现分子链的均匀卤化,卤原子在分子链中的分布不均匀会降低使用性能。现有专利报道未见对反式丁二烯-异戊二烯共聚橡胶的溶液法卤化。普利司通公司CN104379661B公开了一种溶液法部分卤化的二烯烃聚合物,及其在轮胎胎面及其他部位用胶的应用。中国发明专利CN 201110328679公开了一种环氧化反式异戊橡胶在轮胎带束层、胎面及内层胶等部位的应用,可以提高气密性和粘合性。但以上专利并未报道卤化橡胶在帘线层用胶的应用。
发明内容
鉴于现有技术存在的问题,本发明提供一种卤化的反式丁二烯-异戊二烯共聚橡胶及其制备方法和在帘线层用胶中的配方。
本发明中所述的卤化的反式丁二烯-异戊二烯共聚橡胶的卤含量为0.1wt%~82.5wt%,玻璃化温度-72℃~50℃,熔点25℃~85℃。所述的卤化的反式丁二烯-异戊二烯共聚橡胶,应用于轮胎、传送带及其他橡胶制品的帘线层胶,提高橡胶与帘线的结合力。
进行卤化反应时,采用的反式丁二烯-异戊二烯共聚橡胶中丁二烯单元的摩尔含量为5%~70%,异戊二烯与丁二烯在分子链中呈多嵌段分布结构。反式丁二烯-异戊二烯共聚橡胶中反式-1,4-结构摩尔含量大于85%,重均分子量1~120万。
在本发明所述的卤化反应中,卤化为氯化或溴化或氟化或碘化。所述的卤化试剂为溴、氯、碘、氯化溴、氯化碘、溴化碘、氢卤酸、氯化亚砜、N-卤代丁二酰亚胺、N-氯代异丙胺、五卤化磷、三卤化磷、溴化钠、溴化钾、次卤酸中的一种或两种以上复配使用,卤化试剂用量为按摩尔比与反式丁二烯-异戊二烯共聚橡胶为0.1:1~10:1。
本发明提供了一种卤化的反式丁二烯-异戊二烯共聚橡胶的制备方法,包括如下步骤:
(1)采用溶剂溶解反式丁二烯-异戊二烯共聚橡胶,溶解温度为30℃~80℃,溶解时搅拌速度为0~400转/分钟,溶解时间为0.5~10小时,得到反式丁二烯-异戊二烯共聚橡胶溶液;
(2)在步骤(1)得到的反式丁二烯-异戊二烯共聚橡胶溶液中加入卤化试剂,进行卤化反应,卤化反应时温度为30℃~80℃,反应时间为1min~600min,搅拌速度为0~400转/分钟;
(3)当步骤(2)的卤化反应时间达到1min~600min的任一时间点后,调节反应体系pH值,并向反应体系中加入乙醇,析出胶状物,放入真空干燥箱中干燥,得到卤化的反式丁二烯-异戊二烯共聚橡胶。
在上述卤化反应中,所述的溶剂为苯、甲苯、二甲苯、异丙苯、四氢呋喃、二氧六环、氯苯、甲基氯苯、二氯苯、四氯化碳、氯仿、二氯甲烷、环戊烷、甲基环戊烷、环己烷、乙酸乙酯中的一种或多种,溶剂与反式丁二烯-异戊二烯共聚橡胶的重量比为100:1~100:50。
在卤化反应过程中,通过加入氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾的固体或水溶液将反应体系的pH值调节为5.8~7.8,中和卤化反应过程中产生的酸性物质。卤化反应结束后,通过加入乙醇将卤化后的橡胶析出,乙醇用量按体积比为乙醇/反应体系为0.2:1~20~1,所述的干燥为干燥温度30~85度,时间12~48小时。
采用上述方法制备的卤化的反式丁二烯-异戊二烯共聚橡胶,应用于轮胎、输送带等含有帘线层的橡胶制品,其配方为:丁基橡胶0~95,天然橡胶0~95,丁腈橡胶0~95,卤化反式丁二烯-异戊二烯共聚橡胶5~20,炭黑40~65,氧化锌4~10,硬脂酸1~3,葵酸钴0~2,防老剂1~5,硫黄2~5,促进剂1~3。其中,所述的帘线为钢丝帘线、尼龙帘线、聚酯帘线、粘胶帘线。
采用本发明配方制备的帘线层胶,通过添加卤化的反式丁二烯-异戊二烯共聚橡胶,与丁基橡胶并用,使丁基橡胶的硫化速度提高20~50%。制成帘线层胶后,可以提高帘线层的帘线抽出力,较未添加卤化的反式丁二烯-异戊二烯共聚橡胶的帘线抽出力提高15~50%。
具体实施方式
本发明通过如下实例进行进一步说明,如下实例被认为仅是说明而不以任何方式限制本发明。
实施例1本实施例是氯化的反式丁二烯-异戊二烯共聚橡胶的制备。
反式丁二烯-异戊二烯共聚橡胶10g和四氯化碳1000g在60℃下搅拌溶解,搅拌速度为200转/分钟,溶解时间为10小时。将反式丁二烯-异戊二烯的氯苯溶液降温至40℃,向溶液中通入氯气,控制反应温度不超过60℃,反应3小时后,停止通入氯气。向聚合体系中加入氢氧化钠/乙醇溶液约5000ml,得到白色聚合物。置于40℃干燥箱中干燥24小时,得到氯化的反式丁二烯-异戊二烯共聚橡胶。经测试,所得氯化的反式丁二烯-异戊二烯共聚橡胶的氯含量为82.5wt%,玻璃化温度17.8℃,熔点85℃。
实施例2本实施例是氯化的反式丁二烯-异戊二烯共聚橡胶的制备。
反式丁二烯-异戊二烯共聚橡胶50g和二甲苯100g在80℃下搅拌溶解,溶解时间为0.5小时。向上面的溶液中通入氯气,控制反应温度30℃,反应时间为1分钟,停止通入氯气。向聚合体系中加入氢氧化钠/乙醇溶液约2000ml,得到白色聚合物。置于30℃干燥箱中干燥48小时,得到氯化的反式丁二烯-异戊二烯共聚橡胶。经测试,所得氯化的反式丁二烯-异戊二烯共聚橡胶的氯含量为0.35wt%,玻璃化温度-72℃,熔点25℃。
实施例3本实施例是氯化的反式丁二烯-异戊二烯共聚橡胶的制备。
反式丁二烯-异戊二烯共聚橡胶10g和氯苯500g在60℃下搅拌溶解,溶解时间为4小时。向上面的溶液中通入氯气,控制反应温度60℃,反应时间为2分钟,停止通入氯气。向聚合体系中加入氢氧化钠/乙醇溶液约1000ml,得到白色聚合物。置于45℃干燥箱中干燥12小时,得到氯化的反式丁二烯-异戊二烯共聚橡胶。经测试,所得氯化的反式丁二烯-异戊二烯共聚橡胶的氯含量为5.5wt%,玻璃化温度-43℃,熔点35℃。
实施例4本实施例是溴化的反式丁二烯-异戊二烯共聚橡胶的制备。
除了使用溴水作为溴化试剂,其他同实施例3,反应得到溴化的反式丁二烯-异戊二烯共聚橡胶。经测试,所得溴化的反式丁二烯-异戊二烯共聚橡胶的溴含量为3.2wt%,玻璃化温度-10℃,熔点42℃。
实施例5本实施例是氯化的反式丁二烯-异戊二烯共聚橡胶用于帘线层胶的配方。
帘线层胶配方按重量计为:丁基橡胶(IIR1953,山东京博石化有限公司)90,氯化反式丁二烯-异戊二烯共聚橡胶10,炭黑N330 50,氧化锌5,硬脂酸2,防老剂RD 1.5,硫黄2,促进剂DM 2.5。氯化反式丁二烯-异戊二烯共聚橡胶为实施例3得到的氯含量为5.5wt%的氯化反式丁二烯-异戊二烯共聚橡胶,帘线为尼龙帘线。经混炼后,测试硫化特性曲线,160℃下工艺正硫化时间为23min。制样、硫化后,测试帘线抽出力为865N。
对比例1本对比例是与实施例5进行对比。
帘线层胶配方按重量计为:丁基橡胶(IIR1953,山东京博石化有限公司)100,炭黑N330 50,氧化锌5,硬脂酸2,防老剂RD 1.5,硫黄2,促进剂DM 2.5。帘线为尼龙帘线。经混炼后,测试硫化特性曲线,160℃下工艺正硫化时间为35min。制样、硫化后,测试帘线抽出力为425N。
实施例6本实施例是氯化的反式丁二烯-异戊二烯共聚橡胶用于帘线层胶的配方。
除了使用2重量份的溴含量为2.3wt%的溴化反式丁二烯-异戊二烯共聚橡胶代替氯化反式丁二烯-异戊二烯共聚橡胶,帘线为钢丝帘线外,其余同实施例5。经混炼后,测试硫化特性曲线,160℃下工艺正硫化时间为18min。制样、硫化后,测试帘线抽出力为923N。
Claims (10)
1.一种卤化的反式丁二烯-异戊二烯共聚橡胶,其特征在于,所述的卤化的反式丁二烯-异戊二烯共聚橡胶的卤含量为0.1wt%~82.5wt%,玻璃化温度-72℃~50℃,熔点25℃~85℃。
2.根据权利要求1所述的卤化的反式丁二烯-异戊二烯共聚橡胶,其特征在于,所述的反式丁二烯-异戊二烯共聚橡胶中反式-1,4-结构摩尔含量大于85%,重均分子量1~120万,丁二烯单元的摩尔含量为5%~70%。
3.根据权利要求1所述的卤化的反式丁二烯-异戊二烯共聚橡胶,其特征在于,所述的卤化为氯化或溴化或氟化或碘化。
4.一种卤化的反式丁二烯-异戊二烯共聚橡胶的制备方法,包括如下步骤:
(1)采用溶剂溶解反式丁二烯-异戊二烯共聚橡胶,溶解温度为30℃~80℃,溶解时搅拌速度为0~400转/分钟,溶解时间为0.5~10小时,得到反式丁二烯-异戊二烯共聚橡胶溶液;
(2)在步骤(1)得到的反式丁二烯-异戊二烯共聚橡胶溶液中加入卤化试剂,进行卤化反应,卤化温度为30℃~80℃,卤化时间为1min~600min,搅拌速度为0~400转/分钟;
(3)当步骤(2)的卤化反应时间达到1min~600min的任一时间点后,调节反应体系pH值,并向反应体系中加入乙醇,析出胶状物,放入真空干燥箱中干燥,得到卤化的反式丁二烯-异戊二烯共聚橡胶。
5.根据权利要求4所述的制备方法,其特征在于,所述的溶剂为苯、甲苯、二甲苯、异丙苯、四氢呋喃、二氧六环、氯苯、甲基氯苯、二氯苯、四氯化碳、氯仿、二氯甲烷、环戊烷、甲基环戊烷、环己烷、乙酸乙酯中的一种或多种,溶剂与反式丁二烯-异戊二烯共聚橡胶的重量比为100:1~100:50。
6.根据权利要求4所述的制备方法,其特征在于,所述的pH值是通过加入氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、碳酸氢钠、碳酸氢钾的固体或水溶液调节反应体系pH值为5.8~7.8,所述的乙醇用量按体积比为乙醇/反应体系为0.2:1~20~1,所述的干燥为干燥温度30~85度,时间12~48小时。
7.根据权利要求4所述的制备方法,其特征在于,所述的卤化试剂为溴、氯、碘、氯化溴、氯化碘、溴化碘、氢卤酸、氯化亚砜、N-卤代丁二酰亚胺、N-氯代异丙胺、五卤化磷、三卤化磷、溴化钠、溴化钾、次卤酸中的一种或两种以上复配使用,卤化试剂用量为按摩尔比与反式丁二烯-异戊二烯共聚橡胶为0.1:1~10:1。
8.根据权利要求1所述的卤化的反式丁二烯-异戊二烯共聚橡胶,其特征在于,所述的卤化的反式丁二烯-异戊二烯共聚橡胶与丁基橡胶并用,使丁基橡胶硫化速度提高20~50%。
9.根据权利要求1所述的卤化的反式丁二烯-异戊二烯共聚橡胶,其特征在于,所述的卤化的反式丁二烯-异戊二烯共聚橡胶应用于轮胎、传送带及其他橡胶制品的帘线层胶,帘线抽出力提高15~50%,所述的帘线为钢丝帘线、尼龙帘线、聚酯帘线、粘胶帘线。
10.根据权利要求9所述的共聚橡胶,其特征在于,所述的卤化的反式丁二烯-异戊二烯共聚橡胶用于应用于帘线层胶,帘线层胶配方按重量份由以下组份组成:丁基橡胶0~95,天然橡胶0~95,丁腈橡胶0~95,卤化反式丁二烯-异戊二烯共聚橡胶5~20,炭黑40~65,氧化锌4~10,硬脂酸1~3,葵酸钴0~2,防老剂1~5,硫黄2~5,促进剂1~3。
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