CN110804116A - 一种耐寒氯丁橡胶及其制备方法 - Google Patents
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- C—CHEMISTRY; METALLURGY
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- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/14—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
- C08F136/16—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen
- C08F136/18—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen containing chlorine
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- 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
- C08K5/00—Use of organic ingredients
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- 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
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- C08K5/04—Oxygen-containing compounds
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- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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Abstract
本发明属于氯丁橡胶制备技术领域,为了解决硫磺调节型氯丁橡胶在在温度‑30℃就会发生硬化,因此在东北等严寒地带或其它低温环境下,氯丁橡胶的使用受到了限制等问题,提供了一种耐寒氯丁橡胶胶料及其制备方法,由氯丁橡胶,硫化剂,加工助剂,增塑剂,补强剂,防老剂按一定比例制备而成。该胶料使用了单一的氯丁橡胶,解决了橡胶并用存在的差异性,从而影响橡胶特性的问题。同时通过按照不同比例不同种类添加增塑剂措施,降低了其在低温下的结晶性能,能够在低温‑42℃的条件下依然保持橡胶弹性而不发生脆化,极大程度地改善了氯丁橡胶耐低温性能,扩大了氯丁橡胶使用地域与范围。
Description
技术领域
本发明属于氯丁橡胶制备技术领域,具体涉及一种耐寒氯丁橡胶胶料及其制备方法。
背景技术
氯丁橡胶(CR),此产品具有优良的物理机械性能,且耐油、耐候、耐臭氧、耐热、耐燃、耐曲挠性、耐化学药品和良好的气密性。而且广泛应用于制造各种电线、电缆、胶板、雨布、胶囊、气垫、输送带、传动带、密封件、帐篷布、导风筒、救生艇、耐油胶管、耐油胶靴、减震制品等。
但是氯丁橡胶的耐寒性差,尤其是在低温条件下,容易发生硬化、脆化而丧失了其所特有的弹性,限制了氯丁橡胶在低温条件下使用价值。现有氯丁橡胶产品在-30℃时就会发生硬化,因此在东北等严寒地带和其它低温环境下,氯丁橡胶的使用受到了限制。
申请号为201310511433.9,发明名称为《一种耐寒耐油改性氯丁橡胶电缆料》,该专利中提升了传统氯丁橡胶在电缆料的性能,通过使用合成橡胶共用与添加较多助剂实现的,不仅工艺复杂,而且并没有在极大程度提升氯丁橡胶的耐寒性能。
申请号为201710722861.4,发明名称为《一种改性氯丁橡胶及其制备方法》,该专利中是采用了天然橡胶与氯丁橡胶并用实现的,同时在工艺过程中需要额外加入硫化剂,实际应用中增加了生产成本。
文献《耐寒氯丁橡胶的研制》(冯初爽,合成橡胶工业,1992,15卷3期,139 ~ 141),在该文献中通过前期聚合工艺添加其他组分共聚可得到耐寒橡胶,目前国内生产厂家并无此类商品。
发明内容
本发明为了解决硫磺调节型氯丁橡胶在温度-30℃就会发生硬化,因此在东北等严寒地带或其它低温环境下,氯丁橡胶的使用受到了限制等问题,提供了一种耐寒氯丁橡胶胶料及其制备方法,该氯丁橡胶不仅能具有良好的力学性能,而且提高了橡胶的耐寒性能,能够使氯丁橡胶在-40℃以下的条件下使用,极大地扩大了氯丁橡胶的使用范围与地域。同时本发明只采用了单一的氯丁橡胶,需要较少助剂即可达到耐寒效果,同时工艺操作简单,能够有效降低生产成本。
本发明由如下技术方案实现的:一种耐寒氯丁橡胶胶料,以传统的中等结晶性氯丁橡胶为基础配方,氯丁橡胶基础配方以重量份计:氯丁二烯100份,调节剂硫磺4-6份,松香 36份,软水110份,氢氧化钠8份,分散剂4-6份,在40℃条件下进行聚合,当达到实验聚合度时,加入如下终止剂,其终止剂配方以重量份计:有机溶剂0.01-2份,乳化剂0.01-2份,阻聚剂0.0001-0.1份,硫化剂 0.01-10份,抗氧剂0.01-2份,增塑剂0.1-40份;
其中:所述有机溶剂为甲苯、丙酮、二甲苯中的任意一种;
所述的乳化剂为OP-10、平平加、十二烷基本磺酸钠、十二烷基硫酸钠、萘磺酸甲醛缩合钠盐混合乳化剂或松香皂液中的至少一种;
所述的阻聚剂为吩噻嗪、胺类阻聚剂、氮氧自由基类化合物及其衍生物阻聚剂中的任意一种;
所述的硫化剂为硫黄、碱金属氧化物、硫脲类促进剂、秋兰姆类促进剂、噻唑类促进剂、胍类促进剂、胺类促进剂中的至少一种;
所述的抗氧剂为抗氧剂1010、抗氧剂1076、抗氧剂264 或抗氧剂168、液体抗氧剂中至少一种;
所述的增塑剂为苯二甲酸酯类、脂肪二元酸酯类、 脂肪酸酯类、 磷酸酯类、聚酯类、环氧类和其它类合成增塑剂中的至少一种。
所述的硫化剂为碱金属氧化物氧化镁、氧化锌、乙烯硫脲 (NA-22)、二乙基硫脲、二硫化四甲基秋兰姆 (TMTD)、一硫化四甲基秋兰姆 (TS)、二硫化二苯并噻唑 (DM) 和二邻甲苯胍 (DOTG) 中的至少一种。
所述增塑剂为:脂肪二元酸酯类中的癸二酸二辛酯 (DOS)、己二酸二 ( 丁氧基乙氧基 ) 酯 (TP-95), 己二酸二辛脂、苯二甲酸酯类中的邻苯二甲酸二丁酯(DBP),邻苯二甲酸二辛酯;脂肪酸酯类中的乙酰柠檬酸三正丁酯,磷酸脂类中的磷酸三(丁氧基乙)酯,聚酯类中的聚己二酸亚丁基酯,环氧类中的环氧大豆油,其它类合成增塑剂中的二丁基亚甲基双硫代乙二醇酯 (Plastikator88) 中的至少一种。
制备所述一种耐寒氯丁橡胶胶料的方法,具体步骤如下:
(1)将油溶性阻聚剂、硫化机、抗氧剂、增塑剂溶于有机溶剂中,常温条件下磁力搅拌器搅拌均匀,制成油相;(2)将水溶性乳化剂加入软水中,常温条件下磁力搅拌器搅拌均匀,制成水相;(3)将配制好的水相与油相混合进行乳化,配成稳定乳液后待用。
本发明通过两种方式进行耐寒橡胶研制,其一,在聚合过程中进行配方改进改善氯丁橡胶的耐寒性,其二,在氯丁橡胶加工过程中添加较少助剂或是助剂的相互配合实现耐寒效果。两种方法各有特点,同时工艺操作简单,能够有效降低生产成本。通过聚合配方进行氯丁橡胶耐寒性改善,操作简单、易于实现,提高耐寒性能,不增加工艺成本。
具体实施方式
以下通过具体实施例来进一步说明本发明, 以下说明不用来限制本发明范围。
实施例1:室温条件下,将100份单体重量份数,按照吩噻嗪阻聚剂0.001g, N-亚硝基二苯胺0.011g,二硫代四乙基秋兰姆0.15g, 癸二酸二辛酯2.8g,己二酸二辛脂 0.8g,邻苯二甲酸二辛酯0.4g 溶于2g甲苯中,在磁力搅拌至上述物质溶解完全后配制成油相,待用。将乳化剂歧化松香皂液1.5g与软水5g混合均匀配制成水相。将配制好的水油相混合并在磁力搅拌进行乳化,待乳化完全后,加入液体抗氧剂备用。
按照中等结晶性配方制备胶乳,当胶乳比重达到实验目标值后,加入已配好的稳定剂进行终止反应。经过胶乳脱气处理,-15℃冷冻破乳凝聚,瞬间破乳后胶乳便冷冻转鼓上制得胶膜, 胶膜带经过水洗涤1-2min, 然后进入 115℃干燥箱干燥 30min,制备成干胶待用。
该耐寒氯丁橡胶及其制备方法,具体包括以下步骤:
(1)塑炼:按照GB/T 21462-2008,将氯丁橡胶放入开放式炼胶机中在35—45℃条件下塑炼,制备均一的塑炼胶,停放至室温,待混炼使用。
(2)混炼:按照上述配方配比,依次加入增塑剂、硫化剂、补强剂等加工助剂,得到混合均匀的混炼胶,停放6-24小时,待用。
(3)硫化:在本发明步骤2中混炼胶样均匀裁取145mm×122mm×2mm样片,在硫化压力1-20Mpa,硫化温度在120-180℃条件下,进行硫化10-20min,硫化完毕后,将样片取出在室温水中停放10-20min,沥干水分,停放2-4h后进行样品制备,待用。
(4)将上述制备出的胶样,按照测试标准,测试其物理性能、低温脆性实验,硫化性能测试。
本发明通过在配方中改善了中等结晶性能氯丁橡胶自身的耐寒性能,解决了普通氯丁橡胶在低温条件下使用的局限性,克服了普通氯丁橡胶低温结晶、 耐寒性较差的缺点, 能够在低温-42℃的条件下依然保持橡胶弹性而不发生脆化,.极大程度的突破了氯丁橡胶耐低温性能,扩大了氯丁橡胶使用地域与范围。
用本领域常规的生产橡胶制品的方法,本发明的耐寒性氯丁橡胶。 其生产工艺步骤如下:胶样塑炼——橡胶混炼——薄通出片——停放——硫化——停放——检验。
实施例2:室温条件下,将100份单体重量份数,按照吩噻嗪阻聚剂0.001g, N-亚硝基二苯胺0.011g,二硫代四乙基秋兰姆0.15g, 癸二酸二辛酯2.4g,己二酸二辛脂1.2g,邻苯二甲酸二辛酯0.4g 溶于2g甲苯中,在磁力搅拌至上述物质溶解完全后配制成油相,待用。将乳化剂歧化松香皂液1.5g与软水5g混合均匀配制成水相。将配制好的水油相混合并在磁力搅拌进行乳化,待乳化完全后,加入液体抗氧剂备用。
实施例3:室温条件下,将100份单体重量份数,按照吩噻嗪阻聚剂0.001g, N-亚硝基二苯胺0.011g,二硫代四乙基秋兰姆0.15g, 癸二酸二辛酯4.2g,己二酸二辛脂1.2g,邻苯二甲酸二辛酯0.6g 溶于2g甲苯中,在磁力搅拌至上述物质溶解完全后配制成油相,待用。将乳化剂歧化松香皂液1.5g与软水5g混合均匀配制成水相。将配制好的水油相混合并在磁力搅拌进行乳化,待乳化完全后,加入液体抗氧剂备用。
实施例4:室温条件下,将100份单体重量份数,按照吩噻嗪阻聚剂0.001g, N-亚硝基二苯胺0.011g,二硫代四乙基秋兰姆0.15g, 癸二酸二辛酯3.6g,己二酸二辛脂1.8g,邻苯二甲酸二辛酯0.6g 溶于2g甲苯中,在磁力搅拌至上述物质溶解完全后配制成油相,待用。将乳化剂歧化松香皂液1.5g与软水5g混合均匀配制成水相。将配制好的水油相混合并在磁力搅拌进行乳化,待乳化完全后,加入液体抗氧剂备用。
实施例2-4:耐寒氯丁橡胶胶料用本领域常规的生产橡胶制品的方法,按实施例1所述工艺制备耐寒性氯丁橡胶样品。其生产工艺步骤如下:胶样密炼——薄通出片——停放——硫化——停放——检验。
按照实施例1耐寒氯丁橡胶制备方法制的2-4耐寒氯丁橡胶,其检测数据如下表1所示:
表1 耐寒氯丁橡胶性能检测
按照上述胶乳稳定剂配制方法(空白样)与常规橡胶干胶炼制方法进行实例对比如下:
对比例1:室温条件下,将100份单体重量份数,按照吩噻嗪阻聚剂0.001g, N-亚硝基二苯胺0.011g,二硫代四乙基秋兰姆0.15g溶于2g甲苯中,在磁力搅拌至上述物质溶解完全后配制成油相,待用。将乳化剂歧化松香皂液1.5g与软水5g混合均匀配制成水相。将配制好的水油相混合并在磁力搅拌进行乳化,待乳化完全后,加入液体抗氧剂备用。胶样制备所有工艺过程如实施例1所述。
对比例2-5:将常规稳定剂加入制备好的胶乳中,按照实施例1工艺制备出干胶样品,通过塑炼-混炼,在每100份干胶加入实施例1-4配比的增塑剂进行实验对比例2-5。
将常规稳定剂加入制备好胶乳中,按照实施例1工艺制备出干胶样品,通过密炼,在每100份干胶中加入实施例3与实施例4配方配比增塑剂用量,其上述对比实例实验数据结果如下:
表2对比实施例氯丁橡胶性能检测
通过上述实施例与对比实施例实验进行对比,可知普通中等结晶的氯丁橡胶在-35℃即出现脆化,而将上述配比的增塑剂加入纯胶配方或是经过密炼均能改善其耐寒性能,但是其改善效果有限,通过在聚合配方中加入同样配比的增塑剂于稳定剂中,能够显著改善其低温脆性性能,实现其耐寒效果。
本发明的氯丁橡胶的耐寒性能克服了普通氯丁橡胶在低温条件下的限制,极大程度扩大了氯丁橡胶适用范围,其技术优点在于通过聚合配方改进氯丁橡胶本身的耐寒性能,克服了橡胶共用存在的差异性特点而影响橡胶的特点。同时通过按照不同比例不同种类添加增塑剂措施降低其在低温结晶性能,改善了普通氯丁橡胶耐寒性较差性能。
Claims (4)
1.一种耐寒氯丁橡胶胶料,其特征在于:氯丁橡胶基础配方以重量份计:氯丁二烯100份,调节剂硫磺4-6份,松香 36份,软水110份,氢氧化钠8份,分散剂4-6份,在40℃条件下进行聚合,当达到实验聚合度时,加入如下终止剂,其终止剂配方以重量份计:有机溶剂0.01-2份,乳化剂0.01-2份,阻聚剂0.0001-0.1份,硫化剂 0.01-10份,抗氧剂0.01-2份,增塑剂0.1-40份;
其中:所述有机溶剂为甲苯、丙酮、二甲苯中的任意一种;
所述的乳化剂为OP-10、平平加、十二烷基本磺酸钠、十二烷基硫酸钠、萘磺酸甲醛缩合钠盐混合乳化剂或松香皂液中的至少一种;
所述的阻聚剂为吩噻嗪、胺类阻聚剂、氮氧自由基类化合物及其衍生物阻聚剂中的任意一种;
所述的硫化剂为硫黄、碱金属氧化物、硫脲类促进剂、秋兰姆类促进剂、噻唑类促进剂、胍类促进剂、胺类促进剂中的至少一种;
所述的抗氧剂为抗氧剂1010、抗氧剂1076、抗氧剂264 或抗氧剂168、液体抗氧剂中至少一种;
所述的增塑剂为苯二甲酸酯类、脂肪二元酸酯类、 脂肪酸酯类、 磷酸酯类、聚酯类、环氧类和其它类合成增塑剂中的至少一种。
2.根据权利要求1所述的一种耐寒氯丁橡胶胶料,其特征在于:所述的硫化剂为碱金属氧化物氧化镁、氧化锌、乙烯硫脲 (NA-22)、二乙基硫脲、二硫化四甲基秋兰姆 (TMTD)、二硫代四乙基秋兰姆、一硫化四甲基秋兰姆 (TS)、二硫化二苯并噻唑 (DM) 和二邻甲苯胍(DOTG) 中的至少一种。
3.根据权利要求1所述的一种耐寒氯丁橡胶胶料,其特征在于:所述增塑剂为:脂肪二元酸酯类中的癸二酸二辛酯 (DOS)、己二酸二 ( 丁氧基乙氧基 ) 酯 (TP-95), 己二酸二辛脂、苯二甲酸酯类中的邻苯二甲酸二丁酯(DBP),邻苯二甲酸二辛酯;脂肪酸酯类中的乙酰柠檬酸三正丁酯,磷酸脂类中的磷酸三(丁氧基乙)酯,聚酯类中的聚己二酸亚丁基酯,环氧类中的环氧大豆油,其它类合成增塑剂中的二丁基亚甲基双硫代乙二醇酯(Plastikator88) 中的至少一种。
4.制备权利要求1-3所述任意一种耐寒氯丁橡胶终止剂的方法,其特征在于:具体步骤如下:
(1)将油溶性阻聚剂、硫化机、抗氧剂、增塑剂溶于有机溶剂中,常温条件下磁力搅拌器搅拌均匀,制成油相;(2)将水溶性乳化剂加入软水中,常温条件下磁力搅拌器搅拌均匀,制成水相;(3)将配制好的水相与油相混合进行乳化,配成稳定乳液后待用。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113444325A (zh) * | 2021-05-31 | 2021-09-28 | 南京利德东方橡塑科技有限公司 | 一种轨道交通用超耐低温胶料及制动软管 |
CN113801256A (zh) * | 2020-06-17 | 2021-12-17 | 山纳合成橡胶有限责任公司 | 一种分步聚合制备液体氯丁橡胶的方法及其制备的液体氯丁橡胶 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104403059A (zh) * | 2014-11-06 | 2015-03-11 | 山纳合成橡胶有限责任公司 | 一种接枝型氯丁橡胶终止剂及其制备方法 |
-
2019
- 2019-11-04 CN CN201911066238.3A patent/CN110804116A/zh active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104403059A (zh) * | 2014-11-06 | 2015-03-11 | 山纳合成橡胶有限责任公司 | 一种接枝型氯丁橡胶终止剂及其制备方法 |
Non-Patent Citations (2)
Title |
---|
中国石油和石化工程研究会组织编写: "《合成橡胶》", 30 October 2000 * |
张军: "《橡塑制鞋材料及应用》", 28 February 1999 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113801256A (zh) * | 2020-06-17 | 2021-12-17 | 山纳合成橡胶有限责任公司 | 一种分步聚合制备液体氯丁橡胶的方法及其制备的液体氯丁橡胶 |
CN113801256B (zh) * | 2020-06-17 | 2023-12-29 | 山纳合成橡胶有限责任公司 | 一种分步聚合制备液体氯丁橡胶的方法及其制备的液体氯丁橡胶 |
CN113444325A (zh) * | 2021-05-31 | 2021-09-28 | 南京利德东方橡塑科技有限公司 | 一种轨道交通用超耐低温胶料及制动软管 |
CN113444325B (zh) * | 2021-05-31 | 2023-01-31 | 南京利德东方橡塑科技有限公司 | 一种轨道交通用超耐低温胶料及制动软管 |
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