CN111875857A - 一种聚醚鞋底 - Google Patents
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- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 46
- 229920000570 polyether Polymers 0.000 title claims abstract description 46
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004970 Chain extender Substances 0.000 claims abstract description 23
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 21
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 21
- 239000002667 nucleating agent Substances 0.000 claims abstract description 14
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004156 Azodicarbonamide Substances 0.000 claims abstract description 12
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims abstract description 12
- 235000019399 azodicarbonamide Nutrition 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000004088 foaming agent Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 238000004073 vulcanization Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 6
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000010008 shearing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- FWVCSXWHVOOTFJ-UHFFFAOYSA-N 1-(2-chloroethylsulfanyl)-2-[2-(2-chloroethylsulfanyl)ethoxy]ethane Chemical compound ClCCSCCOCCSCCCl FWVCSXWHVOOTFJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 2
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical group CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 abstract description 7
- 229920002635 polyurethane Polymers 0.000 abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 4
- 229920001971 elastomer Polymers 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006260 foam Substances 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 238000005096 rolling process Methods 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005060 rubber Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/14—Soles; Sole-and-heel integral units characterised by the constructive form
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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Abstract
一种聚醚鞋底，包含以下重量份原料：改性顺丁橡胶50‑70份、硫化剂1.8‑2.2份、聚醚20‑30份、硫化促进剂1.5‑3.5份、固体软化剂1‑5份、发泡剂偶氮二甲酰胺3‑5份、交联过氧化二异丙苯0.1‑0.3份、柠檬酸0.1‑0.3份、成核剂TiO21‑2份、扩链剂1‑2份。选用的稀土顺丁橡胶具有链结构规整度高、线性好、自粘性好、加工和物理机械性能优等特点，其耐磨性、抗疲劳性、滚动阻力和抗湿润性均优于锂、钛、钴和镍系等传统顺丁橡胶。成核剂TiO2有效降低了材料的密度，粒径越小的TiO2获得的聚氨酯鞋底的密度越小，泡孔也越均匀细密，进一步增强了聚醚鞋底的耐湿滑性能。
Description
技术领域
本发明涉及一种聚醚鞋底，属于鞋底制备技术领域。
背景技术
聚氨酯(PU)微孔弹性体鞋底材料于20世纪60年代末期在欧洲实现了工业化，70年代进入美国市场80年代起在全球得到了迅猛发展，用微孔聚氨酯弹性体制作的鞋底具有强度高、弹性好、舒适、耐磨、耐折、耐油、耐腐蚀、质轻和防滑等特点,对地面的冲击具有缓冲作用，可制成各种颜色、不同品种的鞋底。主要品种有皮鞋、越野滑雪鞋、凉鞋、拖鞋、运动鞋、旅游鞋和抗静电、耐油的安全鞋等。
聚氨酯鞋底原液分为聚酯型和聚醚型两类。市售聚氨酯鞋底70％是聚酯型的。而聚醚型鞋底是在近几年才上市，克服了聚酯型聚氨酯鞋底某些缺陷，且成本低廉。因而受到人们的大量选用。但是气候恶劣(如寒冷、潮湿、雨雪多)的地区和工作环境，现有的聚醚型鞋底耐湿滑性能较差，因此需要研究一种耐湿滑性能良好的聚醚鞋底。
发明内容
针对上述问题，本发明要解决的技术问题是提供一种聚醚鞋底。
本发明的一种聚醚鞋底包含以下重量份原料：改性顺丁橡胶50-70份、硫化剂1.8-2.2份、聚醚20-30份、硫化促进剂1.5-3.5份、固体软化剂 1-5份、发泡剂偶氮二甲酰胺3-5份、交联过氧化二异丙苯0.1-0.3份、柠檬酸0.1-0.3份、成核剂TiO21-2份、扩链剂1-2份。
进一步优选，所述的聚醚鞋底包含以下重量份原料：改性顺丁橡胶60份、硫化剂2份、聚醚25份、硫化促进剂2份、固体软化剂3份、发泡剂偶氮二甲酰胺4份、交联过氧化二异丙苯0.2份、柠檬酸0.2份、成核剂TiO21.5份、扩链剂1.5份。
进一步优选，所述的改性顺丁橡胶是以稀土钕为催化剂催化丁二烯聚合获得，所述的催化丁二烯聚合获得的含有高的顺式1,4-结构的聚丁二烯。
进一步优选，所述扩链剂选取二甲硫基甲苯二胺。
一种聚醚鞋底制备方法为：将改性顺丁橡胶、发泡剂偶氮二甲酰胺搅拌混合后，加热至100℃-108℃，保温2h-3h，然后加入硫化剂、硫化促进剂、固体软化剂、交联过氧化二异丙苯、柠檬酸、成核剂TiO2、扩链剂，剪切分散 30-60分钟，剪切速率为1500r/min-2000r/min，然后降温至温度为80℃-86℃，保温反应2h-3h，最后加入聚醚，快速搅拌1min-3min，倒入模具中成型后脱模、熟化，制备得到所述的聚醚鞋底。
本发明的有益效果：选用的稀土顺丁橡胶具有链结构规整度高、线性好、自粘性好、加工和物理机械性能优等特点，其耐磨性、抗疲劳性、滚动阻力和抗湿润性均优于锂、钛、钴和镍系等传统顺丁橡胶。成核剂TiO2有效降低了材料的密度，粒径越小的TiO2获得的聚氨酯鞋底的密度越小，泡孔也越均匀细密，进一步增强了聚醚鞋底的耐湿滑性能。
具体实施方式
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1：
一种聚醚鞋底制备方法为：按照聚醚鞋底的重量份原料配比，将改性顺丁橡胶50份、发泡剂偶氮二甲酰胺3份搅拌混合后，加热至100℃，保温2h，然后加入硫化剂1.8份、硫化促进剂1.5份、固体软化剂1份、交联过氧化二异丙苯0.1份、柠檬酸0.1份、成核剂TiO21份、扩链剂1份，剪切分散30 分钟，剪切速率为1500r/min，然后降温至温度为80℃，保温反应2h，最后加入聚醚20份，快速搅拌1min，倒入模具中成型后脱模、熟化，制备得到所述的聚醚鞋底。
实施例2：
一种聚醚鞋底制备方法为：按照聚醚鞋底的重量份原料配比，将改性顺丁橡胶70份、发泡剂偶氮二甲酰胺5份搅拌混合后，加热至108℃，保温3h，然后加入硫化剂2.2份、硫化促进剂3.5份、固体软化剂5份、交联过氧化二异丙苯0.3份、柠檬酸0.3份、成核剂TiO22份、扩链剂2份，剪切分散60 分钟，剪切速率为2000r/min，然后降温至温度为86℃，保温反应3h，最后加入聚醚30份，快速搅拌3min，倒入模具中成型后脱模、熟化，制备得到所述的聚醚鞋底。
实施例3：
一种聚醚鞋底制备方法为：按照聚醚鞋底的重量份原料配比，将改性顺丁橡胶60份、发泡剂偶氮二甲酰胺4份搅拌混合后，加热至105℃，保温2.5h，然后加入硫化剂2份、硫化促进剂3份、固体软化剂4份、交联过氧化二异丙苯0.2份、柠檬酸0.2份、成核剂TiO21.52份、扩链剂1.5份，剪切分散 40分钟，剪切速率为1800r/min，然后降温至温度为85℃，保温反应2.5h，最后加入聚醚25份，快速搅拌2min，倒入模具中成型后脱模、熟化，制备得到所述的聚醚鞋底。
对比例1的制备方法与实施例1相同，但是制备过程中不添加成核剂TiO2，具体制备方法为：将改性顺丁橡胶50份、发泡剂偶氮二甲酰胺3份搅拌混合后，加热至100℃，保温2h，然后加入硫化剂1.8份、硫化促进剂1.5份、固体软化剂1份、交联过氧化二异丙苯0.1份、柠檬酸0.1份、扩链剂1份，剪切分散30分钟，剪切速率为1500r/min，然后降温至温度为80℃，保温反应2h，最后加入聚醚20份，快速搅拌1min，倒入模具中成型后脱模、熟化，制备得到所述的鞋底。
对比列2的制备方法对比例1的制备方法与实施例2相同，但是制备过程中不添加成核剂TiO2，具体方法为将改性顺丁橡胶70份、发泡剂偶氮二甲酰胺5份搅拌混合后，加热至108℃，保温3h，然后加入硫化剂2.2份、硫化促进剂3.5份、固体软化剂5份、交联过氧化二异丙苯0.3份、柠檬酸0.3 份、扩链剂2份，剪切分散60分钟，剪切速率为2000r/min，然后降温至温度为86℃，保温反应3h，最后加入聚醚30份，快速搅拌3min，倒入模具中成型后脱模、熟化，制备得到所述的鞋底。
将实施例1-3和对比例1-2制备的鞋底进行硬度测试和湿止滑系数测试耐磨系数测试，
硬度按照ASTMD2240中规定的A型邵氏硬度进行测试；
湿止滑系数测试方法按照SATRATM144进行测试；
耐磨按照ASTMD5963中规定的方法A(非旋转方法)进行测试。
具体实验数据如下表1所示
表1
由此可见本申请制备的聚醚鞋底耐湿滑性能较为优异。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。
Claims (5)
1.一种聚醚鞋底，其特征在于：所述的聚醚鞋底包含以下重量份原料：改性顺丁橡胶50-70份、硫化剂1.8-2.2份、聚醚20-30份、硫化促进剂1.5-3.5份、固体软化剂1-5份、发泡剂偶氮二甲酰胺3-5份、交联过氧化二异丙苯0.1-0.3份、柠檬酸0.1-0.3份、成核剂TiO21-2份、扩链剂1-2份。
2.根据权利要求1所述的一种聚醚鞋底，其特征在于：所述的聚醚鞋底包含以下重量份原料：改性顺丁橡胶60份、硫化剂2份、聚醚25份、硫化促进剂2份、固体软化剂3份、发泡剂偶氮二甲酰胺4份、交联过氧化二异丙苯0.2份、柠檬酸0.2份、成核剂TiO21.5份、扩链剂1.5份。
3.根据权利要求1所述的一种聚醚鞋底，其特征在于：所述的改性顺丁橡胶是以稀土钕为催化剂催化丁二烯聚合获得，催化丁二烯聚合获得的含有高的顺式1,4-结构的聚丁二烯。
4.根据权利要求1所述的一种聚醚鞋底，其特征在于：所述扩链剂选取二甲硫基甲苯二胺。
5.一种聚醚鞋底制备方法，其特征在于：具体方法为：按照聚醚鞋底的重量份原料配比，将改性顺丁橡胶、发泡剂偶氮二甲酰胺搅拌混合后，加热至100℃-108℃，保温2h-3h，然后加入硫化剂、硫化促进剂、固体软化剂、交联过氧化二异丙苯、柠檬酸、成核剂TiO2、扩链剂，剪切分散30-60分钟，剪切速率为1500r/min-2000r/min，然后降温至温度为80℃-86℃，保温反应2 h-3h，最后加入聚醚，快速搅拌1min-3min，倒入模具中成型后脱模、熟化，制备得到所述的聚醚鞋底。
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