CN109081969A - 弹性复合材料的制造方法 - Google Patents
弹性复合材料的制造方法 Download PDFInfo
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- CN109081969A CN109081969A CN201810607132.9A CN201810607132A CN109081969A CN 109081969 A CN109081969 A CN 109081969A CN 201810607132 A CN201810607132 A CN 201810607132A CN 109081969 A CN109081969 A CN 109081969A
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- elastic composite
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- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 229920001971 elastomer Polymers 0.000 claims abstract description 41
- 239000005060 rubber Substances 0.000 claims abstract description 41
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 229920000260 silastic Polymers 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000004615 ingredient Substances 0.000 claims description 13
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 13
- 239000010734 process oil Substances 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 10
- 238000007306 functionalization reaction Methods 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 239000002109 single walled nanotube Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 10
- 229920002379 silicone rubber Polymers 0.000 abstract description 5
- XZGAWWYLROUDTH-UHFFFAOYSA-N 1,1,1-triethoxy-3-(3,3,3-triethoxypropyltetrasulfanyl)propane Chemical compound CCOC(OCC)(OCC)CCSSSSCCC(OCC)(OCC)OCC XZGAWWYLROUDTH-UHFFFAOYSA-N 0.000 abstract 1
- 238000005096 rolling process Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- 230000035882 stress Effects 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- JSNRRGGBADWTMC-UHFFFAOYSA-N (6E)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene Chemical compound CC(C)=CCCC(C)=CCCC(=C)C=C JSNRRGGBADWTMC-UHFFFAOYSA-N 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- -1 sulphur) Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 229920001194 natural rubber Polymers 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- CXENHBSYCFFKJS-UHFFFAOYSA-N (3E,6E)-3,7,11-Trimethyl-1,3,6,10-dodecatetraene Natural products CC(C)=CCCC(C)=CCC=C(C)C=C CXENHBSYCFFKJS-UHFFFAOYSA-N 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
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- 239000010779 crude oil Substances 0.000 description 1
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- 229920003244 diene elastomer Polymers 0.000 description 1
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- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
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- 238000009472 formulation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
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- 150000003456 sulfonamides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- NELNNGOFUZQQGL-UHFFFAOYSA-N triethoxy-[1-(1-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)C(CC)SSSSC(CC)[Si](OCC)(OCC)OCC NELNNGOFUZQQGL-UHFFFAOYSA-N 0.000 description 1
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
本发明提供一种弹性复合材料的制造方法,包括:将一碳材料以及一硅橡胶材料混合,使该碳材料均匀地分散于该硅橡胶材料中而形成一混炼胶;将该混炼胶与一双‑[三乙氧基硅(丙基)]四硫化物以及一交联剂共同混炼形成一混合物;以及加热该混合物使其硬化而获得该弹性复合材料,依上述方法制成的弹性复合材料具有改善的耐用性。
Description
技术领域
本发明涉及一种弹性复合材料的制造方法,尤指一种可制造出具有改善拉伸应力以及耐用性的制品的弹性复合材料的制造方法。
背景技术
弹性材料广泛应用于各种工业及民生领域,从汽车轮胎、鞋、胶布、运动用品、地板、胶布、输送带等日常生活用品,到电子、半导体工业、及太空机件等精密产业都有需求,其种类也包罗万象,如丁腈橡胶(nitrile rubber)、硅橡胶(silicone rubber)、氟素橡胶(fluoro carbon rubber)、苯乙烯-丁二烯橡胶(styrene butadiene rubber)等。
其中,以橡胶举例来说,其组成和配方是在经历过多次演进、改良、开发而有目前的多种型态:最初由橡胶树采集天然橡胶,再利用橡胶硫化的方法来改善天然橡胶性质,后来更以煤、石油、天然气为主要原料,透过人工方式依需求制造出各式各样的合成橡胶,而其中因为配方组成的不同,也赋予这些橡胶制品独特的物理特性。
例如,美国专利公告号US9228077B2提出的一种橡胶组合物中,含有橡胶成分(A)、法尼烯(farnesene)的聚合物(B)、以及二氧化硅(C),且该聚合物在该橡胶组合物中的含量为1至100重量份。使用该专利的该橡胶组合物制成的轮胎具有优异的滚动阻抗性能且可抑制机械强度以及硬度的下降;又或者如美国专利公告号US9593228 B2所提出的可硫化橡胶混合物,包含:(A)至少一经羧基及/或羟基及/或其盐类功能化的二烯橡胶;(B)至少一淡色填料;(C)三羟甲丙烷(trimethylolpropane);(D)至少一脂肪酸,且其中以100重量份的成分(A)为基准,成分(C)及(D)量的总和为0.1至20重量份,该可硫化橡胶混合物可应用在车辆轮胎胎纹上,具有高耐磨耗性能及低滚动阻抗等优点。
然而,对于质量的追求往往是没有止尽的。特别是多数的弹性材料在使用过程中常面临磨耗问题,也容易随着使用时间增加而面临老化问题,上述种种仍是目前研究团队亟欲改善突破的议题。
发明内容
本发明的主要目的,在于解决已知硅橡胶的耐用性不够理想的缺点。
为了达到上述目的,本发明提供一种用于制造弹性复合材料的配方、以及弹性复合材料的制造方法,依该配方制成的制品具有更耐用的优点,进而提升该制品的寿命。
据此,本发明提供一种用于制造弹性复合材料的配方,包含:一硅橡胶材料;一占总成分的重量百分比介于0.0005%~10%之间的碳材料,该碳材料为选自由单壁纳米碳管、多壁纳米碳管、石墨烯、氧化石墨烯及其组合所组成的组;一占总成分的重量百分比介于0.0005%~15%的双-[三乙氧基硅(丙基)]四硫化物(Bis(triethoxysilylpropyl)tetrasulfide);以及一占总成分的重量百分比介于0.5%~2%之间的交联剂。
本发明还提供一种弹性复合材料的制造方法,包括以下步骤:
将一碳材料以及一硅橡胶材料混合,使该碳材料均匀地分散于该硅橡胶材料中而形成一混炼胶,其中,该碳材料占该混炼胶的重量百分比介于0.01%~20%之间;
将该混炼胶与一双-[三乙氧基硅(丙基)]四硫化物以及一交联剂共同混炼形成一混合物,其中该交联剂占该混合物的重量百分比介于0.5%~2%之间;以及
加热该混合物使其硬化而获得该弹性复合材料。
本发明还提供一种弹性复合材料的制造方法,包括以下步骤:
将一碳材料以及一橡胶加工油混合,使该碳材料均匀地分散于该橡胶加工油中而形成一复合物,其中,该碳材料占该复合物的重量百分比为0.005%至10%之间;
将该复合物与一双-[三乙氧基硅(丙基)]四硫化物以及一交联剂共同混炼形成一混合物,其中该交联剂占该混合物的重量百分比介于0.5%~2%之间;以及
加热该混合物使其硬化而获得该弹性复合材料。
本发明同时提供一种轮胎胎面胶,包括上述的配方。
本发明同时提供一种轮胎胎面胶,是由上述的方法制得。
因此,通过本发明的配方所制得的制品,相较于已知硅橡胶制品而言,至少具有以下优点:
1.以本发明的用于制造弹性复合材料的配方所制得的制品,经测试其不仅在耐用性方面有所改善,在拉伸强度也有提升,且可延长其硬化时间,有助于提升弹性复合材料加工性。
2.本发明通过在该硅橡胶材料中加入特定比例的碳材料及双-[三乙氧基硅(丙基)]四硫化物,有效地降低损耗因子tanδ,因此以本发明的用于制造弹性复合材料的配方制得的轮胎具有较低的滚动阻力、降低油料耗费而具有节能的效果。
具体实施方式
涉及本发明的详细说明及技术内容,将组合实施例说明如下:
本发明的用于制造弹性复合材料的配方主要包含一硅橡胶材料、一碳材料、一双-[三乙氧基硅(丙基)]四硫化物、以及一交联剂。
本发明一实施例中,该硅橡胶材料可为一天然橡胶或合成橡胶,但本发明对此并无特别限制,本领域具有通常知识者可依所欲制得的弹性复合材料选择适当的橡胶种类使用。
该碳材料可为单壁纳米碳管、多壁纳米碳管、石墨烯、氧化石墨烯或其组合。该碳材料占总成分的重量百分比介于0.0005%~10%、优选介于0.005%~3%之间。在本发明一优选实施例中,该碳材料可经一官能化处理而具有选自由羧基、羟基、及其组合的取代基团。该官能化处理,举例来说,可将该碳材料加入温度约为70℃的混合酸中,煮30分到8小时之后,将该碳材料过滤,并以该碳材料:清水为1:100的比例润洗,再次将该碳材料过滤并烘干即完成。
在上述的官能化处理步骤中,该混合酸可为硝酸与硫酸以体积比1:3混合而成,且该碳管与该混合酸的比例可为1:100。然而,应理解上述的该官能化处理方法、温度、时间及比例关系属本领域具有通常知识者可视情况改变的范畴,只要可以使该碳材料具有选自由羧基、羟基、及其组合的取代基团的方法都可以应用于本发明中,而不仅限于上述方法。
该双-[三乙氧基硅(丙基)]四硫化物的加入有助于使该硅橡胶材料与该碳材料之间的结合由物理键结转为化学键结,因而可提升如拉伸强度等基本物性。本发明一实施例中,该双-[三乙氧基硅(丙基)]四硫化物占总成分的重量百分比介于0.0005%~15%之间、优选介于0.005%~10%之间、更优选介于0.05%~5%之间。
而适用于本发明的交联剂包括但不限于:含硫化合物(如硫磺)、过氧化物、金属氧化物、酯类化合物、胺类化合物、树脂类化合物、硒、或碲,然而,只要该交联剂在约150℃至195℃高温下会与橡胶分子进行化学反应形成三维网状结构体即可。且本发明一实施例中,该交联剂占总成分的重量百分比介于0.5%~2%之间。
除了上述的交联剂外,为了软化、增塑、或者润滑等目的,也可进一步添加一添加剂,适用于本发明的该添加剂可为氧化锌、硬脂酸、或者可为噻唑型或磺酰胺型的促进剂,但本领域具有通常知识者可依需求而选用,本发明对此并无特别限制,只要该添加剂占总成分的重量百分比5%以下即可。
本发明一实施例中,该用于制造弹性复合材料的配方可更包括一填料,该填料选自于碳黑、白垩、碳纤维、玻璃纤维及其组合所组成的组。至于该填料占总成分的重量百分比可介于10%~65%之间、较佳介10%~50%之间。
本发明一实施例中,该用于制造弹性复合材料的配方可另外包括一占总成分的重量百分比介于0.00001%~25%之间的橡胶加工油。本发明对于橡胶加工油的种类并于特别的限制,举例来说,可使用石蜡油、环烷基油、或改性芳香烃油等橡胶加工油,本领域具有通常知识者可依需求而选用适当的橡胶加工油。
至于制备该弹性复合材料的方法,举例来说,可将一碳材料以及一硅橡胶材料混合,使该碳材料均匀地分散于该硅橡胶材料中而形成一混炼胶,使该碳材料占该混炼胶的重量百分比介于0.01%~20%之间;接下来,将该混炼胶与一双-[三乙氧基硅(丙基)]四硫化物以及一占该混合物的重量百分比介于0.5%~2%之间的交联剂共同混炼形成一混合物之后,加热该混合物使其硬化而获得该弹性复合材料,加热温度可为常用于橡胶硬化(硫化)的温度,即150℃至185℃之间。
或者,在本发明另一实施例中,该弹性复合材料可由另一方法制造:将一碳材料以及一橡胶加工油混合,使该碳材料均匀地分散于该橡胶加工油中而形成一复合物,使该碳材料占该复合物的重量百分比介于0.005%~10%之间。接下来,将该复合物与一双-[三乙氧基硅(丙基)]四硫化物以及一占该混合物的重量百分比介于0.5%~2%之间的交联剂共同混炼形成一混合物之后,加热该混合物使其硬化而获得该弹性复合材料,加热温度可为常用于橡胶硬化(硫化)的温度,即150℃至185℃之间。
在上述制造方法中,更包括在该混合物中加入一填料,使得该填料占总成分的重量百分比介于10%~65%之间。且如前文所述,该填料可选自于碳黑、白垩、碳纤维、玻璃纤维及其组合所组成的组。
除此之外,在上述制造方法中,还包括将该碳材料经一官能化处理而具有选自由羧基、羟基、及其组合的取代基团。由于该碳材料表面具有羧基或羟基,故经该官能化处理后,更容易与该双-[三乙氧基硅(丙基)]四硫化物反应产生化学键结,可提升弹性复合材的拉伸强度、电性等基本物性。
上述使该碳材料均匀地分散于该硅橡胶材料中、或是使该碳材料均匀地分散于该橡胶加工油中的方法,举例来说,可利用如混炼机(mixing mill)、捏合机(kneader)、密炼机(banbury)来进行分散,然而,只要可确实地使该碳材料分散在该硅橡胶材料或该橡胶加工油中即可,本发明对此没有特别的限制。
实施例
接下来将依下表1的不同配方,分别制造出比较例1、实施例1、实施例2、实施例3、以及实施例4的弹性复合材料以进行后续的物理性测试。测试包括拉伸应力、M300、以及损耗因子tanδ,结果如下表2所示。
表1:单位(重量百分比)
表2
表2的硫化时间(T 90@175℃)是依据ASTM D2084及ISO3417国际标准规范,通过硫变仪分析在高温时(150℃~195℃)一含硫橡胶复材的橡胶硫化程度与硫化时间的关系曲线,本发明是设定在175℃进行分析;M300(kg/cm2)代表拉伸300%时的应力值,越高代表越刚硬;tanδ的数值越低表示滚动阻力越小。经由上表2结果可发现:当添加该双-[三乙氧基硅(丙基)]四硫化物的时候,在拉伸应力及M300项目中都比未添加的比较例1有更好的表现。
在tanδ的项目中也观察到:添加该双-[三乙氧基硅(丙基)]四硫化物的实施例1至4组别的tanδ数值都较比较例1的tanδ数值低,代表当利用本发明的配方制造为轮胎使用时(例如,以此配方制造的一胎面胶),可有效地降低该轮胎的滚动阻力,节省车辆的油耗,达到节能的效果。
综上所述,本发明具有以下特点:
1.以本发明的用于制造弹性复合材料的配方所制得的制品,经测试其不仅在拉伸应力方面有所改善,且可延长其硬化时间,有助于提升弹性复合材料加工性。
2.本发明通过在该硅橡胶材料中加入特定比例的碳材料及双-[三乙氧基硅(丙基)]四硫化物,有效地降低损耗因子tanδ,因此本发明的用于制造弹性复合材料的配方制得的轮胎具有较低的滚动阻力、降低油料耗费而具有节能的效果。
以上已将本发明做一详细说明,以上所描述的仅为本发明的一优选实施例而已,其不能限定本发明实施的范围。凡依本发明申请范围所作的均等变化与修饰等,皆应仍属本发明的专利涵盖范围内。
Claims (4)
1.一种弹性复合材料的制造方法,其特征在于该制造方法包括:
将一碳材料以及一硅橡胶材料混合,使该碳材料均匀地分散于该硅橡胶材料中而形成一混炼胶,其中,该碳材料占该混炼胶的重量百分比介于0.01%~20%之间,该碳材料是选自由单壁纳米碳管、多壁纳米碳管、石墨烯、氧化石墨烯及其组合所组成的组,且该碳材料是经一官能化处理而具有选自由羧基、羟基、及其组合的取代基团;
将该混炼胶与一双-[三乙氧基硅(丙基)]四硫化物以及一交联剂共同混炼形成一混合物,其中该交联剂占该混合物的重量百分比介于0.5%~2%之间;以及
加热该混合物使其硬化而获得该弹性复合材料。
2.如权利要求1所述的弹性复合材料的制造方法,其特征在于还包括在该混合物中加入一填料,其中填料占总成分的重量百分比介于10%~65%之间,该填料选自于碳黑、白垩、碳纤维、玻璃纤维及其组合所组成的组。
3.一种弹性复合材料的制造方法,其特征在于该制造方法包括:
将一碳材料以及一橡胶加工油混合,使该碳材料均匀地分散于该橡胶加工油中而形成一复合物,其中,该碳材料占该复合物的重量百分比为0.005%至10%之间,该碳材料是选自由单壁纳米碳管、多壁纳米碳管、石墨烯、氧化石墨烯及其组合所组成的组,且该碳材料经一官能化处理而具有选自由羧基、羟基、及其组合的取代基团;
将该复合物与一双-[三乙氧基硅(丙基)]四硫化物以及一交联剂共同混炼形成一混合物,其中该交联剂占该混合物的重量百分比介于0.5%~2%之间;以及
加热该混合物使其硬化而获得该弹性复合材料。
4.如权利要求3所述的弹性复合材料的制造方法,其特征在于该橡胶加工油占总成分的重量百分比介于0.00001%~25%之间。
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Also Published As
Publication number | Publication date |
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JP2019001979A (ja) | 2019-01-10 |
US20180362725A1 (en) | 2018-12-20 |
TW201905091A (zh) | 2019-02-01 |
TWI614311B (zh) | 2018-02-11 |
DE102018113984A1 (de) | 2018-12-20 |
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