CN109312104B - 轮胎的密封层 - Google Patents

轮胎的密封层 Download PDF

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CN109312104B
CN109312104B CN201780038422.XA CN201780038422A CN109312104B CN 109312104 B CN109312104 B CN 109312104B CN 201780038422 A CN201780038422 A CN 201780038422A CN 109312104 B CN109312104 B CN 109312104B
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P·阿戈雷蒂
G·培祖罗
J·N·豪斯
F·马道
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    • 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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    • 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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
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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
    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C—CHEMISTRY; METALLURGY
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    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K2003/2272—Ferric oxide (Fe2O3)
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K2201/00—Specific properties of additives
    • C08K2201/01—Magnetic additives
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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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Abstract

一种轮胎的密封层，其由至少包含聚合物基料和填料的橡胶配混料制成，所述填料包含尺寸在1与100nm之间的纳米颗粒形式的磁性材料。

Description

轮胎的密封层
技术领域
本发明涉及用于制备轮胎的密封层的配混料。
背景技术
为了抵消来源于轮胎的刺穿的效果，长期以来已知利用配置在轮胎的内腔内的密封层。这样的密封层可以与轮胎内的充气气体接触，或者另外覆盖有保护聚合物或弹性体层。特别地，密封层通常配置在内腔的胎面胶条处的中心区域上。
特别地，密封层的目标是为了包围和粘附至刺穿胎面的物体，因此由于瞬时"密封"而防止轮胎的漏气。另外，如果刺穿物体脱离，则密封层的材料将会填充由该物体留下的孔洞，由此将其密封。
部分的轮胎研究关注于改进密封层的有效性，特别注意到其流变特性。事实上，密封层的粘度必须保证相对于刺穿物体以及相对于上述的任意孔洞的密封作用，以及独立于轮胎的静态或动态条件的其在内腔内的稳定性。
本发明的发明人已制成了一种轮胎的密封层，其技术特性是保证密封性能的改进。
发明内容
本发明的目的是一种轮胎的密封层，其由至少包含聚合物基料和填料的橡胶配混料制成；所述密封层的特征在于，所述填料包含尺寸在1与100nm之间的纳米颗粒形式的磁性材料。
优选地，所述聚合物基料包含基本上饱和的聚合物。
这里和下文中，"基本上饱和的聚合物"是指用小于15mol％的二烯单体制成的聚合物。
优选地，橡胶配混料包含5至50phr、更优选15至30phr的所述磁性材料。
优选地，所述磁性材料为磁性铁氧体(magnetic ferrite)。
优选地，所述磁性铁氧体包括在由钡铁氧体、锶铁氧体、钴铁氧体、锰铁氧体、磁赤铁矿(maghemite)(γ-Fe2O3)或其混合物组成的组内。
优选地，包含基本上饱和的聚合物的所述聚合物基料为卤代丁基橡胶和/或丁基橡胶。
另一目的是一种轮胎，其包括根据本发明的密封层。
具体实施方式
以下为仅仅通过说明的方式给出的非限制性实施方案的实例。
制备了五种配混料(A-E)，其中前三种(A-C)表示三个比较例，而第四种和第五种(D和E)是根据本发明的指示制成的配混料的实施例。
特别地，比较配混料A涉及当前用于制备密封层的配混料，比较配混料B与比较配混料A的不同之处在于：添加磁性铁氧体，其颗粒具有大于100nm的尺寸，而比较配混料C与比较配混料A的不同之处在于：炭黑已经由磁性铁氧体代替，所述磁性铁氧体的颗粒具有大于100nm的尺寸。
本发明的配混料D与比较配混料A的不同之处在于：已添加了磁性铁氧体，其颗粒具有在1与100nm之间的尺寸，而本发明的配混料与比较配混料A在以下方面相区别：炭黑已由磁性铁氧体代替，所述磁性铁氧体的颗粒具有在1与100nm之间的尺寸。
本质上，比较配混料B和C与本发明的各个的("各个的"是指炭黑的存在或不存在)配混料D和E在磁性铁氧体颗粒的尺寸方面不同。
表I中，列出五种配混料的以phr计的组成。
表I
Figure BDA0001913700920000031
BR-IIR代表溴化丁基橡胶。
具有式Fe2O3的磁性铁氧体*(磁铁矿)由INOXIA公司出售，并且具有53μm的尺寸和5200Kg/m2的密度。
具有式Fe2O3的磁性铁氧体**(磁铁矿)由IO-LI-TEC公司出售，并且具有在20与30nm之间的尺寸和5175Kg/m2的密度。
以下为混炼步骤的过程。
-混炼步骤-
将表I中列出的成分混炼在一起，并且在100℃下保持搅拌10分钟的时间。
从如上所述制成的各配混料，生产相关的密封层。
对在其上在相同的条件下施加源于配混料A-E的各个的密封层的轮胎进行为了证实上述各层的密封性的试验。具体地，将密封层直接挤出至轮胎的内腔的表面上。
试验涉及在用标准钉子(相同类型的钉子)进行轮胎的刺穿之后的压力保持，和一旦移除钉子时钉子的由密封剂覆盖的程度。
特别地，用静止轮胎和在轮胎于旋转(20Hz)中的条件下皆进行压力保持试验。
充气至相同的内压之后的轮胎经历相同的刺穿条件，随后移除钉子。对于进行了试验的各个轮胎，在刺穿(随后移除物体)之后24h时测量压力保持。
如上所述，关于各层的密封能力的试验之一涉及评估进行刺穿的钉子的由密封层覆盖的程度。
表II中，列出涉及气压保持和钉子的覆盖程度二者的值。为了更直接地评价由本发明赋予的优势，表II的值以相对于关于配混料A所获得的结果的指数形式表示。
报道的值越高，相关联的层的密封能力越好。
表II
A B C D E
刺穿钉子的覆盖程度 100 103 105 110 115
在静态条件下的压力保持 100 101 103 105 110
在动态条件下的压力保持 100 100 102 103 110
从表II的结果中，清楚的是，纳米颗粒形式的磁性材料在密封层(与本发明的配混料D和E相关联的层)内的存在保证了与关于通常使用的密封层(与本发明的配混料A相关联的层)所发现的相比更高的密封性能。
另外，配混料B和C的值与关于各个的配混料D和E的值的比较显示了磁性材料的颗粒的尺寸如何在相同的磁性材料赋予密封层的优势上发挥基本作用。的确，本发明人已经实验上证明了，如果磁性材料的颗粒具有大于100nm的尺寸，则密封层的粘弹性能是这样的：它们抵消了使用磁性材料本身的优势。
最后，已经发现了，磁性材料在密封层内的存在导致其还与其它的金属的轮胎部件相互作用，因而确保了该层在刺穿填充步骤期间的保持。

Claims (8)

1.一种轮胎的密封层，其由至少包含聚合物基料和填料的橡胶配混料制成；所述密封层的特征在于，所述填料包含尺寸在1与100nm之间的纳米颗粒形式的磁性材料。
2.根据权利要求1所述的密封层，其特征在于，所述聚合物基料包含基本上饱和的聚合物。
3.根据权利要求1或2所述的密封层，其特征在于，所述橡胶配混料包含5至50phr的所述磁性材料。
4.根据权利要求1或2所述的密封层，其特征在于，所述橡胶配混料包含15至30phr的所述磁性材料。
5.根据权利要求1或2所述的密封层，其特征在于，所述磁性材料为磁性铁氧体。
6.根据权利要求5所述的密封层，其特征在于，所述磁性铁氧体包括在由钡铁氧体、锶铁氧体、钴铁氧体、锰铁氧体、磁赤铁矿(γ-Fe2O3)或其混合物组成的组内。
7.根据权利要求1或2所述的密封层，其特征在于，包含基本上饱和的聚合物的所述聚合物基料为卤代丁基橡胶和/或丁基橡胶。
8.一种轮胎，其包括根据前述权利要求任一项所述的密封层。
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PCT/EP2017/065004 WO2017220523A1 (en) 2016-06-22 2017-06-20 Tyre sealant layer

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CN101044197A (zh) * 2004-08-28 2007-09-26 德古萨有限责任公司 含纳米级磁性填料的橡胶复合物
EP2070677A1 (en) * 2007-12-15 2009-06-17 The Goodyear Tire & Rubber Company Tire with indicia containing composite magnetic nanoparticles

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US6476110B1 (en) * 2000-02-18 2002-11-05 Continental Ag Rubber composition containing solid magnetizable particles of greater stiffness than the rubbery compounds
WO2001060639A1 (en) * 2000-02-18 2001-08-23 Continental Tire North America, Inc. Incorporating high levels of magnetic particulate into the rubber matrix of rubber compounds
JP2010159371A (ja) * 2009-01-09 2010-07-22 Sumitomo Rubber Ind Ltd タイヤ

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CN101044197A (zh) * 2004-08-28 2007-09-26 德古萨有限责任公司 含纳米级磁性填料的橡胶复合物
EP2070677A1 (en) * 2007-12-15 2009-06-17 The Goodyear Tire & Rubber Company Tire with indicia containing composite magnetic nanoparticles

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