CN104540870A - 含有由环烯烃共聚物制成的阻隔材料的橡胶材料 - Google Patents
含有由环烯烃共聚物制成的阻隔材料的橡胶材料 Download PDFInfo
- Publication number
- CN104540870A CN104540870A CN201380042707.2A CN201380042707A CN104540870A CN 104540870 A CN104540870 A CN 104540870A CN 201380042707 A CN201380042707 A CN 201380042707A CN 104540870 A CN104540870 A CN 104540870A
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- Prior art keywords
- multipolymer
- double bond
- elastomeric material
- rubber
- ring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 58
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims abstract description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 19
- -1 cyclic olefin Chemical class 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 12
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- QPJORFLSOJAUNL-UHFFFAOYSA-N dibenzo[a,d][7]annulene Chemical compound C1=CC2=CC=CC=C2CC2=CC=CC=C21 QPJORFLSOJAUNL-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- C08J7/04—Coating
- C08J7/048—Forming gas barrier coatings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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- C—CHEMISTRY; METALLURGY
- 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
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- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D145/00—Coating compositions based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D165/00—Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G2261/3324—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from norbornene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G2261/41—Organometallic coupling reactions
- C08G2261/418—Ring opening metathesis polymerisation [ROMP]
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
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- C08G2261/612—Permeability for gases
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
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- C—CHEMISTRY; METALLURGY
- 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
- C08J2445/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/31826—Of natural rubber
- Y10T428/31833—Next to aldehyde or ketone condensation product or addition polymer from unsaturated monomers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Mechanical Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
本文描述了某种共聚物用于降低橡胶材料的透气性的用途。还描述了提供有共聚物形式的阻隔材料的橡胶材料。所述共聚物可通过以下物质的开环易位聚合来制备:a)一种第一烯烃单体,其选自具有至少一个内环C-C双键的环烯烃单体,其中在双键的α-位上不存在带有氢原子的叔碳原子,以及b)一种第二烯烃单体,其选自具有一个内环C-C双键的环烯烃单体,其中在双键的至少一个α-位上存在带有氢原子的叔碳原子,其中所述共聚物至少在一定程度上被氧化,其中用于制备具有至少两个C-C双键的共聚物的多环烯烃单体的量为零或小于1mol%,基于全部单体计。
Description
本发明涉及某种共聚物用于降低橡胶材料的透气性的用途。本发明还涉及提供有共聚物形式的阻隔材料的橡胶材料。所述共聚物可通过以下物质的开环易位聚合来制备:a)一种第一烯烃单体,其选自具有至少一个内环C-C双键的环烯烃单体,其中在双键的α-位上不存在带有氢原子的叔碳原子,以及b)一种具有C-C双键的第二烯烃单体,其选自具有一个内环C-C双键的环烯烃单体,其中在双键的至少一个α-位上存在带有氢原子的叔碳原子,其中所述共聚物至少在一定程度上被氧化。
在充气轮胎中,重要的是确保压缩空气或填充气体具有所需的压力值和必要的气体体积以使轮胎的功能性能力的运行维持最长时间。为此,常规充气轮胎的内部通常具有不透气或具有最低透气性的橡胶层。所述轮胎内层用于密封充有气体的内部,并且在无内胎轮胎中作为内胎的代替。可使用的材料的实例为含卤代丁基的可硫化橡胶混合物或丁基橡胶。
在EP 1847558 A1或美国专利申请61/257063中记载了通过开环易位聚合而制备的聚合物(开环聚环烯烃(polyalkenamers))。由环辛烯或环戊二烯起始通过环烯烃的开环易位聚合而制备的均聚物通常为脆性材料,其为热固性的或不能形成膜,并且不适于形成柔性涂层、或具有差的阻隔特性、或具有不能调节到所需值的玻璃化转变温度。US 4025708、US 3778420、EP 0488135、WO 2009/154849、WO 00/46255和WO02/26858还记载了开环聚环烯烃。所述文献没有记载氧化的开环聚环烯烃用于阻气性应用的用途。
通过由环烯烃开环易位聚合制备的某些共聚物作为气体阻挡层用于橡胶材料的用途记载于申请号为PCT/EP2012/051992的国际专利申请,其不是在先出版物。
本发明的目的是提供替代的阻隔材料,其旨在用于橡胶产品,特别是用于充气轮胎,并且其可以简单、廉价和有效的方式使用,和/或其具有良好或改进的气体阻隔特性。
本发明提供了一种共聚物用于降低橡胶材料的透气性的用途,其中所述共聚物可通过以下物质的开环易位聚合制备:
a)至少一种第一烯烃单体,其选自具有至少一个内环C-C双键的环(优选单环)烯烃单体,其中在双键的α-位上不存在带有氢原子的叔碳原子,以及
b)至少一种第二烯烃单体,其选自具有一个(即单个)内环C-C双键的环烯烃单体,其中在双键的至少一个α-位上存在带有氢原子的叔碳原子,
其中所述共聚物至少在一定程度上被氧化,以及
其中用于制备具有至少两个C-C双键的共聚物的多环烯烃单体的量为零或小于1mol%,基于全部单体计。
本发明还提供了通过提供上述更详细描述的共聚物形式的阻隔材料而改性的橡胶材料,其中所述共聚物至少在一定程度上被氧化。
优选共聚物以厚度为至少1μm的聚合物层的形式使用。优选烯烃单体a)与多环烯烃单体b)的摩尔比为99:1至1:99、优选90:10至10:90、特别优选50:50至80:20。
本发明还提供包含本发明橡胶材料的充气轮胎。
本发明还提供通过提供气体阻隔特性而改性橡胶材料的方法,其中将至少一种上述共聚物——将在下文详细描述——施用于橡胶材料或引入橡胶材料中。
在本发明中,已提供有共聚物的橡胶材料具有气体阻隔特性(例如,涉及到空气、氧气、氮气、氩气、二氧化碳、水蒸气等),其中通过使用本发明的共聚物,可产生阻隔特性,或增加其阻隔水平。表述“阻隔特性”意指与未涂覆的基底相比,关于某些物质的传输率或渗透性降低。氧气或气体阻隔特性可例如通过实施例中所描述的渗透性试验来测量。优选本发明的涂覆基底的氧气传输速率小于未处理基底的值的30%、特别是小于15%、或小于5%,例如0.1%至3%(于23℃和85%的相对湿度下测量)。
本发明所用的共聚物可通过开环易位聚合来制备。异位反应是非常常见的两种化合物之间的化学反应,其中一个基团在两种反应物之间交换。如果这是有机异位反应,其可从形式上代表双键上取代基的交换。然而,特别重要的反应为金属络合物催化的有机环烯烃化合物的开环异位反应(“开环易位聚合”缩写为ROMP),其中该方法提供了获取聚烯烃的途径。所用的催化金属络合物特别为通式结构Met=CR2的金属卡宾络合物,其中R为有机部分。因为金属卡宾络合物非常容易水解,因此异位反应可在无水有机溶剂或在烯烃本身中进行(参见例如US-A2008234451,EP-A 0824125)。为了避免去除大量溶剂或未反应烯烃的复杂的纯化步骤,还可在水性介质中进行烯烃的异位反应(DE 19859191;美国专利申请61/257063)。
本发明所用的共聚物由以下物质形成:
a)至少一种第一烯烃单体,其选自具有至少一个内环C-C双键的环烯烃单体,其中在双键的α-位上不存在带有氢原子的叔碳原子,以及
b)至少一种第二烯烃单体,其选自具有一个内环C-C双键的环烯烃单体,其中在双键的至少一个α-位上存在带有氢原子的叔碳原子,
其中用于制备具有至少两个C-C双键的共聚物的多环烯烃单体的量为零或小于1mol%,优选小于0.9mol%或小于0.8mol%,基于全部单体计。
共聚物优选包括纯烃,即非杂原子取代的烃。优选地,在位于内环双键的α-位上的叔碳原子处,共聚物至少在一定程度上被氧化。
烯烃单体a)与烯烃单体b)的摩尔比优选为99:1至1:99、优选90:10至10:90、特别优选50:50至80:20。
烯烃单体a)的实例为环丁烯、环戊烯、2-甲基环戊-1-烯、4-甲基环戊-1-烯、环己烯、2-甲基环己-1-烯、4-甲基环己-1-烯、1,4-二甲基环己-1-烯、3,3,5-三甲基环己-1-烯、环庚烯、1,2-二甲基环庚-1-烯、顺环辛烯、反环辛烯、2-甲基环辛-1-烯、4-甲基环辛-1-烯、5-甲基环辛-1-烯、环壬烯、环癸烯、环十一烯、环十二烯、环辛二烯、环戊二烯和环己二烯,并且本文特别优选具有C-C双键的单环烯烃,特别是顺环辛烯。
优选的仅具有单个C-C双键的环烯烃单体b)为3-烷基环-1-烯以及还有双环烯烃(例如降冰片烯),所述3-烷基环-1-烯优选烷基上具有1至10或1至4个C原子且优选环烯烃环上具有5至8个C原子。合适的化合物的实例为3-甲基环戊-1-烯、3-丁基环戊-1-烯、3-甲基环己-1-烯、3-甲基环辛-1-烯、3-丙基环戊-1-烯和3-甲基环辛-1-烯。特别优选降冰片烯。优选不使用任何多环二烯作为烯烃单体b)。术语多环意指具有至少两个环体系的化合物。
在一个优选的实施方案中,共聚物可通过顺环辛烯和降冰片烯的开环易位聚合形成。
本发明中所使用的共聚物优选在水性介质中制备。本文的开环异位反应可通过如下步骤进行:在聚合容器中使用水和分散剂作为初始进料;将有机金属卡宾络合物用作催化剂溶解于环烯烃中;将环烯烃/金属络合物溶液引入分散剂的水溶液中;将所得的环烯烃/金属络合物粗乳液转化为环烯烃/金属络合物细乳液;并在室温下反应以得到水性聚烯烃分散体。用于开环异位反应的方法优选使用至少一份水、至少一份分散剂和至少一份单体以平均液滴直径大于或等于≥2μm的水性单体粗乳液的形式作为初始进料,然后,随着能量的引入,将单体粗乳液转化为平均液滴直径为小于或等于≤1500nm的单体细乳液,然后在聚合温度下,将所得单体细乳液加入至任选剩余的残留量的水、任选剩余的残留量的分散剂、任选剩余的残留量的单体和全部量的用作催化剂的有机金属卡宾络合物中。
有机金属卡宾络合物可用作异位催化剂。金属的实例为第六、第七或第八过渡族的过渡金属,优选钼、钨、锇、铼或钌,其中优选锇和钌。特别优选使用钌-亚烷基络合物。此类型的异位催化剂公开于现有技术,并且记载于例如G.H.Grubbs(ed.)“Handbook of Metathesis”,2003,Wiley-VCH,Weinheim、WO 93/20111、WO 96/04289、WO 97/03096、WO 97/06185、J.Am.Soc.1996,第784至790页、Dlton Trans.2008,第5791至5799页,以及Coordination Chemistry Reviews,2007,251,第726至764页中。
在溶液中或水性分散体中用于涂覆的共聚物的浓度优选为至少1重量%,特别是5重量%,以及最高达50重量%或最高达70重量%。在水性分散体中共聚物的含量主要为10至60重量%,或15至55重量%,特别是20至50重量%。
在pH值为4和温度为20℃下,优选的共聚物水性分散体的粘度为10至150000mPas,或200至5000mPas(在20℃和20rpm下,通过Brookfield粘度计使用转轴4测量)。分散于水性分散体中的共聚物颗粒的平均颗径为例如0.02至100μm,优选0.05至10μm。其可例如借助于光学显微镜、光散射、流体动力色谱法或冷冻断裂电子显微镜测定。
共聚物的氧化可通过暴露于含氧环境,优选使用辐射能、热能和/或氧化促进剂而实现。例如,共聚物可在光照和室温(20℃)下在空气中被氧化,例如将共聚物或共聚物膜或涂覆有共聚物的基底暴露例如二到三周。氧化可用辐射能、热能、γ辐射和/或化学氧化促进剂(例如已知用于此目的的过渡金属化合物)加速。可用的氧化剂的实例为氧气和过氧化物。
橡胶材料的橡胶组分可例如选自二烯橡胶、天然橡胶、丁基橡胶、合成聚异戊二烯、聚丁二烯、苯乙烯-丁二烯共聚物、异戊二烯-丁二烯橡胶、苯乙烯-异戊二烯-丁二烯橡胶、丙烯腈-丁二烯橡胶、乙烯-丙烯橡胶和氯丁橡胶。
优选橡胶材料包括充气轮胎的组分,特别是充气轮胎的内层,或包括充气轮胎的胎体。
在一个实施方案中,橡胶材料本身提供有至少一种上述共聚物的溶液或水性分散体。在另一个实施方案中,将含橡胶制品——特别是充气轮胎——的组分使用阻隔材料进行改性并引入到含橡胶制品中,优选充气轮胎。例如,充气轮胎的织物帘线嵌入物(textile cord insert)可通过提供本发明所用的共聚物而改性。
本发明还提供了用于改性橡胶材料的方法,其中将本文描述的至少一种共聚物施用于橡胶材料或引入到橡胶材料中。改性可例如由一种或多种以下方法实现:浸渍、喷涂、铺展、涂布、压延。用于涂布法的分散体或溶液可包括其他的添加剂或助剂,例如调节流变性的增稠剂、润湿助剂、有机或无机填充剂或粘合剂。
优选共聚物以共聚物的水性分散体形式应用,并且通过在支撑基底上干燥分散体而形成膜。
本发明还提供包含本发明橡胶材料的充气轮胎。本文的共聚物可通过一种或多种以下方法应用:
-施用于轮胎内层的至少一部分表面或整个表面;
-引入到轮胎内层的材料中;
-以膜的形式、以无支撑箔片的形式或以箔片衬背的涂层的形式,其中除了基于橡胶的轮胎内层外,可将膜或箔片引入轮胎内部,或将膜或箔片作为轮胎内层的替代引入轮胎内部;
-以充气轮胎的纤维帘线嵌入物的粘合剂或涂层的形式;
-以两个以上支撑箔片之间的层压的形式引入到轮胎内部。
膜可以喷涂膜或铺展膜的形式例如通过使用辊涂、刮涂、喷涂或铸涂的方法而应用。材料还可以箔片的形式应用,其充当衬背,并且然后通过粘合剂粘合或交联(硫化)附着于胎体上。合适的箔片衬背的实例为基于橡胶、聚烯烃、聚酯、聚酰胺和聚氨酯的箔片衬背。
作为替代,还可以两个支撑箔片之间的层压的形式使用共聚物,其中层压随后通过粘合剂粘合或交联附着于胎体上。
共聚物还可以自支撑膜的形式使用。
该用途可例如通过在涂布机上将涂层组合物涂覆于由塑料制成的支撑性箔片上而实现。在使用网形式的材料的情况下,则通常由槽通过涂布辊应用聚合物分散体,并且借助于喷枪匀化。
其他应用涂层的成功方法的实例为使用反向凹版印刷法、使用喷涂法或使用刮刀辊法或使用本领域技术人员已知的其他涂布方法。此处的基底在至少一侧上具有涂层,即可在一侧或两侧上涂覆。
为了在箔片的粘合性上实现进一步的改进,支撑性箔片可预先经过电晕处理,或作为一个替代,例如,可使用如聚乙烯亚胺的粘合促进剂。应用至片状形式的材料上的量例如为优选1至800g(聚合物,固体)/m2,优选1至400g/m2,或5至200g/m2。一旦将涂层组合物施用于基底,则蒸发溶液或分散体介质。为此,例如在连续操作的情况下,可使材料穿过可配置有红外源设备的干燥通道。然后使经涂覆和干燥的材料穿过冷却辊并最终被卷起。干燥涂层的厚度为至少1μm,优选1至400μm,特别优选5至200μm。支撑性箔片的厚度通常在10μm至1cm的范围内。本文中在共聚物层的表面上的共聚物至少在一定程度上被氧化。在相对较厚的层的情况下,涂层的内部区域可包括未氧化的共聚物。
本发明中经涂覆的基底呈现优异的气体阻隔效果。
实施例
使用以下均聚物分散体和共聚物分散体(共聚物的单体比例基于摩尔比计):
分散体D1(对比):
30%的水性开环聚环辛烯(polyoctenamer)分散体,由顺环辛烯使用钌-亚烷基催化剂通过开环易位聚合(ROMP)制备。
数均粒径:378nm
分散体D2:
30%的水性开环聚(降冰片烯-共-环辛烯)分散体,由降冰片烯和顺环辛烯(50:50)使用钌-亚烷基催化剂通过开环易位聚合(ROMP)制备。
数均粒径:499nm
分散体D3:
30%的水性开环聚(降冰片烯-共-环辛烯)分散体,由降冰片烯和顺环辛烯(20:80)使用钌-亚烷基催化剂通过开环易位聚合(ROMP)制备。
数均粒径:307nm
开环聚环烯烃箔片的氧化程度的测定:
聚合物的氧化程度可用红外光谱法测定(购自Thermo FischerScientific的Nexus 470,具有Diamant ATR单元(Smart Orbit ATR)的FTIR光谱仪)。评估方法使用1710+/-5cm-1处的羰基谱带以1855+/-5cm-1至1498+/-5cm-1的范围为基线的消光度,以及还使用970+/-5cm-1处的C-C双键谱带以1001+/-5cm-1至918+/-5cm-1的范围为基线的消光度。使用羰基基团和C-C双键的消光度计算商值。表1示出结果。
表1:开环聚环烯烃在室温下(约20℃)暴露于空气中三周之前和三周之后的氧化程度
样品 | 暴露前C=O/C=C | 暴露后C=O/C=C |
D1 | 0.01 | 0.01 |
D3 | 0.03 | 1.71 |
自支撑开环聚环烯烃箔片的氧气渗透率的测定:
通过将开环聚环烯烃分散体注入尺寸为15cm×10cm×0.5cm(长×宽×高)的硅胶模具中而制备箔片。将流延分散体膜在25℃下干燥48h,然后在65℃的温度下热调理10分钟,然后在室温下储存三周。
干燥和潮湿的氧气渗透率值用MOCON2/21测量,其测量原理基于载气法。在0%的湿度下进行干燥测量:ASTM D3985;在增加的湿度下进行潮湿测量:ASTM F1927。在载气法中,将该情况下面积为5cm2的掩蔽样品膜(无支撑材料)装入到每侧均有空腔的气密室中。载气(95%的N2和5%的H2)在大气压力下从样品的一侧通过,并且测试气体(100%的O2)在大气压力下从另一侧通过。通过样品扩散的测试气体被载气夹带并传输至库伦传感器。因此可测定氧气的浓度随时间的变化。所有的测量均在23℃和限定的相对湿度(RH)下进行。样品的两侧均暴露于限定的湿度下。设备和样品的调理为约半小时。用于测量的机器运行时间为1至4天。在每个样品上均进行两次测定。为了使用该测量法,在计算中通过使用箔片的平均厚度将样品的传输速率(cm3/(m2*天))标准化为1μm和1巴,所述平均厚度在5个不同位点处测定。该标准化得到渗透速率[cm3μm/(m2*天*巴)]。
表2整理了该结果(干燥:于0%湿度下)。
表2:自支撑开环聚环烯烃箔片的氧气渗透率
*)24小时后的传输(未氧化的)
结果示出了未氧化的样品D3(暴露前)和D1呈现出比本发明的氧化的样品D2和D3(暴露后)明显更差的氧气阻隔效果。
自支撑开环聚环烯烃箔片的水蒸气渗透率的测定:
如上所述制备箔片。水蒸气渗透率通过使用MOCON3/33在85%的相对湿度下测量,其测量原理同样基于载气法。依据ASTM F1249操作设备。在载气法中,将该情况下面积为5cm2的掩蔽样品膜(无支撑材料)装入到每侧均有空腔的气密室中。载气(干燥的N2)在大气压下从样品的一侧通过,并且测试气体(N2和水蒸气)在大气压下从另一侧通过。通过样品扩散的测试气体被载气夹带并传输至选择性传感器。所使用的水蒸气测量仪器为IR传感器。因此可测定水蒸气的浓度随时间的变化。该测量在23℃下进行。设备调理为约30分钟。用最大精度将相对湿度设为85%以测量样品的传输速率,然后用计算机校正湿度水平设置中的小计量误差。本文认为在测量区域内传输速率与相对湿度之间线性相关。为了使用该测量法,在计算中通过使用箔片的平均厚度将样品的传输速率(cm3/(m2*天))标准化,所述平均厚度在5个不同位点处测定。该标准化得到渗透速率(g*μm/(m2*天))。
表3列出结果。箔片的厚度为439μm。
表3:自支撑开环聚环烯烃箔片的水蒸气渗透率
经开环聚环烯烃涂覆的橡胶箔片的氧气渗透率的测定:
通过测定涂覆有开环聚(降冰片烯-共-环辛烯)的天然橡胶基底的氧气渗透率来测量氧气阻隔效果。氧气阻隔用MOCON2/21测量,其测量原理基于载气法(ASTM D3985)。在23℃下用合成气体(21%的氧气)进行该测量。在每个样品上均进行两次测定。在0%和85%的相对湿度下测量氧气阻隔效果。
样品1:
未涂覆的天然橡胶(Erwin Telle GmbH,Nuremberg),
基底厚度:346μm
样品2:
用乙醇清洁厚度为346μm的天然橡胶基底(Erwin Telle GmbH,Nuremberg),用分散体D2开环聚(降冰片烯-共-环辛烯)进行涂覆,在50℃下干燥10min,然后在室温保持14天。涂覆在天然橡胶基底上的开环聚(降冰片烯-共-环辛烯)的厚度为35μm。
表4整理了氧气阻隔效果的结果:
表4:橡胶基底上的氧气阻隔效果
Claims (19)
1.一种共聚物用于降低橡胶材料的透气性的用途,其中所述共聚物通过以下物质的开环易位聚合制备:
a)至少一种第一烯烃单体,其选自具有至少一个内环C-C双键的环烯烃单体,其中在双键的α-位上不存在带有氢原子的叔碳原子,以及
b)至少一种第二烯烃单体,其选自具有一个内环C-C双键的环烯烃单体,其中在双键的至少一个α-位上存在带有氢原子的叔碳原子,
其中所述共聚物至少在一定程度上被氧化,以及
其中用于制备具有至少两个C-C双键的共聚物的多环烯烃单体的量为零或小于1mol%,基于全部单体计。
2.前述权利要求的用途,其中所述共聚物以共聚物的水性分散体的形式用于制备阻隔膜。
3.前述权利要求任一项的用途,其中所述烯烃单体a)与所述烯烃单体b)的摩尔比为99:1至1:99,和/或其中共聚物以层厚度为至少1μm使用。
4.前述权利要求任一项的用途,其中在处于内环双键的α-位的叔碳原子上,所述共聚物至少在一定程度上被氧化。
5.前述权利要求任一项的用途,其中所述共聚物通过顺环辛烯和降冰片烯的开环易位聚合制备。
6.用共聚物形式的阻隔材料改性的橡胶材料,所述共聚物由以下物质的开环异位聚合制备:
a)至少一种第一烯烃单体,其选自具有至少一个内环C-C双键的环烯烃单体,其中在双键的α-位上不存在带有氢原子的叔碳原子,以及
b)至少一种第二烯烃单体,其选自具有一个内环C-C双键的环烯烃单体,其中在双键的至少一个α-位上存在带有氢原子的叔碳原子,
其中共聚物至少在一定程度上被氧化,以及
其中用于制备具有至少两个C-C双键的共聚物的多环烯烃单体的量为零或小于1mol%,基于全部单体计。
7.前述权利要求的橡胶材料,其中在处于内环双键的α-位的叔碳原子上,所述共聚物至少在一定程度上被氧化。
8.权利要求6或7的橡胶材料,其中所述共聚物以层厚度为至少1μm使用,且在共聚物层表面上的共聚物至少在一定程度上被氧化。
9.权利要求6至8任一项的橡胶材料,其中所述烯烃单体a)与所述烯烃单体b)的摩尔比为99:1至1:99。
10.权利要求6至9任一项的橡胶材料,其中所述共聚物通过顺环辛烯和降冰片烯的开环易位聚合制备。
11.权利要求6至10任一项的橡胶材料,其中所述橡胶材料的橡胶成分选自二烯橡胶、天然橡胶、丁基橡胶、合成聚异戊二烯、聚丁二烯、苯乙烯-丁二烯共聚物、异戊二烯-丁二烯橡胶、苯乙烯-异戊二烯-丁二烯橡胶、丙烯腈-丁二烯橡胶、乙烯-丙烯橡胶和氯丁橡胶。
12.权利要求6至11任一项的橡胶材料,其包括充气轮胎的组分。
13.前述权利要求的橡胶材料,其包括充气轮胎的内层或包括充气轮胎的胎体。
14.充气轮胎,其包含权利要求6至13中任一项的橡胶材料。
15.前述权利要求的充气轮胎,其中所述共聚物通过一种或多种以下方法应用:
-施用于轮胎内层的至少一部分表面或整个表面;
-引入到轮胎内层的材料中;
-以膜的形式、以无支撑箔片的形式或以薄片衬背的涂层的形式,其中除了基于橡胶的轮胎内层外,将膜或箔片引入轮胎内部,或将膜或箔片作为轮胎内层的替代引入轮胎内部;
-以充气轮胎的纤维帘线嵌入物的粘合剂或涂层的形式;
-以两个以上支撑箔片之间的层压的形式引入到轮胎内部。
16.通过提供气体阻隔性而改性橡胶材料的方法,其中将至少一种共聚物施用于橡胶材料或插入到橡胶材料中,且所述共聚物通过以下物质的开环易位聚合制备:
a)至少一种第一烯烃单体,其选自具有至少一个内环C-C双键的环烯烃单体,其中在双键的α-位上不存在带有氢原子的叔碳原子,以及
b)至少一种第二烯烃单体,其选自具有一个内环C-C双键的环烯烃单体,其中在双键的至少一个α-位上存在带有氢原子的叔碳原子,
其中所述共聚物至少在一定程度上被氧化,以及
其中用于制备具有至少两个C-C双键的共聚物的多环烯烃单体的量为零或小于1mol%,基于全部单体计。
17.前述权利要求的方法,其中所述改性通过一种或多种以下方法实现:通过饱和浸渍,或通过喷涂,或通过铺展、涂布或压延。
18.前述方法权利要求任一项的方法,其中所述共聚物以共聚物的水性分散体形式施用,并且通过在基底上干燥分散体而形成膜。
19.前述方法权利要求任一项的方法,其中所述共聚物的氧化通过暴露于含氧环境,优选使用辐射能或热能和/或氧化促进剂而实现。
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PCT/EP2013/066287 WO2014026865A1 (de) | 2012-08-13 | 2013-08-02 | Kautschukmaterial mit barrierematerial aus cycloolefin-copolymeren |
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