CN1125169A - 容易与轮胎内衬分离的轮胎硫化胶囊 - Google Patents
容易与轮胎内衬分离的轮胎硫化胶囊 Download PDFInfo
- Publication number
- CN1125169A CN1125169A CN95109566A CN95109566A CN1125169A CN 1125169 A CN1125169 A CN 1125169A CN 95109566 A CN95109566 A CN 95109566A CN 95109566 A CN95109566 A CN 95109566A CN 1125169 A CN1125169 A CN 1125169A
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- Prior art keywords
- capsule
- rubber
- weight
- isobutene
- polymer
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Links
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
- B29D30/0601—Vulcanising tyres; Vulcanising presses for tyres
- B29D30/0654—Flexible cores therefor, e.g. bladders, bags, membranes, diaphragms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/44—Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles
- B29C33/48—Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles with means for collapsing or disassembling
- B29C33/50—Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles with means for collapsing or disassembling elastic or flexible
- B29C33/505—Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles with means for collapsing or disassembling elastic or flexible cores or mandrels, e.g. inflatable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
- B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
- C08L15/02—Rubber derivatives containing halogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
- B29D30/0601—Vulcanising tyres; Vulcanising presses for tyres
- B29D30/0654—Flexible cores therefor, e.g. bladders, bags, membranes, diaphragms
- B29D2030/0655—Constructional or chemical features of the flexible cores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2021/00—Use of unspecified rubbers as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明公开一种用于烃橡胶如充气轮胎的硫化模压的可膨胀胶囊。所述胶囊是一种包含异丁烯重复单元的交联弹性体，并且胶囊成分包含石墨。一种优选的异丁烯弹性体是溴化的异丁烯和对甲基苯乙烯的共聚物。所述胶囊具有增强的润滑性、较弱的对轮胎内衬的粘附性和较低的拉伸形变。上述性能的提高使得我们能够模制得到具有较少由擦伤或变形胶囊引起的缺陷的烃橡胶如轮胎。它们也增加了胶囊的使用寿命，降低了轮胎硫化的成本。
Description
本发明涉及轮胎硫化胶囊，该胶囊包含石墨和丁基橡胶聚合物或共聚物，包括卤化丁基橡胶和/或对甲基苯乙烯与异丁烯的卤化共聚物。它还涉及使用上述胶囊来硫化轮胎的方法。
常规的充气橡胶车辆轮胎是通过将绿色即未硫化和未成型轮胎在模压机中模塑而生产的。用一种内部流体可膨胀胶囊将绿色轮胎向外挤压靠着模具表面(有时称为阴模表面)。通过这种方法绿色轮胎紧靠外面的模具表面，该表面限定了轮胎花纹和侧壁的形状。通过加热和加压将轮胎在高温下模塑。
在通常的实践中，胶囊的膨胀是通过向胶囊腔体内部施加内压来完成的。所述压力是由流体如气体、热水和/或蒸汽来提供的。它们也参与轮胎的硫化所需的热量传递。然后，通常让轮胎在模具中稍微冷却，有时还辅以向胶囊中加入冷水或冷却水。然后，打开模具，排出胶囊内流体的压力使其凹下并从轮胎模具中取出轮胎。轮胎硫化胶囊的上述用途对于本领域的技术人员是熟知的。
人们认识到，在胶囊的膨胀阶段，胶囊的外部接触表面和轮胎内部表面之间有着明显的相对运动。类似地，在轮胎被模塑和硫化之后，在放瘪和从轮胎中取出胶囊时，在胶囊的外部接触表面和轮胎的硫化内部表面之间也有着显著的相对运动。
在轮胎硫化以后和在轮胎硫化周期的胶囊塌陷期间，胶囊表面常常粘在轮胎的内表面上。这一粘附如果不加以控制，便可能导致胶囊表面粗糙。这样便会减少胶囊的耐久性并产生有缺陷的轮胎。因此，通常的作法是用润滑剂预先涂覆绿色或未硫化轮胎的内表面，以便在整个模塑操作过程中提供胶囊的外表面与轮胎内表面的润滑性。上述润滑剂也被称为胶囊润滑剂，它常常是分散于溶剂或水中的硅氧烷聚合物。
应当明白，在工业制造的设定中，轮胎与其硫化胶囊的分离与胶囊与相邻轮胎表面的分离行为(以免粘附)和润滑行为(以增加滑动性)均密切相关。分离情况是指避免粘附即分离的基本能力，而润滑情况涉及增加表面滑动并使胶囊相对于轮胎运动的能力
丁基橡胶通常被用于轮胎硫化胶囊。丁基橡胶是主成分异丁烯与能赋予足以使丁基橡胶交联的不饱和度的少量二烯单体(通常是异戊二烯)的共聚物。Exxon仍在生产随后将被溴化的异丁烯与对甲基苯乙烯的共聚物。这些共聚物可用于许多使用丁基橡胶的场合。
美国专利4863650公开了在硅氧烷脱模剂膜中使用填充剂以达到消光的方法，所述填充剂如高岭土、白垩、岩石粉、硅石、碳黑和石墨。美国专利4310427公开了将干燥粉末撒在“绿色”轮胎的内表面上以提供润滑和分离的方法，所述干燥粉末例如云母、滑石和石墨。美国专利3967978公开了在润滑剂中使用细固体颗粒如云母或石墨的方法。
因此，人们期望能提供具有较低的胶囊对硫化轮胎的粘附性、较长的屈挠寿命和热稳定性得到提高、特别是热拉伸形变低的硫化胶囊。
我们发现石墨能够增加润滑性(降低摩擦系数)、降低丁基橡胶硫化胶囊对轮胎内衬的粘附性和减少胶囊生长(降低热拉伸形变)。溴化的异丁烯和对甲基苯乙烯的共聚物被发现在用于硫化胶囊时具有增强的热稳定性并且用作硫化胶囊具有提高的性能。
适宜混入硫化胶囊的石墨可以是天然的或合成的。石墨是在胶囊成分的混合过程中加入的，因此分散于整个模塑的胶囊之中。在马达加斯加、锡兰、墨西哥、朝鲜、澳大利亚、苏联和中国有天然石墨。合成橡胶可以由含碳材料制得，例如通过在电阻炉(electricresistance furnace)中将石油焦炭加热至大约3000℃制得。优选的石墨(有助于均匀分散)是粉末形式，使得大于80％(重量)的石墨通过325目筛(美国标准)，大于90％(重量)的石墨通过上述筛目更好，大于99％(重量)的石墨通过上述筛目最好。在表I中使用了上述石墨，它可从美国新泽西州Ticonderoga的Dixon公司以合成1442的名称得到。
石墨的用量以0.1-30phr为宜，0.5-20phr更好，优选1-5、10或15phr。phr是指橡胶组合物中每100重量份橡胶所对应的重量份数。phr是大多数橡胶配料师使用的标准术语，因为当所有成分均相对于100份橡胶而不是全部成分重量计算时，便于配方的改变和比较。橡胶或橡胶状聚合物是可交联的、Tg值在0℃以下、优选-20℃以下的主要是非结晶性的聚合物
这一应用优选的橡胶是至少一种异烯烃单体与对烷基苯乙烯单体的聚合物，并且该聚合物最好是溴化的。上述异烯烃可以具有4-7个碳原子。烷基苯乙烯的烷基可以具有1-11个碳原子。胶囊成分中的橡胶最好至少50％、至少75％、80％、85％或95％(重量)更好是一种或多种至少具有源自一种或多种异烯烃和对烷基苯乙烯的重复单元的聚合物。上述一种或多种异烯烃最好是不低于80％、90％或95％(重量)的异丁烯。上述对烷基苯乙烯最好是80％、90％或95％(重量)或更高的对甲基苯乙烯。异丁烯聚合物最好包含1-20％(重量)对甲基苯乙烯，含2-15％(重量)对甲基苯乙烯更好。异丁烯聚合物最好包含80-99％(重量)异丁烯、包含85-98％(重量)异丁烯更好。聚合物中溴含量最好不超过5％(重量)，优选在聚合物中占0.2-1.5或2.5％(重量)。可选地含有不超过5％或8％(重量)、最好是0.5-3％(重量)的具有4-8个碳原子的二烯单体。优选的异丁烯与对甲基苯乙烯的共聚物实际上不含异戊二烯和其它共轭二烯。特别优选的溴化共聚物是Exxon公司的门尼粘度ML(1＋8)125℃为50±5的Exxpro，其对甲基苯乙烯含量为大约5％(重量)，异丁烯含量为94或95％(重量)，总溴含量为0.8％(重量)。公开号为0,344,021的欧洲专利申请(该文献被并入本文作为参考)描述了这种聚合物的制备方法。
可选地，其它丁基橡胶也可以与异丁烯-对甲基苯乙烯共聚物合并使用也可作为其替代物使用。在胶囊组合物的全部橡胶聚合物中最好至少50％、至少75％、80％、85％或90％(重量)更好为源自异丁烯和一种或多种共轭二烯的丁基橡胶，优选异戊二烯。最好异戊二烯占1-5％(重量)，其余(例如95-99％(重量))为异丁烯。它们包括丁基橡胶、卤代的丁基橡胶如氯丁橡胶和溴丁橡胶。也可加入少量(例如少于全部橡胶状聚合物的10％或20％)的基于二烯的弹性体如异戊二烯橡胶作硫化促进剂或用于其它目的。氯丁橡胶也称为聚(氯丁二烯)。它在下述树脂固化体系中是常规的助硫化剂。在橡胶成分中，尽管氯丁橡胶作为含卤素弹性体具有独立的功能，但仍相对于100重量份橡胶计算。胶囊的100重量份橡胶中最好至少有50％、75％、80％、85％或90％(重量)的异丁烯聚合物或共聚物。
丁基橡胶胶囊可以用硫硫化或树脂硫化体系硫化。硫硫化体系对于具有不饱和残基的异丁烯聚合物是不理想的，因为这样可以导致当用作硫化胶囊时返原和/或模量增加。代表性的硫化树脂的用量可以是1-10phr并包括常规酚醛树脂。常常将间甲苯酚/酚醛树脂硫化体系用于此目的。这样的胶囊组合物的硫化体系对于本领域的技术人员是公知的。例如，参见美国专利第3031423号，该专利的全文并入本文作为参考。表I示出了使用苯酚—甲醛并含有少量硫的树脂硫化体系。用来硫化丁基橡胶的反应性酚醛树脂可从市场购得并且是本领域熟知的。
硫化胶囊的硫化橡胶组合物也可含有常规添加剂，包括填充剂、胶溶剂、硬脂酸、促进剂、硫硫化剂、硫化用树脂、抗臭氧剂、抗氧剂、加工油、活化剂、引发剂、增塑剂、蜡、过早硫化抑制剂、增量油等。
如果要使用硫硫化体系，则硫的用量为每100份橡胶0.1-10(phr)份。代表性的硫硫化剂包括硫；能给出硫的硫化剂，例如二硫化胺、聚合物聚硫醚；或硫与烯烃的加合产物。缩写phr在本文中代表相对于胶囊或轮胎组合物中每100重量份橡胶的重量份数。硫的用量优选在0.5-7phr之间。
用于硫硫化体系的促进剂的用量可以是0.1-5phr，0.5-2.5phr更好。这类促进剂是公知的，包括胺、二硫化物、胍、硫脲、硫醇、噻唑、秋兰姆、亚磺酰胺、二硫代氨基甲酸酯和黄原酸酯。在这类促进剂中，有许多对于硫化胶囊体系不是太快就是太慢，但它们可以少量使用，或者上述各类促进剂中的一些特定的化合物可能适用于硫化胶囊。可以使用两种或更多种促进剂的混合物。
填充剂包括增强型填充剂如用量可以为25-75或85phr的碳黑。典型的可用的碳黑包括例如乙炔黑，N110，N121，N220，N231，N234N242，N293，N299，N326，N330，N332，N339，N343，N347，N351，N358，N375，N472，N539，N550，N683，N754和N765。
最好向硫化胶囊组合物中加入抗氧剂和抗臭氧剂。抗氧剂可以避免氧化性交联和氧化性链断裂，从而使得在暴露于氧化条件下尤其是在高温下时，橡胶的模量和断裂性能保持不变。通常用于橡胶化合物的抗氧剂和具体用于丁基橡胶的抗氧剂是本领域公知的。用量为0.1—10phr较好，大约2-6phr更好。抗臭氧剂是能避免由于暴露于臭氧中而引起链断裂的化合物。它们也是本领域公知的。抗氧剂和抗臭氧剂包括一元酚、二酚、硫酚、多元酚、氢醌衍生物、亚磷酸盐、磷酸盐混合物、硫酯、萘胺、二酚胺以及其它二芳基胺衍生物、对苯二胺、二胺、喹啉和混合胺。
最好在硫化胶囊组合物中混入填充剂。其用量为0-200phr，为30-100phr更好。优选的填充剂是碳黑。销售商如Degussa有各种粒径和不同表面反应性的碳黑。在硫化胶囊中优选使用增强型填充剂。除碳黑外还可使用硅石，硅石通常被描述为沉淀硅石、发烟硅石(fume silicas)和各种含有大量二氧化硅的天然材料。
石墨与碳黑有关，在胶囊成分中可以看作是石墨部分替代了一些碳黑。然而，石墨起着与碳黑不同的作用，并且碳黑用量的减少是为了保持或基本保持所需的粘合剂(橡胶)与填充剂的比率。
根据油和蜡与丁基橡胶和橡胶成分的其它成分的相容性，可以在硫化胶囊成分中使用各种油和蜡。它们可以被均匀分散或最好从组合物中相分离(迁移至表面)。蜡包括微晶蜡和石蜡。油包括脂-萘芳族树脂、聚乙二醇、石油、酯增塑剂、硫化植物油、松焦油、酚醛树脂、石油树脂、聚合物酯和松香。油和蜡的用量可以是0-20phr，是0-10phr更好。它们通常被认为是增塑剂和模量改性剂。脂肪酸如硬脂酸、棕榈酸和油酸的用量可以是0.1-5phr，优选大约0.2-1phr。可以存在例如大约0.5-10phr的氧化锌。
下面给出混合和模塑硫化胶囊的一般方法和实例。在班伯里密炼机或相当的设备中，将橡胶聚合物、80％(重量)碳黑、油、蜡、氧化锌和可选的石墨(若需要)混合、分散直到混合物的温度达165℃。将物料倾入薄板辊轧机(sheet-off mill)中并冷却。在第二混合阶段将冷却的物料加到班伯里密炼机或相当的设备中。然后在混合过程中加入20％(重量)碳黑，直至班伯里密炼机的温度达150℃。将物料再次加到薄板辊轧机上并冷却。在第三混合阶段中，加入硫化物(包括任何异戊二烯橡胶、树脂、促进剂和硫)并混合直至混合物的温度达115℃。然后卸出物料并冷却。
可以在注塑机或压铸机中模塑硫化胶囊。如果选用压铸模塑，则将班伯里密炼机出来的物料挤出成棒装。用硫化计测定适宜的时间，以便在特定的温度下获得最佳硫化。实际的硫化时间取决于加热速率和硫化胶囊的厚度。硫化胶囊的形状最好为环性的。在实施例中被测定的硫化胶囊材料是在171℃硫化了60分钟的。
本发明的硫化胶囊可用来模塑和硫化各种烃材料包括充气车辆轮胎和其它非车辆应用的充气轮胎。其它在带有胶囊的模压机中硫化的烃制品包括软管、各种套筒和空气弹簧(用于市售车辆的冲击吸收弹簧)。硫化胶囊具有良好的润滑性、理想的从硫化烃橡胶上脱离的特性和由于增强了润滑性而导致的较长的使用寿命。
制得的硫化胶囊最好能达到以下的一般性能：300％模量为4.0-8.0MPa，断裂强度为5-14MPa，断裂伸长为400—1000％，肖氏A硬度为35-65，热拉伸形变为5-20％(ASTM D412，在50％伸长率和190℃下16小时)，对丁基橡胶内衬的热剥离附着力为40-100N。硫化胶囊的300％模量为4—6MPa，断裂强度为8-11MPa，断裂伸长为600—800％，肖氏A硬度为40-50，热拉伸形变为12-17％，热剥离附着力为45-90N则更好。硫化胶囊在177℃老化24小时后的性能最好能达到300-800％、300-500％更好的断裂伸长，4.5-7.5MPa的300％模量，4.5-7.5MPa的断裂强度，55-65的肖氏A硬度，13.0-18.0％的热拉伸形变和0.4-1.0的润滑下的摩擦系数(ASTM D4518)。
下述表I示出了丁基橡胶硫化胶囊的对照例和实施例I。实施例I及其对照例表明了石墨对胶囊性能的影响。
表I
| 对照例(重量份) | 实施例1(重量份) | |
| 溴化的异丁烯/对甲基苯乙烯共聚物(ExxproTM) | 100g | 100g |
| 碳黑 | 55.0 | 55.0 |
| 加工油 | 6.0 | 6.0 |
| 石墨(Sythetic 1442) | 0 | 3.0 |
| 加工助剂1 | 5.50 | 5.50 |
| 硫化剂2 | 9.15 | 9.15 |
| 硫 | 0.75 | 0.75 |
| 老化前物理性能 | ||
| 断裂强度MPa | 9.78 | 9.64 |
| 断裂伸长率％ | 748 | 730 |
| 肖氏A硬度100℃ | 45 | 47 |
| 热拉伸形变％16小时，190℃，50％伸长率 | 22 | 19 |
| 自身热剥离附着力(无润滑剂)N | 109 | 82 |
| 对内衬的摩擦系数(无润滑剂) | 3.71 | 3.45 |
| 对卤化丁基橡胶内衬的剥离附着力(95℃，无润滑剂)N | 40 | 11 |
| 热拉伸形变％16小时，190℃，50％伸长率 | 22 | 22 |
| 热拉伸形变％316小时，190℃，50％伸长率 | 30 | 20 |
表I示出了由于混入3.0phr石墨而导致的硫化胶囊组合物的差异。溴化的异丁烯—对甲基苯乙烯是在实施例I和对照例中都使用的橡胶状聚合物。在三个混合步骤的第一个混合步骤中加入石墨使其得到良好的分散。反应性苯酚一甲醛硫化剂是与硫型硫化剂一起使用的。溴化的异丁烯—对甲基苯乙烯可以起卤素源的作用。在实施例I中模量比对照例中的高。自身热剥离附着力在实施例I中稍低，但也高的足以接受了。相对于内衬的摩擦系数在实施例中有所降低，这是合乎需要的。相对于囟代丁基橡胶内衬的95℃玻璃附着力降低了72.5％，这是非常合乎需要的。热拉伸形变试验值以低为好，因为这表明在使用中更能抵抗胶囊长大。胶囊长大则胶囊伸长并变大。这使得轮胎难于硫化并增加了成型和硫化缺陷的可能性。
对试样的拉伸试验是本领域公知的并可得到模量、断裂强度和伸长率值。
剥离附着力测定试验在95℃下两种不同基底之间的界面粘合。在进行试验前，将界面改性剂(如果需要)加到胶囊基底的界面上。所述改性剂包含分散于水中并用发烟硅石稠化的可乳化的硅油。将在侧面开有小窗(5mm宽，100mm长)的MylarTM，(聚酯)片置于胶囊材料与第二个基底材料(可以是未硫化的轮胎内衬材料或另一胶囊基底)之间。Mylar片上的小窗在胶囊试样与另一基底如轮胎内衬试样之间开辟了一块已知的界面粘合区。在胶囊材料和另一基底上加上织物底层并用胶粘剂和/或缝合的方法固定。将两个带有织物底层和Mylar片的装配好的基底的试样在隔膜硫化模具中于150℃和100psi(0.69MPa)的隔膜内压力下硫化28分钟。随后将装配的试样切成有Mylar纵向上和中心的小窗部分的1″(2.54cm)宽的条，两基底材料用手操作使其略微分开。然后将它们装在InstronTM型力位移试验机上，其形式应使得分离基底之间的剥离角度为180°。力位移试验机以51mm/min的速度将基底分开并记录所用的力。在粘着区所用的平均力除以试样宽度被记录为附着力值。
本文所述的硫化胶囊可用于胶囊或隔膜型模压机，用来硫化烃橡胶组合物最好是充气轮胎。这些模压机除隔膜或胶囊外最好具有一个或多个模塑表面。将未硫化的烃组合物置于模具中、合模，将胶囊或隔膜充气(通常用加热的气体如蒸汽吹胀)。这样便把未硫化组合物夹在胶囊或隔膜与一个或多个其它模具表面之间。烃橡胶一般流入并服从一个或多个其它模具表面的结构和形状，它们通常是金属或其合金并在模具操作时被固定紧。进一步加热未硫化组合物会使其硫化(也称为硫化或交联)，这就固定了服从一个或多个硬模具表面的制品的最终形状。然后将胶囊放气(解除内部压力)，以便取下模制品。根据制品的形状，可物理地移动一个或多个其它模塑表面以进一步打开模具以便取出制品。
尽管根据专利法规已提出了最佳和优选的实施方案，但本发明的范围不限于此，而受限于所附权利要求的范围。
Claims (3)
1.烃橡胶组合物的硫化模压方法，它使用可膨胀胶囊协助将所述烃橡胶组合物成型和硫化，其中胶囊成分的特征在于一种或多种异丁烯橡胶状聚合物至少占胶囊的橡胶状聚合物的50％(重量)，并且有0.1—30重量份石墨分散于整个所述胶囊中，其中所述重量份基于在所述胶囊成分中100重量份橡胶状聚合物计。
2.一种可膨胀硫化胶囊，其特征在于包含：
一种或多种异丁烯橡胶状聚合物和可选的一种或多种其它橡胶状聚合物，其中所述异丁烯橡胶状聚合物具有至少50％(重量)异丁烯单元，并且占所述胶囊的橡胶状聚合物的至少50％(重量)；
分散于整个胶囊中的0.1-30重量份的石墨；和
所述一种或多种异丁烯聚合物或共聚物的硫化剂，其中，所述重量份基于胶囊中100重量份所述一种或多种异丁烯聚合物和所述可选的橡胶状聚合物计。
3.使用可膨胀橡胶胶囊将烃橡胶硫化的方法，所述方法的特征在于包括：
将未硫化的橡胶组合物插入中间具有可膨胀橡胶胶囊和一个或多个模具表面的硫化模具中，
合模并通过加热和向所述胶囊空腔内部加入流体使其向外膨胀低住未硫化烃橡胶的内表面，强迫所述未硫化烃橡胶低住至少一个其它模具表面，
在加热和加压条件下将烃橡胶硫化，
使所述可膨胀胶囊瘪掉，并
从所述硫化模具中取出硫化的烃材料，其中可膨胀胶囊包含：
至少50重量份一种或多种具有至少50％(重量)异丁烯单元的异丁烯聚合物，
可选的其它橡胶状聚合物，
0.1-30重量份分散于整个所述胶囊中的石墨，和
一种或多种所述一种或多种异丁烯聚合物的硫化剂，其中所述重量份数基于100重量份在所述胶囊中的所述一种或多种异丁烯聚合物和所述可选的橡胶状聚合物计。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US313,953 | 1989-02-22 | ||
| US313953 | 1994-09-28 | ||
| US08/313,953 US5538218A (en) | 1994-09-28 | 1994-09-28 | Tire curing bladder with improved release from the tire innerliner |
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| Publication Number | Publication Date |
|---|---|
| CN1125169A true CN1125169A (zh) | 1996-06-26 |
| CN1057955C CN1057955C (zh) | 2000-11-01 |
Family
ID=23217898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95109566A Expired - Fee Related CN1057955C (zh) | 1994-09-28 | 1995-09-28 | 容易与轮胎内衬分离的轮胎硫化胶囊 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5538218A (zh) |
| EP (1) | EP0711642A3 (zh) |
| JP (1) | JPH08109285A (zh) |
| KR (1) | KR960010752A (zh) |
| CN (1) | CN1057955C (zh) |
| BR (1) | BR9504116A (zh) |
| CA (1) | CA2135032A1 (zh) |
| TR (1) | TR199501156A2 (zh) |
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| CN100475516C (zh) * | 2003-10-31 | 2009-04-08 | 倍耐力轮胎公司 | 用于轮胎硫化处理装置的可膨胀囊、其制造方法及用于制造车轮轮胎的方法 |
| CN101903186A (zh) * | 2007-12-18 | 2010-12-01 | 米其林技术公司 | 特别用于轮胎制造的橡胶组合物 |
| CN104291780A (zh) * | 2014-09-19 | 2015-01-21 | 明光瑞泰工业有限公司 | 一种加工新型自行车轮胎的水胎 |
| CN105722571A (zh) * | 2014-05-19 | 2016-06-29 | 横滨橡胶株式会社 | 橡胶组合物、橡胶组合物金属叠层体及硫化橡胶制品 |
| CN110461584A (zh) * | 2017-03-30 | 2019-11-15 | 米其林集团总公司 | 用于轮胎的固化囊膜 |
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| US6013218A (en) * | 1994-09-28 | 2000-01-11 | The Goodyear Tire & Rubber Company | Tire cure bladders cured with brominated phenolic resigns and containing PTFE and/or graphite |
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| US6015525A (en) * | 1998-09-03 | 2000-01-18 | The Goodyear Tire & Rubber Company | Tire cure bladder composition with alkylphenoxypoly (alkyleneoxy) alkanol |
| KR20010100739A (ko) * | 2000-05-08 | 2001-11-14 | 신형인 | 블래더와 인너부의 이형 및 윤활 효과 개선을 위한 블래더고무조성물 |
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| CN100475516C (zh) * | 2003-10-31 | 2009-04-08 | 倍耐力轮胎公司 | 用于轮胎硫化处理装置的可膨胀囊、其制造方法及用于制造车轮轮胎的方法 |
| CN100519169C (zh) * | 2003-10-31 | 2009-07-29 | 倍耐力轮胎公司 | 轮胎制造设备的可膨胀胶囊及制造法和车辆轮胎的制造法 |
| CN101903186A (zh) * | 2007-12-18 | 2010-12-01 | 米其林技术公司 | 特别用于轮胎制造的橡胶组合物 |
| CN101903186B (zh) * | 2007-12-18 | 2016-06-15 | 米其林集团总公司 | 特别用于轮胎制造的橡胶组合物 |
| CN105722571A (zh) * | 2014-05-19 | 2016-06-29 | 横滨橡胶株式会社 | 橡胶组合物、橡胶组合物金属叠层体及硫化橡胶制品 |
| CN105722571B (zh) * | 2014-05-19 | 2017-03-01 | 横滨橡胶株式会社 | 橡胶组合物、橡胶组合物金属叠层体及硫化橡胶制品 |
| CN104291780A (zh) * | 2014-09-19 | 2015-01-21 | 明光瑞泰工业有限公司 | 一种加工新型自行车轮胎的水胎 |
| CN110461584A (zh) * | 2017-03-30 | 2019-11-15 | 米其林集团总公司 | 用于轮胎的固化囊膜 |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9504116A (pt) | 1996-07-30 |
| US5538218A (en) | 1996-07-23 |
| EP0711642A2 (en) | 1996-05-15 |
| KR960010752A (ko) | 1996-04-20 |
| CN1057955C (zh) | 2000-11-01 |
| TR199501156A2 (tr) | 1996-06-21 |
| JPH08109285A (ja) | 1996-04-30 |
| EP0711642A3 (en) | 1996-12-11 |
| CA2135032A1 (en) | 1996-03-29 |
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