CN102964520B - 共轭二烯橡胶的制造方法及其组合物 - Google Patents
共轭二烯橡胶的制造方法及其组合物 Download PDFInfo
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- CN102964520B CN102964520B CN201110438866.7A CN201110438866A CN102964520B CN 102964520 B CN102964520 B CN 102964520B CN 201110438866 A CN201110438866 A CN 201110438866A CN 102964520 B CN102964520 B CN 102964520B
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- conjugated diene
- diene rubber
- rubber
- tripoli
- modified
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- 239000013536 elastomeric material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
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- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
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- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
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- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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Abstract
本发明涉及共轭二烯橡胶的制造方法及其组合物。该方法包括:在碳氢溶剂中,利用阴离子聚合法以有机碱金属聚合共轭二烯或共轭二烯与乙烯基芳香烃化合物,以形成含有机碱金属的共轭二烯橡胶。将含有机碱金属的共轭二烯橡胶的活性端与至少一种有机硅烷化合物反应以生成改性共轭二烯橡胶。将该改性共轭二烯橡胶与水接触的同时或之后,再利用可行的热源脱除溶剂与水分,其中该改性共轭二烯橡胶的偶合率<40%,遇水后的偶合率≥50%,经过本制法处理后的初始门尼粘度MVi与经过90℃、相对湿度80%及40hr储存试验后的门尼粘度MVs之差≤10;以及硅土(silica)与共轭二烯橡胶混合。
Description
技术领域
本发明涉及一种共轭二烯橡胶的制造方法,特别涉及具优良储存稳定性的共轭二烯橡胶的制造方法及其组合物。
背景技术
溶聚丁苯橡胶(solution styrene butadiene rubber,SSBR)为丁二烯与苯乙烯单元所组成。首先由美国Phillips公司提出批次式制程(batch process)及Firestone公司提出连续式制程(continuous process),并率先实现工业化生产。由于溶聚丁苯橡胶具有比乳聚丁苯橡胶(emulsion styrene butadiene rubber,ESBR)更优异的机械性能和滚动阻力,因而广泛应用于汽车工业及其他橡胶制品。随着近来汽车对耗油量的要求降低,对用于轮胎的橡胶材料的特性需求也随之增加。共轭二烯基橡胶(conjugated diene-basedrubber)具有低滚动阻抗、优良磨耗阻抗,并因抗湿滑(wet-skid resistance)而产生更优异的操纵稳定性,使其需求性增加。
另一方面,业界已提出将用于轮胎的橡胶组成添加硅土(silica compound)或硅土与碳黑(carbon black)的混合物作为补强剂(reinforcing agent)。含有硅土或硅土与碳黑混合物的轮胎胎面(tire tread)具有低滚动阻抗及抗湿滑而产生更优异的操纵稳定性。
在已公开的相关技术中,美国专利US 4,185,042揭露了一种用于SBS嵌段共聚物的偶合剂,将含锂的高分子与偶合剂(expoxy-R2-Si(OR)2R1)反应,所获得的聚合物的偶合率>90%且无Si-OR基存在于聚合物中。
美国专利US 5,015,692揭露了一种氨基硅烷偶合丁苯橡胶,将含锂的高分子的二烯高分子链末端与偶合剂(R1R2R3-Si-(CH2)n-N-R4R5)反应改性,然而其并未揭露硅烷氧化合物改性的聚丁苯橡胶。
美国专利US 5,219,938揭露了一种两阶段改性的步骤,通过使用两种改性剂,先将含锂的高分子的二烯高分子链末端与偶合剂RnSiCl4-n或RnSnCl4-n反应改性,接着再与偶合剂(R5R6R7-Si-(CH2)n-N-R8R9)反应改性。
美国专利US 5,665,812揭露了一种含环氧基及烷氧基硅烷基改性的聚丁苯橡胶,以环氧化的硅烷氧化合物(Y-R1-Si(OR2)3)改性丁苯橡胶。
美国专利US 7,288,594揭露了以两种不同的硅烷化合物两阶段改性含锂的丁苯橡胶。另,美国专利US 7,807,747揭露以相同的硅烷化合物两阶段改性含锂的丁苯橡胶。
然而,上述现有技术皆未揭露改善改性共轭二烯橡胶储存稳定性的制程方法。就实际应用而言,业界亟需改善共轭二烯橡胶的储存稳定性、维持硅土的高反应性并维持较佳的物理特性,本发明的共轭二烯橡胶及共轭二烯橡胶组合物使用于轮胎、鞋底、地板材料、及震动阻绝材料等,并且特别适合用于轮胎,以增进轮胎胎面的低滚动阻抗及促进抗湿滑而产生更优异的操纵稳定性及可靠度。
发明内容
本发明的实施例的目的在于提供改性的共轭二烯橡胶的制造方法,使改性的共轭二烯橡胶具有较佳的储存稳定性,维持与硅土的高反应性,并具有较佳的物理特性。
根据本发明的一实施方式,提供一种共轭二烯橡胶的制造方法及其组合物,包括:在碳氢溶剂中,利用阴离子聚合法(anionic polymerization)以有机碱金属(organicalkali metal)聚合共轭二烯或共轭二烯及乙烯基芳香烃化合物,以形成含有机碱金属的共轭二烯橡胶。将含碱金属的共轭二烯橡胶的活性端与至少一种有机硅烷化合物反应以生成改性的共轭二烯橡胶。将该改性的共轭二烯橡胶进行大量水接触的同时或之后,再利用可行的热源脱除溶剂与水分,其中该改性的共轭二烯橡胶的偶合率小于40%,该改性的共轭二烯橡胶遇水后的偶合率至少为50%以上,更优选为60%以上,最优选为70%以上,以及经过本制法处理后的初始门尼粘度(Mooney viscosity)MVi与经过90℃、相对湿度80%及40小时储存试验后的门尼粘度MVs之间的差异小于或等于10。
所述有机硅烷化合物包含以下化学式的化合物:
其中R1、R2为C1~C12烷基、C6~C18芳基、或烯丙基;
R3为C1~C12烷基、或C6~C18芳基;
R4为C1~C12烷氧基、C1~C12烷基、C6~C18芳基、或烯丙基;
Y为含O和/或N原子的官能团。
优选Y为环氧烷基(epoxy)、叔胺基(amino)、仲胺或伯胺基(amine)、酯基、醛基、酮基、丙烯酸基(acrylic acid)、丙烯酸酯基(acrylate)、咪唑啉基(imidazoline),或上述的任意组合。在另一实施例中,所述改性的共轭二烯橡胶经与水接触后产生以下分子式的组合:
其中Y为含O和/或N原子的官能团;A为共轭二烯聚合物或共轭二烯及乙烯基芳香烃的共聚物。
优选Y为环氧烷基(epoxy)、叔胺基(amino)、仲胺或伯胺基(amine)、酯基、醛基、酮基、丙烯酸基(acrylic acid)、丙烯酸酯基(acrylate)、咪唑啉基(imidazoline),或上述的任意组合。
本发明的另一实施方式为改性的共轭二烯橡胶与水接触,其比例与使用的溶剂重量比为0.1以上,更优选为0.5以上,最优选为1以上。pH值为4至12,更优选为5至11,最优选为6至10。两者接触时的温度可为20至150℃,更优选为30至140℃,最优选为40至130℃,两者接触的时间为5分钟至10小时,更优选的是10分钟至8小时,最优选的是30分钟至6小时。改性的共轭二烯橡胶与水接触的同时或之后可利用蒸汽、电热、热空气或其他热源脱除溶剂,再经过熟知的干燥方式,例如:机械脱水、烘箱干燥或隧道干燥(apron dryer)方式处理。
应注意的是,经水接触的同时或之后,利用可行的热源脱除溶剂与水分,所述的已改性的共轭二烯橡胶与水接触后或同时的热源处理方法包含蒸汽汽提(steamstripping)、热气汽提(hot gas stripping)或机械干燥(mechanical drying)方法。
根据本发明另一实施方式,提供一种共轭二烯橡胶组合物,包括:改性的共轭二烯橡胶,其中该改性的共轭二烯橡胶的偶合率小于40%,该改性的共轭二烯橡胶遇水后的偶合率至少为50%以上,以及在经过蒸汽提馏后的初始门尼粘度MVi与在经过90℃、相对湿度80%及40小时储存试验后的门尼粘度MVs之间的差异小于或等于10;以及硅土(silica)。
本发明所提供的聚合物可为共轭二烯单体聚合物,或者为共轭二烯单体(例如丁二烯(butadiene)或异戊二烯(isoprene))与芳香族乙烯基单体(例如苯乙烯(styrene)或甲基苯乙烯(methyl styrene))的共聚物。本发明各实施例所提供的聚合方法包含使用有机碱金属的阴离子聚合法。本发明各实施例所提供的聚合物性质包含初始分子量为150~450kg/mole,有机硅烷化合物与含碱金属的聚共轭二烯橡胶的摩尔数比值为≥1.1,优选为≥1.2,最优选者为≥1.4,经改性后的门尼粘度为20~150,优选为30~140,更优选为35~130。
本发明的单体并不仅限于苯乙烯、丁二烯及异戊二烯,其上述的任何合适的衍生物皆可用于本发明。举例而言,芳香族乙烯基单体可以独立地选自以下项目所组成的群组:苯乙烯(styrene)、甲基苯乙烯(methylstyrene)及其所有异构物、乙基苯乙烯(ethylstyrene)及其所有异构物、环己基苯乙烯(cyclohexylstyrene)、乙烯联苯(vinylbiphenyl)、1-乙烯-5-己基萘(1-vinyl-5-hexyl naphthalene)、乙烯萘(vinylnaphthalene)、乙烯蒽(vinyl anthracene)及其上述各项的任何组合;共轭二烯单体独立地选自以下项目所组成的群组:1,3-丁二烯(1,3-butadiene)、2,3-二甲基-1,3-丁二烯(2,3-dimethyl-1,3-butadiene)、3-丁基-1,3-辛二烯(3-butyl-1,3-octadiene)、异戊二烯(isoprene)、1-甲基丁二烯(1-methylbutadiene)、2-苯基-1,3-丁二烯(2-phenyl-1,3-butadiene)及其上述各项的任何组合。
在进行聚合时,最好是使用有机锂化合物之有机碱金属作为催化剂引发剂是较佳的选择,而得到活性聚合物,其在分子链末端有碳锂离子,因而在加入单体后可再进行聚合而使分子链成长。有机锂起始剂的具体例子包括正丙基锂、异丙基锂、正丁基锂、仲丁基锂、叔丁基锂、正戊基锂、苯基锂、甲苯基锂等,优选为正丁基锂、仲丁基锂。聚合时所用的有机锂起始剂的用量取决于所欲获得聚合物的分子量,通常以全部单体的实际使用量为基准,其重量百分比落入0.005至5的范围内。
聚合反应在溶剂介质的存在中进行,适用于此聚合反应中的溶剂如惰性有机溶剂,其意为在聚合反应中不会参与反应的溶剂,此类溶剂包括丁烷、异丁烷、戊烷、正戊烷、异戊烷、2,2,4-三甲基戊烷、异己烷、正己烷、异庚烷、正庚烷、异辛烷、正辛烷的脂肪族碳氢化合物;或者像环己烷、甲基环己烷、乙基环己烷、环戊烷、环庚烷、甲基环戊烷的环烷族;或者甲苯、二甲苯、乙苯、二乙苯及丙苯等芳香烃化合物,适用于本发明的优选溶剂为环己烷与正己烷,或环己烷与丁烷的混合物。
共轭二烯橡胶的聚合溶液浓度一般为5至35%,优选为10至30%。
在一般情况下,若单纯使用惰性有机溶剂作为聚合介质,乙烯基芳香烃或共轭二烯的聚合速率较慢且两者的聚合反应性差异相当大,此时可通过加入极性溶剂的方式克服。适用于本发明的极性溶剂的具体例子包括四氢呋喃、二***、环戊醚、二丙醚、乙二醇二甲醚、乙二醇二***、二甘醇、二甲醚、甲***等醚类化合物,优选为四氢呋喃及二***。极性溶剂的存在一般皆会增加乙烯基(vinyl)的含量,适用于本发明的乙烯基范围为5~85%,可依据不同极性溶剂的属性而调整其用量使其乙烯基落于此范围内。
聚合的起始温度可于10至80℃,最终温度可于30至150℃,温度操控方法可使用绝热反应方式,也可采用恒温控制,或者采用部分冷却方式。
本发明的共轭二烯橡胶可藉由与其他橡胶成分混合而被使用为共轭二烯橡胶组合物。所述其他橡胶成分的具体例子包括传统苯乙烯-丁二烯共聚物橡胶、聚丁二烯橡胶、丁二烯-异戊二烯共聚物橡胶、及丁基橡胶。具体例子更包括天然橡胶、乙烯-丙烯共聚物橡胶、及乙烯-辛烯共聚物橡胶。上述组成可以两种或多种型式的混合应用。
从省油的观点来看,于本发明以另一橡胶成分混合本发明的共轭二烯橡胶的例子中,当所述橡胶成分全部的总量为100重量份(parts by weight)时,本发明的共轭二烯橡胶的混合含量优选为至少10重量份,且更优选为至少20重量份。
再者,本发明的共轭二烯橡胶可藉由与添加剂等混合而被使用为共轭二烯橡胶组合物。可使用已知的添加剂作为上述添加剂,且其具体例子包括硫化剂例如硫;硫化促进剂例如噻唑基(thiazole-based)硫化促进剂、秋兰姆基(thiuram-based)硫化促进剂或次磺酰胺基(sulfenamide-based)硫化促进剂;硫化活化剂例如硬脂酸或氧化锌;有机过氧化物;补强剂例如硅土或碳黑;填充剂例如碳酸钙或滑石;硅烷偶合剂;填充油;加工助剂;抗氧化剂及润滑剂。
当使用本发明的共轭二烯橡胶组合物时,其中补强剂与本发明的共轭二烯橡胶混合,优选是使用硅土作为所述补强剂。
本发明的共轭二烯橡胶组合物的形成系藉由混合硅土与本发明的共轭二烯橡胶,所混合硅土的含量相对于100重量份的本发明的共轭二烯橡胶成分(本发明共轭二烯橡胶的总含量)通常为10至200重量份。从省油的观点来看,所混合的量优选为至少20重量份,且更优选为至少30重量份。从补强效果的观点视之,优选为不超过180重量份,且更优选为不超过150重量份。
当使用非硅土的补强剂与本发明的共轭二烯橡胶混合时,从省油的观点来看,所述非硅土补强剂的混合含量,相对于100重量份的共轭二烯橡胶成分所混合补强剂的总含量优选为不超过120重量份,且更优选为不超过100重量份。从补强效果的观点来看,优选为至少1重量份,且更优选为至少3重量份。而非硅土补强剂的优选的具体例子为碳黑。
藉由将本发明的共轭二烯橡胶与另一橡胶成份、添加剂等混合制造共轭二烯橡胶组合物的方法,可使用例如习知的混合器,像是滚轮,或万马力密闭式批量混合机(Banburymixer),或密炼机(internal mixer)用以捏和(knead)各组成份的方法。
关于上述捏和的条件,除了硫化剂或硫化促进剂外,当添加剂、填充剂、硅土和/或其他补强剂混合时,捏合的温度通常为50℃至200℃,优选为80℃至150℃,并且捏合的时间通常为30秒至30分钟,优选为1分钟至30分钟。当硫化剂或硫化促进剂混合时,所述捏合的温度通常不超过100℃,优选为室温至90℃。由硫化剂或硫化促进剂混合的组成可使用例如压力硫化(press vulcanization)的硫化处理方式加以实施。所述硫化处理的温度通常为120℃至200℃,优选为140℃至180℃。
本发明的共轭二烯橡胶与共轭二烯橡胶组合物具有优异的可加工性。再者,其省油性佳。更有甚者,其具有良好的抓地性能、耐磨耗性、强度等。
本发明的共轭二烯橡胶及共轭二烯橡胶组合物系使用于轮胎、鞋底、地板材料、及震动阻绝材料等,并且特别适合用于轮胎,以增进轮胎胎面的低滚动阻抗及促进抗湿滑而产生的操纵稳定性及可靠度。
根据本发明,所提供的共轭二烯橡胶,即使在使用硅土作为补强剂时,也具有优异的可加工性及良好的省油性。本发明另提供制造所述共轭二烯橡胶的方法及含所述共轭二烯橡胶与硅土混合的组合物。
依本发明的制法产出的产品可与硅土混合后获得良好的滚动阻抗、耐磨耗性与抗拉强度,其硅土的用量为本发明共轭二烯橡胶的10%至200%,也就是100重量份的本发明共轭二烯橡胶中使用10重量份至200重量份的硅土。
用以作为补强填充材的沉析硅土为例如合成非晶质硅土,例如藉由酸化(acidification)可溶性硅酸盐(例如硅酸钠或硅酸盐与铝酸盐的共沉析)而获得。一般而言,此类沉析硅土为本领域技术人员所熟知。
所述合成硅土(沉析硅土)的BET比表面积,以氮气量测,可为例如介于范围约50至约300平方公尺/公克之间,另可选替介于范围约100至约250平方公尺/公克之间。
所述硅土也可具有邻苯二甲酸二丁酯(dibutylphthalate,DBP)吸收值,例如范围介于约100cc/g至约500cc/g之间,优选范围介于约120cc/g至约350cc/g之间。
各种商业市售的合成硅土可考虑使用于本发明中,特别是沉析硅土,包括但不限定于例如由PPG Industries所提供的商业市售硅土,例如商标Hi-Sil trademark型号210、243等;由Rhodia公司所提供的商业市售硅土,例如商品型号Zeosil 1165MP和Zeosil165GR;由EVONIK公司所提供的商业市售硅土,例如商品型号VN2、VN3、7000GR、9000GR;以及由Huber所提供的商业市售硅土,例如商品型号Zeopol 8745。
用于橡胶轮胎胎面的硅土补强剂可与偶合剂一并使用。
所述偶合剂可使橡胶中的硅土具有补强的效果,许多偶合剂已为本领域技术人员所熟知。所述偶合剂例如可与硅土颗粒预混合,或预反应,或者于橡胶/硅土制程阶段或混合阶段加入橡胶混合物中。如果偶合剂和硅土于橡胶/硅土制程阶段或混合阶段各别地加入橡胶混合物中,可考虑将所述偶合剂于原位(in situ)与硅土混合。
特别是,所述偶合剂可包括例如烷氧基硅烷,其具有结构成分或部分(烷氧基部分)能够与硅土表面(例如硅土表面的硅氢氧基(silanol group))反应,并且其结构成分或部分能够与橡胶反应,特别是含有碳-碳双键或未饱和的硫化橡胶。于此模式中,则偶合剂作用为硅土与橡胶之间的连接架桥,且藉由硅土来提高橡胶补强性的方法亦为本技术领域中具通常知识者所熟知。
以上所教示用以混合硅土与橡胶的各种偶合剂,例如含有聚硫化成分或结构的硅烷偶合剂,例如双-(3-烷氧基甲硅烷基)聚硫化物(bis-(3-alkoxysilylalkl)polysulfide),其包含从大约2到4的范围(例如从大约2到3的范围或大约3到4的范围)连接硫原子于聚硫化物架桥,例如双-(3-三乙氧基硅丙基)聚硫化物(bis-(3-triethoxysilylpropyl)polysulfide)。
为使本发明能更明显易懂,下文特举实施例,并结合附图,作详细说明如下。
附图说明
图1是显示比较例1与实施例1橡胶的储存稳定性测试的MV变化结果的示意图。
具体实施方式
以下以各实施例详细说明并结合附图说明的范例,作为本发明的参考依据。
鉴于上述目的,根据本发明的主要实施例和实施方式,提供含硅烷氧化合物(alkoxysilane compound)的改性共轭二烯橡胶适合用于制造轮胎胎面(tire tread)。然而,硅烷氧化合物的共轭二烯橡胶中具有Si-OR基,在含湿气的环境下并不稳定。所述聚共轭二烯橡胶的门尼粘度(Mooney viscosity,简称MV)在储放过程中会逐渐增加,对橡胶合成及轮胎业界而言为亟需解决的问题。所述聚共轭二烯橡胶的门尼粘度(MV)在储放过程中会逐渐增加的反应机制如下:
SBR-Si-OR+RO-Si-SBR→→SBR-Si-O-Si-SBR+ROH
SBR-Si-OH+HO-Si-SBR→→SBR-Si-O-Si-SBR+H2O
以上所举的SBR为共轭二烯橡胶的种类之一。
经水解缩合反应后,多个硅烷氧改性的共轭二烯橡胶逐渐形成具多重分链的共轭二烯橡胶,造成聚合物分子量的增加。虽然具多重分链的共轭二烯橡胶在含湿气的环境较稳定,然而其与硅土的反应性却相对降低。
根据本发明另些实施例,可替选改性的共轭二烯橡胶为以下分子式的组合:
其中Y为含O和/或N原子的官能团,优选Y为环氧烷基(epoxy)、叔胺基(amino)、仲胺或伯胺基(amine)、酯基、醛基、酮基、丙烯酸基(acrylic acid)、丙烯酸酯基(acrylate)、咪唑啉基(imidazoline),或上述的任意组合,例如-CH2CH2CH2-N(CH2CH3)2。A为共轭二烯聚合物或共轭二烯及乙烯基芳香烃的共聚物。
比较例1与实施例1
提供高压釜反应器,其初始容量约5公升以氮气充填。填入2750克的环己烷(cyclohexane),82.5克的四氢呋喃(tetrahydrofuran,缩写为THF),61克的苯乙烯(styrene)及244克的1,3-丁二烯(1,3-butadiene)于高压釜反应器中。接着,添加5.03毫摩尔(mmole)的丁基锂(n-butyl lithium),初始高分子化的温度控制在30℃。
于高分子化反应的末段,加入1.47毫摩尔(mmole)的(N,N-二甲基-3-胺丙基)三甲氧基硅烷((N,N-dimethyl-3-aminopropyl)trimethoxysilane)。经凝胶渗透层析仪(GPC)分析后,硅烷与活性共轭二烯橡胶的摩尔比约为1.4。接着,添加2,6-二叔丁基对甲酚(2,6-di-tert-butyl-p-cresol)于高分子溶液中。接着,于烘箱中将1500克的高分子溶液直接脱除溶剂干燥。干燥后的改性的共轭二烯橡胶定义为比较例1橡胶。
接着,将残余的高分子溶液去溶剂化,在该改性的共轭二烯橡胶与大量水接触后,利用可行的热源脱除溶剂与水分,例如在90℃下实施蒸汽提馏(steam stripping)步骤,水量与溶剂的重量比例为1以上,pH介于6~10之间,持续3小时,并将此橡胶于110℃下进行热轧(hot roll)干燥,经蒸汽提馏后的改性的共轭二烯橡胶定义为实施例1橡胶。
值得注意的是,本发明通过将改性的共轭二烯橡胶与水接触,其比例与使用的溶剂重量比为0.1以上,更优选为0.5以上,最优选为1以上。pH值为4至12,更优选为5至11,最优选为6至10。两者接触时的温度可为20至150℃,更优选为30至140℃,最优选为40至130℃,两者接触的时间为5分钟至10小时,更优选的是10分钟至8小时,最优选的是30分钟至6小时。改性的共轭二烯橡胶与水接触的同时或之后可利用蒸汽、电热、热空气或其他热源脱除溶剂,再经过熟知的干燥方式,例如:机械脱水、烘箱干燥或隧道干燥(apron dryer)方式处理。
经水接触后,利用可行的热源脱除溶剂与水分后,所述的已改性的共轭二烯橡胶与水接触后或同时的处理方法包含蒸汽汽提(steam stripping)、热气汽提(hot gasstripping)或机械干燥(mechanical drying)方法。
末端具有含碱金属的共轭二烯橡胶的摩尔数系以添加的单体重量除以GPC经聚苯乙烯(polystyrene)校正后未经有机硅烷化合物处理的分子量Mi而得。本文中所用的分子量均以GPC的聚苯乙烯为基准的分子量。
比较例1与实施例1橡胶的解析性质比较列于表1:
[表1]
在表1中,门尼粘度(Mooney Viscosity(ML1+4,100℃))是指预热1分钟且在100℃下持续4分钟的条件下测量的。偶合率(Coupling Ratio(C/R%))用凝胶渗透层析仪(GPC)及折射率仪测量,指分子量高于未偶合前分子量的聚合物占全部聚合物的比例,在测量时以四氢呋喃(tetrahydrofuran)作为移动相(mobile phase)。微结构(苯乙烯含量,乙烯基含量)以傅立叶转换红外线光谱仪(FTIR)测量。
比较例1与实施例1橡胶的储存稳定性测试的条件和结果如表2所示。实施例1橡胶的MV值于储存稳定性测试的过程中几乎维持定值,而比较例1橡胶的MV值于储存稳定性测试的过程中,MV值由60逐渐增加至90。另外,比较例1与实施例1橡胶的储存稳定性测试的MV变化结果,如图1所示。
[表2]
时间(小时) | 3 | 8 | 24 | 30 | 40 | |
实施例1 | MV | 87 | 90 | 92 | 92 | 91 |
比较例1 | MV | 60 | 66 | 78 | 82 | 90 |
实施例2-5
实施例2-5所使用的聚合步骤基本上与实施例1相似,为求简明之故,在此省略相同的叙述,不同之处在于实施例2为加入咪唑啉基丙基三甲氧基硅烷(imidazolinepropyltrimethoxysilane),实施例3为加入3-(2,3-环氧丙氧)丙基三甲氧基硅烷(3-glycidoxypropyltrimethoxysilane),实施例4为加入N,N-双(三甲基硅烷基)氨丙基乙基二乙氧基硅烷((N,N-bis(trimethylsilyl)aminopropylethyldiethoxysilane)),实施例5为加入3-二甲基氨乙基二乙氧基-甲基硅烷(3-dimethylaminoethyldiethoxy-methylsilane)。实施例2-5所合成的共轭二烯橡胶的解析性质比较列于表3:
[表3]
阿克隆磨耗(率):15°磨耗角,3300转,荷重2.72kg
以比较例1为指标100%,其余实施例与比较例比较的全部的比较指标数字越高越好。
本发明实施例的优点在于,通过提供含烷氧基硅烷基改性剂及蒸汽提馏(steamstripping)步骤,使改性的共轭二烯橡胶具有较佳的储存稳定性,维持与硅土的高反应性,并具有较佳的物理特性。本发明各实施例所提供的聚合物可为共轭二烯单体聚合物,或者为共轭二烯单体(例如丁二烯(butadiene)或异戊二烯(isoprene))与芳香族乙烯基单体(例如苯乙烯(styrene)或甲基苯乙烯(methyl styrene))的共聚物。本发明各实施例所提供的聚合方法包含使用有机碱金属的阴离子聚合法。本发明各实施例所提供的聚合物性质包含改性剂含锂聚共轭二烯橡胶的比值为≥1.1,经改性后的门尼粘度为20~150,经蒸汽提馏后的门尼粘度为30~150。经改性后的偶合率为<40%,而经蒸汽提馏后的偶合率为≥50%。经过蒸汽提馏后的初始门尼粘度MVi与经过90℃、相对湿度80%及40小时储存试验后的门尼粘度MVs之间的差异为≤10,测试机台型号ALPHA MOONEY MV 2000。
为了达到省油效果,将100重量份的聚合物、78.4重量份的的硅土(商品名称Ultrasil 7000GR,由EVONIK公司制造)、6.9重量份的硅烷偶合剂(商品名称Si69,由EVONIK公司制造)、50.0重量份的填充油、1.5重量份的抗氧化剂(商品名称Antigene 3C)、2重量份的硬脂酸、2重量份的氧化锌、1.5重量份的蜡、1.4重量份的硫、及2重量份硫化促进剂(商品名称CZ和D各1重量份)捏和以形成组合物。所述组合物可藉由两滚轮机模铸成片板膜,将所述片板膜加热至160℃,维持45分钟,进行硫化,由此获得硫化片板膜。
所述硫化片板于60℃下的损耗正切(loss tangent,tanδ(60℃))可藉由使用粘弹仪(viscoelastometer)量测,量测条件为1%的应变和10Hz的频率。例如,以比较例作为标准,令比较例1为100%,则实施例值愈高者,节能效果愈佳。所述硫化片板于0℃下的损耗正切(tanδ(0℃))可藉由使用粘弹仪量测,量测条件为0.5%的应变和10Hz的频率。例如,以比较例作为标准,令比较例1为100%,则实施例值愈高者,抓地煞车安全效果愈佳。
本发明虽以各种实施例揭露如上,但其并非用以限定本发明的范围,任何本领域技术人员,在不脱离本发明的精神和范围内,可做些许的更动与润饰。本发明的保护范围因以所附权利要求书的范围为准。
Claims (12)
1.一种共轭二烯橡胶的制造方法,包括:
在碳氢溶剂中,利用阴离子聚合法(anionic polymerization)以有机碱金属(organicalkali metal)聚合共轭二烯或共轭二烯及乙烯基芳香烃化合物,以形成含碱金属的共轭二烯橡胶;
将含碱金属的共轭二烯橡胶的活性端与至少一种有机硅烷化合物反应以生成改性的共轭二烯橡胶,其中该有机硅烷化合物选自以下项目所组成的群组:(N,N-二甲基-3-胺丙基)三甲氧基硅烷,咪唑啉基丙基三甲氧基硅烷,3-(2,3-环氧丙氧)丙基三甲氧基硅烷,N,N-双(三甲基硅烷基)氨丙基乙基二乙氧基硅烷,及3-二甲基氨乙基二乙氧基-甲基硅烷;以及
将该改性的共轭二烯橡胶与水接触,其比例与使用的溶剂重量比为0.1以上,在接触的同时或之后再利用热源脱除溶剂与水分;
其中该改性的共轭二烯橡胶的偶合率(coupling ratio)小于40%,该改性的共轭二烯橡胶遇水后的偶合率至少为50%以上,以及经过水处理及脱除溶剂与水分后的初始门尼粘度MVi与经过90℃、相对湿度80%及40小时储存试验后的门尼粘度MVs之间的差异小于或等于10。
2.根据权利要求1所述的共轭二烯橡胶的制造方法,其中,该共轭二烯独立地选自以下项目所组成的群组:1,3-丁二烯(1,3-butadiene)、2,3-二甲基-1,3-丁二烯(2,3-dimethyl-1,3-butadiene)、3-丁基-1,3-辛二烯(3-butyl-1,3-octadiene)、异戊二烯(isoprene)、1-甲基丁二烯(1-methylbutadiene)、2-苯基-1,3-丁二烯(2-phenyl-1,3-butadiene)及其上述各项的任何组合。
3.根据权利要求1所述的共轭二烯橡胶的制造方法,其中,该改性的共轭二烯橡胶与水接触后或同时的处理方法包含蒸汽汽提(steam stripping)、热气汽提(hot gasstripping)或机械干燥(mechanical drying)方法。
4.根据权利要求1所述的共轭二烯橡胶的制造方法,其中,该乙烯基芳香烃化合物独立地选自以下项目所组成的群组:苯乙烯(styrene)、甲基苯乙烯(methylstyrene)及其所有异构物、乙基苯乙烯(ethylstyrene)及其所有异构物、环己基苯乙烯(cyclohexylstyrene)、乙烯联苯(vinyl biphenyl)、1-乙烯-5-己基萘(1-vinyl-5-hexylnaphthalene)、乙烯萘(vinyl naphthalene)、乙烯蒽(vinyl anthracene)及其上述各项的任何组合。
5.根据权利要求1所述的共轭二烯橡胶的制造方法,其中,该有机硅烷化合物与含碱金属的共轭二烯橡胶的比值大于或等于1.1。
6.根据权利要求1所述的共轭二烯橡胶的制造方法,其中,将该改性的共轭二烯橡胶与水接触的步骤包括将该改性的共轭二烯橡胶与pH值为4至12的水接触,两者接触时的温度为20至150℃,两者接触的时间为5分钟至10小时。
7.一种共轭二烯橡胶组合物,包括:
如权利要求1所述方法合成的共轭二烯橡胶;和
硅土(silica)。
8.根据权利要求7所述的共轭二烯橡胶组合物,其中,相对于100重量份的共轭二烯橡胶,硅土用量为10-200重量份。
9.根据权利要求7所述的共轭二烯橡胶组合物,其中,硅土为合成硅土,其BET比表面积范围介于50至300平方公尺/公克之间,以及所述硅土具有范围介于100cc/g至500cc/g之间的邻苯二甲酸二丁酯吸收值。
10.根据权利要求7所述的共轭二烯橡胶组合物,其中进一步包含碳黑,且相对于100重量份的共轭二烯橡胶,所述碳黑为1-120重量份。
11.根据权利要求7所述的共轭二烯橡胶组合物,其中进一步包含聚硫化物硅烷(polysulfide silane)作为偶合剂。
12.根据权利要求7所述的共轭二烯橡胶组合物,其中,该改性的共轭二烯橡胶遇水后的偶合率至少为60%以上。
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