CN106905484A - 含有硼基团的官能化弹性体 - Google Patents
含有硼基团的官能化弹性体 Download PDFInfo
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- CN106905484A CN106905484A CN201611165926.1A CN201611165926A CN106905484A CN 106905484 A CN106905484 A CN 106905484A CN 201611165926 A CN201611165926 A CN 201611165926A CN 106905484 A CN106905484 A CN 106905484A
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- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Abstract
本发明涉及含有硼基团的官能化弹性体。本发明涉及1,3‑丁二烯或异戊二烯与式I或V的单体的共聚物，其中，R1为共价键、亚苯基、含有1至10个碳原子的直链或支链的烷二基、或者一个或多个亚苯基与一个或多个含有1至10个碳原子的直链或支链的烷二基的组合；R2和R3独立地为含有1至10个碳原子的直链或支链烷基；或者R5为含有1至20个碳原子的直链或支链烷二基、或者桥接芳族基团。本发明进一步涉及包含共聚物的橡胶组合物、和含有橡胶组合物的充气轮胎。本发明进一步涉及制造这样的共聚物的方法。
Description
技术领域
本发明涉及含有硼基团的官能化弹性体。
背景技术
在工业上以大规模生产有规立构的二烯聚合物并将其用作轮胎胶料的重要组分。具有高水平的立体有规性的二烯聚合物几乎仅使用配位聚合催化剂来制备，所述催化剂通常容易因极性官能度而中毒。由于该中毒效应，与配位催化剂相容的单体类型通常被限制为简单的烃。在轮胎工业中公知的是，即使将低水平的官能度并入某些轮胎聚合物(经由阴离子聚合或乳液聚合而制备)中，也会显著地改进含有这样的聚合物的轮胎的性能。令人遗憾的是，目前尚不存在将这样的官能化技术应用于有规立构的二烯聚合物的可靠方法，但极可能的是这样的聚合物将显示出与已知的未官能化的聚合物相比更优越的轮胎特性。
EP189174公开了2-烷氧基甲硅烷基-1,3-丁二烯单体的聚合和共聚。
WO2004/007602公开了用于1,4-二烯、苯乙烯的聚合以及用于两种单体的共聚的催化剂。本发明的催化剂的特征包括高度的立体选择性、催化活性和对极性杂质的存在的耐受性。所述催化剂结合了专属于基于Ni的二烯聚合催化剂的特征(高立体选择性和催化活性)以及明确的对极性物质的存在的特点和耐受性。
Sunada等人(Journal of Applied Polymer Science，第97卷，1545—1552(2005)公开了三乙氧基甲硅烷基改性的聚氯丁二烯(CR)胶乳，其通过将2-(3-三乙氧基甲硅烷基丙基)-1,3-丁二烯与氯丁二烯的乳液共聚来合成。
US 8,063,152公开了官能化剂，其特别可用于对活性橡胶聚合物进行官能化从而使聚合物与填料、例如炭黑和二氧化硅更相容。这些官能化剂由具有选自下述的结构式的含硼化合物组成：
和
其中，R选自氢原子、烷基和芳基，其中，R1、R2和R3可以相同或不同，并且选自烷基和芳基，且其中，R4表示亚烷基或者桥接芳基。
发明内容
本发明涉及1,3-丁二烯或异戊二烯与式I或V的单体的共聚物，
其中，R1为共价键、亚苯基、含有1至10个碳原子的直链或支链的烷二基（alkane diylgroup）、或者一个或多个亚苯基与一个或多个含有1至10个碳原子的直链或支链的烷二基的组合；R2和R3独立地为含有1至10个碳原子的直链或支链烷基；或者R5为含有1至20个碳原子的直链或支链烷二基、或者桥接芳族基团。
本发明进一步涉及包含共聚物的橡胶组合物、和含有橡胶组合物的充气轮胎。
本发明进一步涉及制造这样的共聚物的方法。
因此，本发明公开了以下实施方案。
方案1. 选自1,3-丁二烯和异戊二烯的单体与选自式I或V的单体的共聚物，
其中，R1为共价键、亚苯基、含有1至10个碳原子的直链或支链的烷二基、或者一个或多个亚苯基与一个或多个含有1至10个碳原子的直链或支链的烷二基的组合；R2和R3独立地为含有1至10个碳原子的直链或支链烷基；或者R5为含有1至20个碳原子的直链或支链烷二基、或者桥接芳族基团。
方案2. 如方案1所述的共聚物，其中，顺式1,4微结构含量大于80重量%。
方案3. 如方案1所述的共聚物，其包含至少95重量%的顺式1,4微结构含量。
方案4. 如方案1所述的共聚物，其包含0.1至40重量%的衍生自式I或V的单体的单元。
方案5. 如方案1所述的共聚物，其包含0.5至20重量%的衍生自式I或V的单体的单元。
方案6. 如方案1所述的共聚物，其包含1至5重量%的衍生自式I或V的单体的单元。
方案7. 如方案1所述的共聚物，其中，式I的单体是(E)-4,4,5,5-四甲基-2-(3-甲基丁-1,3-二烯-1-基)-1,3,2-二氧杂硼杂环戊烷。
方案8. 如方案1所述的共聚物，其中所述单体具有下述结构
。
方案9. 橡胶组合物，其包含方案1所述的共聚物。
方案10. 充气轮胎，其包含方案9所述的橡胶组合物。
方案11. 制造共聚物的方法，其包括将选自1,3-丁二烯和异戊二烯的单体与选自式I或V的单体进行聚合的步骤，
其中，R1为共价键、亚苯基、含有1至10个碳原子的直链或支链的烷二基、或者一个或多个亚苯基与一个或多个含有1至10个碳原子的直链或支链的烷二基的组合；R2和R3独立地为含有1至10个碳原子的直链或支链烷基；或者R5为含有1至20个碳原子的直链或支链烷二基、或者桥接芳族基团。
方案12. 如方案11所述的方法，其中，式V的单体是(E)-4,4,5,5-四甲基-2-(3-甲基丁-1,3-二烯-1-基)-1,3,2-二氧杂硼杂环戊烷。
方案13. 如方案11所述的方法，其中，式V的单体具有下述结构
。
方案14. 如方案11所述的方法，其中，聚合催化剂具有式II，
其中BArF 4 -是四(3,5-双(三氟甲基)苯基)硼酸根。
方案15. 如方案11所述的方法，其中，所述芳族桥接基团选自下述结构：
描述
公开的是1,3-丁二烯或异戊二烯与式I或V的单体的共聚物，
其中，R1为共价键、亚苯基、含有1至10个碳原子的直链或支链的烷二基、或者一个或多个亚苯基与一个或多个含有1至10个碳原子的直链或支链的烷二基的组合；R2和R3独立地为含有1至10个碳原子的直链或支链烷基；或者R5为含有1至20个碳原子的直链或支链烷二基、或者桥接芳族基团。
还公开的是包含共聚物的橡胶组合物、和含有橡胶组合物的充气轮胎。
还公开的是制造这样的共聚物的方法。
共聚物是经由将非官能化的二烯单体和官能化的二烯单体进行聚合而生产的。
在一个实施方案中，非官能化的二烯单体是1,3-丁二烯或异戊二烯。
在一个实施方案中，官能化的二烯单体是式I或V的单体，
其中，R1为共价键、亚苯基、含有1至10个碳原子的直链或支链的烷二基、或者一个或多个亚苯基与一个或多个含有1至10个碳原子的直链或支链的烷二基的组合；R2和R3独立地为含有1至10个碳原子的直链或支链烷基；或者R5为含有1至20个碳原子的直链或支链烷二基、或者桥接芳族基团。
在一个实施方案中，桥接芳族基团选自下述结构：
共聚物具有高度的立体有规性。在一个实施方案中，共聚物具有基于共聚物的聚丁二烯含量计大于80重量%的顺式1,4微结构含量。在一个实施方案中，共聚物具有基于共聚物的聚丁二烯含量计大于95重量%的顺式1,4微结构含量。
共聚物具有归属于衍生自非官能化的单体的单元的主要重量部分、以及归属于衍生自官能化的单体的单元的次要重量部分。在一个实施方案中，共聚物包含0.1至40重量%的衍生自官能化的二烯单体的单元。在一个实施方案中，共聚物包含0.5至20重量%的衍生自官能化的二烯单体的单元。在一个实施方案中，共聚物包含1至5重量%的衍生自官能化的二烯单体的单元。
共聚物通过在镍配位催化剂的存在下非官能化的单体和官能化的单体的聚合而生产。在一个实施方案中，催化剂是(烯丙基)(芳烃)Ni(II)化合物。适合的(烯丙基)(芳烃)Ni(II)化合物可以如在O’Connor等人(Organometallics 2009，28 2372-2384)中所述地来生产。催化剂通常为具有适合的抗衡阴离子的阳离子形式。在一个实施方案中，抗衡阴离子为四(3,5-双(三氟甲基)苯基)硼酸根(即BArF 4 -)。在一个实施方案中，催化剂是如式II中所示的(烯丙基)(均三甲苯)Ni(II)+ BArF 4 -络合物，
使用(烯丙基)(芳烃)Ni(II)催化剂的聚合可以按照如在O’Connor等人(Journal of Applied Polymer Science，Part A: Polymer Chemistry，第48卷，1901-1912 (2010))中所述的方法来完成。共聚可以通过0至60℃的温度下的溶液聚合来进行。用于溶液聚合的适合的溶剂包括甲苯、二氯甲烷和庚烷等。
可以将共聚物配混在橡胶组合物内。
橡胶组合物除包含官能化的共聚物之外，还可以任选包含一种或多种含有烯属不饱和性的橡胶或弹性体。短语“含有烯属不饱和性的橡胶或弹性体”或者“基于二烯的弹性体”意图包括天然橡胶和其多种原始和再生形式、以及多种合成橡胶。在本发明的说明书中，除非另有规定，术语“橡胶”和“弹性体”可以互换地使用。术语“橡胶组合物”、“混炼胶”、和“橡胶胶料”是互换地用来指代已掺混或混合有多种成分和材料的橡胶，并且这样的术语对于橡胶混合或橡胶配混领域的技术人员而言是公知的。代表性的合成聚合物是丁二烯和其同系物和衍生物、例如甲基丁二烯、二甲基丁二烯和戊二烯的均聚产物；以及共聚物，例如由丁二烯或者其同系物或衍生物与其他不饱和单体形成的那些。后者当中有乙炔类，例如乙烯基乙炔；烯烃，例如异丁烯，其与异戊二烯共聚从而形成丁基橡胶；乙烯基化合物，例如丙烯酸、丙烯腈(其与丁二烯聚合从而形成NBR)、甲基丙烯酸和苯乙烯，后一化合物与丁二烯聚合从而形成SBR；以及乙烯基酯和多种不饱和醛、酮和醚，例如丙烯醛、甲基异丙烯基酮、和乙烯基乙基醚。合成橡胶的具体实例包括氯丁橡胶(聚氯二烯)、聚丁二烯(包括顺式-1,4-聚丁二烯)、聚异戊二烯(包括顺式-1,4-聚异戊二烯)、丁基橡胶；卤化丁基橡胶，例如氯化丁基橡胶或溴化丁基橡胶；苯乙烯/异戊二烯/丁二烯橡胶；1,3-丁二烯或异戊二烯与单体例如苯乙烯、丙烯腈和甲基丙烯酸甲酯的共聚物，以及三元乙丙橡胶，也称为乙烯/丙烯/二烯单体(EPDM)，并特别是乙烯/丙烯/双环戊二烯三元共聚物。可以使用的橡胶的其他实例包括烷氧基-甲硅烷基末端官能化的溶液聚合的聚合物(SBR、PBR、IBR和SIBR)、硅偶联和锡偶联的星型支化聚合物。优选的橡胶或弹性体是聚异戊二烯(天然或合成)、聚丁二烯和SBR。
在一个方面，至少一种其他的橡胶优选具有至少两种基于二烯的橡胶。例如，两种或更多种橡胶的组合是优选的，例如顺式1,4-聚异戊二烯橡胶(天然或合成，尽管天然为优选)、3,4-聚异戊二烯橡胶、苯乙烯/异戊二烯/丁二烯橡胶、衍生自乳液和溶液聚合的苯乙烯/丁二烯橡胶、顺式1,4-聚丁二烯橡胶、和乳液聚合制备的丁二烯/丙烯腈共聚物。
在本发明的一个方面中，可以使用具有约20%至约28%键合苯乙烯的相对常规的苯乙烯含量的衍生自乳液聚合的苯乙烯/丁二烯(E-SBR)，或者对于一些应用而言，使用具有中等至相对高的键合苯乙烯含量、即约30%至约45%的键合苯乙烯含量的E-SBR。
通过乳液聚合制备的E-SBR意指苯乙烯和1,3-丁二烯以水性乳液的方式共聚。这些对于本领域技术人员而言是公知的。键合苯乙烯含量可以例如从约5%变化至约50%。在一个方面，E-SBR还可以以例如在三元共聚物中约2至约30重量%的键合丙烯腈的量含有丙烯腈从而形成作为E-SBAR的三元共聚物橡胶。
在共聚物中含有约2至约40重量%的键合丙烯腈的乳液聚合制备的苯乙烯/丁二烯/丙烯腈共聚物橡胶也被预期为用于本发明中的基于二烯的橡胶。
溶液聚合制备的SBR(S-SBR)典型地具有约5%至约50%、优选约9%至约36%的键合苯乙烯含量。S-SBR可以例如通过在有机烃溶剂的存在下的有机锂催化来方便地制备。
在一个实施方案，可以使用顺式1,4-聚丁二烯橡胶(BR)。这样的BR可以例如通过1,3-丁二烯的有机溶液聚合来制备。BR可以方便地被表征为例如具有至少90%的顺式1,4-含量。
顺式1,4-聚异戊二烯和顺式1,4-聚异戊二烯天然橡胶对于橡胶领域的技术人员而言是公知的。
如在本文中并且根据常规实践而使用的术语“phr”是指“每100重量份橡胶或弹性体而言的各材料的重量份”。
橡胶组合物还可以包含多至70 phr的操作油。操作油可以作为典型用来使弹性体增容的增量油而被包含在橡胶组合物中。操作油还可以通过在橡胶配混的过程中直接添加油而被包含在橡胶组合物中。所使用的操作油可以包括存在于弹性体中的增量油、以及在配混过程中添加的操作油两者。适合的操作油包括如在本领域中已知的多种油，包括芳族油、链烷烃油、环烷烃油、植物油和低PCA油，例如MES、TDAE、SRAE和重环烷烃油。适合的低PCA油包括具有如通过IP346方法确定的少于3重量%多环芳族含量的那些。IP346方法的程序可以见于英国石油学会出版的Standard Methods for Analysis & Testing of Petroleum and Related Products和British Standard 2000 Parts，2003，第62版。
橡胶组合物可以包含二氧化硅、炭黑或二氧化硅和炭黑的组合。
橡胶组合物可以包含约1至约150 phr的二氧化硅。在另一个实施方案中，可以使用10至100 phr的二氧化硅。
通常采用的可以用于橡胶胶料中的含硅颜料包括常规的热解和沉淀含硅颜料(二氧化硅)。在一个实施方案中，使用沉淀二氧化硅。在本发明中采用的常规的含硅颜料是沉淀二氧化硅，例如通过酸化可溶硅酸盐、例如硅酸钠而得到的那些。
这样的常规二氧化硅可以被表征为例如具有如使用氮气测量的BET表面积。在一个实施方案中，BET表面积可以为约40至约600平方米每克。在另一个实施方案中，BET表面积可以为约80至约300平方米每克。测量表面积的BET方法在Journal of the American Chemical Society，第60卷，第304页 (1930)中描述。
常规的二氧化硅还可以被表征为具有约100至约400、替代地为约150至约300的邻苯二甲酸二丁酯(DBP)吸收值。
可以期望常规的二氧化硅具有例如0.01至0.05微米的如通过电子显微镜确定的平均最终粒度，尽管二氧化硅颗粒可能在尺寸方面甚至更小或者可能更大。
可以使用多种市售的二氧化硅，在本文中仅举例而非限制地例如可商业获自PPGIndustries的Hi-Sil商标下具有210、243等名称的二氧化硅；可获自Rhodia的具有例如Z1165MP和Z165GR名称的二氧化硅；以及可获自Degussa AG的具有例如VN2和VN3等名称的二氧化硅。
通常采用的炭黑可以以1至150 phr的量与二氧化硅组合被用作常规填料。在另一个实施方案中，可以使用10至100 phr的炭黑。尽管炭黑可以与二氧化硅一起使用，但在一个实施方案中，除了对轮胎赋予黑色而需要的1至10 phr的量之外，基本上不使用炭黑。这样的炭黑的代表性实例包括N110、N121、N134、N220、N231、N234、N242、N293、N299、N315、N326、N330、N332、N339、N343、N347、N351、N358、N375、N539、N550、N582、N630、N642、N650、N683、N754、N762、N765、N774、N787、N907、N908、N990和N991。这些炭黑具有9至145 g/kg的碘吸收和34至150 cm3/100 g的DBP数。
可以在组合物中使用二氧化硅和炭黑的组合。在一个实施方案中，二氧化硅与炭黑的重量比大于或等于1。
可以在橡胶组合物中使用其他填料，其包括但不限于颗粒状填料，包括超高分子量聚乙烯(UHMWPE)；交联的颗粒状聚合物凝胶，包括但不限于在美国专利6,242,534；6,207,757；6,133,364；6,372,857；5,395,891；或6,127,488中公开的那些；以及增塑淀粉复合填料，包括但不限于在美国专利5,672,639中公开的那些。这样的其他填料可以以1至30phr的量使用。
在一个实施方案中，橡胶组合物可以含有常规的含硫有机硅化合物。在一个实施方案中，含硫有机硅化合物为3,3'-双(三甲氧基或三乙氧基甲硅烷基丙基)多硫化物。在一个实施方案中，含硫有机硅化合物是3,3’-双(三乙氧基甲硅烷基丙基)二硫化物和/或3,3'-双(三乙氧基甲硅烷基丙基)四硫化物。
在另一个实施方案中，适合的含硫有机硅化合物包括在美国专利6,608,125中公开的化合物。在一个实施方案中，含硫有机硅化合物包括3-(辛酰硫基)-1-丙基三乙氧基硅烷，CH3(CH2)6C(=O)-S-CH2CH2CH2Si(OCH2CH3)3，其可作为NXTTM商业获自MomentivePerformance Materials。
在另一个实施方案中，适合的含硫有机硅化合物包括在美国专利公开2003/0130535中公开的那些。在一个实施方案中，含硫有机硅化合物是来自Degussa的Si-363。
含硫有机硅化合物在橡胶组合物中的量将根据所使用的其他添加剂的水平而改变。通常而言，化合物的量将为0.5至20 phr。在一个实施方案中，所述量将为1至10 phr。
容易被本领域技术人员理解的是，橡胶组合物将通过在橡胶配混领域通常已知的方法来配混，例如混合多种硫可硫化的成分橡胶与多种通常使用的添加剂材料、例如硫供体、固化助剂，例如活化剂和防焦剂，以及加工添加剂、例如油、树脂(包括增粘树脂)、和增塑剂，填料、颜料、脂肪酸、氧化锌、蜡、抗氧化剂和抗臭氧剂和塑解剂。如本领域技术人员已知的，取决于硫可硫化和硫已硫化的材料(橡胶)的预期用途，对上述添加剂进行选择并通常以常规量使用。硫供体的代表性实例包括元素硫(游离硫)、胺二硫化物、聚合多硫化物、和硫烯烃加合物。在一个实施方案中，硫-硫化剂为元素硫。硫-硫化剂可以以0.5至8 phr、替代地为1.5至6 phr的量使用。如果使用，增粘树脂的典型量为约0.5至约10 phr，通常为约1至约5 phr。加工助剂的典型量为约1至约50 phr。抗氧化剂的典型量为约1至约5 phr。代表性的抗氧化剂可以是例如二苯基对苯二胺等，例如在The Vanderbilt Rubber Handbook (1978)，第344至346页中公开的那些。抗臭氧剂的典型量为约1至5 phr。如果使用，可以包括硬脂酸的脂肪酸的典型量为约0.5至约3 phr。氧化锌的典型量为约2至约5phr。蜡的典型量为约1至约5 phr。通常使用微晶蜡。塑解剂的典型量为约0.1至约1 phr。典型的塑解剂可以是例如五氯硫吩和二苯甲酰氨基二苯基二硫化物。
使用促进剂来控制硫化需要的时间和/或温度并改进硫化橡胶的特性。在一个实施方案中，可以使用单促进剂体系，即第一促进剂。一种或多种第一促进剂可以以约0.5至约4、替代地为约0.8至约1.5 phr的总量来使用。在另一个实施方案中，可以使用第一和第二促进剂的组合，其中第二促进剂以较少的量，例如约0.05至约3 phr使用，从而活化并改进硫化橡胶的特性。可以期望这些促进剂的组合对最终的特性产生协同效应，并且在某种程度上好于通过使用任一单独促进剂生产的那些特性。此外，可以使用不受常规加工温度影响但在普通的硫化温度下产生令人满意的固化的迟效性促进剂。还可以使用硫化防焦剂。可以在本发明中使用的促进剂的适合类型是胺类、二硫化物类、胍类、硫脲类、噻唑类、秋兰姆类、次磺酰胺类、二硫代氨基甲酸酯类和黄原酸类。在一个实施方案中，第一促进剂是次磺酰胺。如果使用第二促进剂，第二促进剂可以为胍、二硫代氨基甲酸酯或秋兰姆化合物。
混合橡胶组合物可以通过橡胶混合领域的技术人员已知的方法来完成。例如，典型地将成分在至少两个阶段，即至少一个非生产性阶段、然后是一个生产性混合阶段中混合。最后的包括硫-硫化剂的硫化剂典型地在最后阶段中被混合，所述阶段常规而言被称为“生产性”混合阶段，其中，混合通常在低于进行一个或多个非生产性混合阶段的一个或多个混合温度的温度或最终温度下进行。术语“非生产性”和“生产性”混合阶段对于橡胶混合领域中的技术人员而言是公知的。橡胶组合物可以经历热机械混合步骤。热机械混合步骤通常包括在混合器或挤出机中机械加工适合的时间段以产生140℃和190℃之间的橡胶温度。热机械加工的适当持续时间根据操作条件、以及组分的体积和性质而改变。例如，热机械加工可以为1至20分钟。
橡胶组合物可以被并入轮胎的多种橡胶组件中。例如，橡胶组件可以为胎面(包括胎面冠部和胎面基部)、胎侧、三角胶芯、胎圈包布、胎侧镶件、钢丝包胶(wirecoat)或内衬。在一个实施方案中，组件是胎面。
本发明的充气轮胎可以是赛用轮胎、乘用轮胎、航空轮胎、农用轮胎、推土机轮胎、非公路轮胎（off-the-road）、卡车轮胎等。在一个实施方案中，轮胎是乘用轮胎或卡车轮胎。轮胎还可以是子午线轮胎或斜交轮胎。
本发明的充气轮胎的硫化通常在约100℃至200℃的常规温度下进行。在一个实施方案中，硫化在约110℃至180℃的温度下进行。可以使用任何通常的硫化方法，例如在硫化机（press）或模具中加热、用过热蒸汽或热空气加热。这样的轮胎可以通过对本领域技术人员而言已知且将是显而易见的多种方法来成型、定型、模制和固化。
通过下述实施例来举例说明本发明，所述实施例仅出于举例说明的目的而不认为是限制本发明的范围或者其可以实践的方式。除非另有明确说明，份和百分比都以重量计给出。
具体实施方式
实施例1
Ni催化剂II的合成被描述于文献(O’Connor等人，Organometallics 2009，28 2372-2384)中。替代地，该络合物与Mg-盐和过量的NaBArF 4的混合物可以通过按照实施例2中列出的程序来生成。
实施例2
在该实施例中，举例说明了Ni(II)配位催化剂的合成。式III的化合物以如下方式被转化为式II的化合物。在100 mlSchlenk管中，将化合物III (8 mmol)与NaBArF 4 (8 mmol)和均三甲苯(20 mmol)在40 ml的二乙醚中合并，并冷却至-78℃。5分钟后，在搅拌下逐滴添加8 ml的二乙醚中的1 M烯丙基溴化镁，并在完成烯丙基溴化镁的添加后通过交换冷却浴将温度升高至-20℃。在-20℃下60分钟后，移除冷却浴并将混合物暖热至25℃，在25℃下将醚蒸馏除去从而留下粗固体。然后添加二氯甲烷(30 ml)，并搅拌混合物，接着过滤固体。对二氯甲烷溶液添加庚烷(10 mL)，并将所得到的混合物在高真空下浓缩至干从而留下6.85 g的固体，其含有约50%收率的基于Ni的催化剂II。
实施例3
在下述实施例中，举例说明了1,3-丁二烯与(E)-4,4,5,5-四甲基-2-(3-甲基丁-1,3-二烯-1-基)-1,3,2-二氧杂硼杂环戊烷(式IV)的共聚。
(E)-4,4,5,5-四甲基-2-(3-甲基丁-1,3-二烯-1-基)-1,3,2-二氧杂硼杂环戊烷。
官能性单体(E)-4,4,5,5-四甲基-2-(3-甲基丁-1,3-二烯-1-基)-1,3,2-二氧杂硼杂环戊烷可以按照如在Chemistry - A European Journal (2013)，19，(28)，9127-9131中所述的方法来合成。替代地，(E)-4,4,5,5-四甲基-2-(3-甲基丁-1,3-二烯-1-基)-1,3,2-二氧杂硼杂环戊烷可以通过下述程序以最佳收率来合成。
2-甲基丁-1-烯-3-炔的合成
根据Defranq, E.; Zesiger, T.; Tabacchi, R. Helv. Chim. Acta 1993, 76, 425-430.：将215 g 2-甲基丁-3-炔-2-醇 (2.5 mol，1当量)填入配备有滴液漏斗和蒸馏装置的1 L三颈烧瓶中。将接收烧瓶冷却至-78℃。将319 g乙酸酐(3.13 mol，1.25当量)和12g硫酸(0.12 mol，0.05当量)填入滴液漏斗中，并以50℃为起始经2小时进行逐滴添加。添加50mL后，将温度升高至70℃，并且开始产物的蒸馏(bp.：33℃/1 atm)。在完成添加后，将温度升高至80℃。用冰水洗涤产物从而除去乙酸和醇的残留物，并将其用硫酸钠干燥。
收率：55% (90 g，1.36 mol，相对于2-甲基丁-3-炔-2-醇)，清澈液体
1H NMR (400 MHz, 25 ℃, CDCl3): δ 5.38 (m, 1H, H-3), 5.29 (m, 1H, H-3),2.86 (s, 1H, H-2), 1.90 (t, 4 J 1-3 = 1.3 Hz, 3H, H-1)。
(E)-4,4,5,5-四甲基-2-(3-甲基丁-1,3-二烯-1-基)-1,3,2-二氧杂硼杂环戊烷
的合成
与由Hoveyda等人出版的程序类似，2-甲基丁-1-烯-3-炔的硼氢化在铜催化下完成(Lee, Y.; Jang, H.; Hoveyda, A. H. J. Am. Chem.Soc.2009，131，18234-18235)：在无水无氧的条件下将3.8 g (30 mmol，1当量)频哪醇硼烷、2.2 g 2-甲基丁-1-烯-3-炔 (33mmol，1.1当量)、4 mg (10 µmol，0.3 mol%) 1,3-(2,6-二异丙基苯基)亚咪唑烷-2-基（imidazolidin-2-ylidene）)氯化铜(I)和8 mg (13 µmol、0.4 mol%)叔丁醇锂搅拌2天。在真空中除去挥发物，并经由球对球蒸馏(bulb to bulb distillation)来纯化残留物。
收率：定量
1H NMR (400 MHz, 25 ℃, C6D6): δ = 7.47 (d, 3 J 4-3 = 18 Hz, 1H, H4), 5.82(dt, 3 J 3-4 = 18 Hz, 4 J 3-1 = 0.5 Hz, 1H, H3), 4.90 – 5.05 (m, 2H, H1), 1.68 (m,3H, H7), 1.09 (m, 12H, H6)
13C NMR (400 MHz, 25 ℃, C6D6): δ = 152.7 (C3), 143.4 (C2), 120.0 (C1),117.2 (b, C4), 83.1 (C5), 24.9 (C6), 17.7 (C7)。
实施例4
在该实施例中，举例说明了1,3-丁二烯与式IV的单体的共聚。实施聚合从而生产四种如表1所示的共聚物样品。
如在实施例3中所述合成式IV的官能性单体。
将式IV的单体以甲苯溶液(对于样品1-3而言甲苯总体积为15 mL，并且对于样品4为35 mL)的形式添加至经火焰干燥的Schlenk烧瓶中，并且接着用橡胶隔膜密封烧瓶。通过将其在-78℃下冷凝进甲苯中(样品1-3)或通过在反应温度下使甲苯饱和(样品4)的方式添加丁二烯。通过在所说明的反应温度下添加甲苯(5 mL)中的催化剂而引发聚合。使聚合在该温度下运行所说明的时间。添加0.5 mL的NEt3来终止聚合。小心地在减压下除去残留的丁二烯，并将聚合物在BHT (大约100 mg/100 mL)的存在下在MeOH中沉淀。将所形成的聚合物在50℃下在减压下干燥过夜从而给出所说明的以g计的收率的聚(丁二烯-共聚-(E)-4,4,5,5-四甲基-2-(3-甲基丁-1,3-二烯-1-基)-1,3,2-二氧杂硼杂环戊烷)。分析样品，在表1中给出结果。分子量Mn和多分散度(PDI)使用GPC在THF中相对聚苯乙烯标准物来测量。玻璃化转变温度Tg使用DSC来测量。聚合物的微结构通过NMR分析(1H和13C)来确定。
1 如所说明的，将催化剂以两部分加入至样品1和3中。
Claims (10)
1.选自1,3-丁二烯和异戊二烯的单体与选自式I或V的单体的共聚物，
其中，R1为共价键、亚苯基、含有1至10个碳原子的直链或支链的烷二基、或者一个或多个亚苯基与一个或多个含有1至10个碳原子的直链或支链的烷二基的组合；R2和R3独立地为含有1至10个碳原子的直链或支链烷基；或者R5为含有1至20个碳原子的直链或支链烷二基、或者桥接芳族基团。
2.如权利要求1所述的共聚物，其特征在于顺式1,4微结构含量大于80重量%。
3.如权利要求1所述的共聚物，其包含0.1至40重量%的衍生自式I或V的单体的单元。
4.如权利要求1所述的共聚物，其包含1至5重量%的衍生自式I或V的单体的单元。
5.如权利要求1所述的共聚物，其特征在于所述单体具有下述结构
。
6.橡胶组合物，其特征在于权利要求1所述的共聚物。
7.充气轮胎，其特征在于权利要求6所述的橡胶组合物。
8.制造共聚物的方法，其特征在于将选自1,3-丁二烯和异戊二烯的单体与选自式I或V的单体进行聚合的步骤，
其中，R1为共价键、亚苯基、含有1至10个碳原子的直链或支链的烷二基、或者一个或多个亚苯基与一个或多个含有1至10个碳原子的直链或支链的烷二基的组合；R2和R3独立地为含有1至10个碳原子的直链或支链烷基；或者R5为含有1至20个碳原子的直链或支链烷二基、或者桥接芳族基团。
9.如权利要求8所述的方法，其特征在于式V的单体具有下述结构
。
10.如权利要求8所述的方法，其特征在于聚合催化剂具有式II，
其中BArF 4 -是四(3,5-双(三氟甲基)苯基)硼酸根。
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| BR102015031720A2 (pt) | 2016-11-16 |
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| US9988479B2 (en) | 2018-06-05 |
| US20160177009A1 (en) | 2016-06-23 |
| EP3042786A1 (en) | 2016-07-13 |
| EP3042786B1 (en) | 2017-11-22 |
| JP6670090B2 (ja) | 2020-03-18 |
| BR102016029677A2 (pt) | 2017-06-27 |
| CN107011486A (zh) | 2017-08-04 |
| US20160177012A1 (en) | 2016-06-23 |
| JP2017149934A (ja) | 2017-08-31 |
| JP2017160412A (ja) | 2017-09-14 |
| JP6893780B2 (ja) | 2021-06-23 |
| US20160177008A1 (en) | 2016-06-23 |
| BR102016028549A2 (pt) | 2017-06-27 |
| US9994663B2 (en) | 2018-06-12 |
| CN107011486B (zh) | 2020-01-14 |
| US10087275B2 (en) | 2018-10-02 |
| US9969831B2 (en) | 2018-05-15 |
| JP6795963B2 (ja) | 2020-12-02 |
| BR102015031720B1 (pt) | 2020-06-09 |
| JP6795962B2 (ja) | 2020-12-02 |
| JP2017160413A (ja) | 2017-09-14 |
| CN106905485B (zh) | 2019-06-25 |
| JP2016135847A (ja) | 2016-07-28 |
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