CN1413230A - 高度中和的乙烯共聚物以及它们在高尔夫球中的应用 - Google Patents
高度中和的乙烯共聚物以及它们在高尔夫球中的应用 Download PDFInfo
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Abstract
具有高弹性(高回复系数)和柔性(低Atti压缩)的热塑性塑料及它们在高尔夫球成分中的应用。熔融可加工、高度中和的乙烯酸共聚物及通过将脂肪族、单官能度有机酸加入酸共聚物中,然后中和掉超过90%的存在的酸基团而制备它们的工艺。
Description
发明背景
本申请是美国专利申请系列09/558,894的延续部分,本申请要求共同未决的美国专利申请系列09/422,142的优先权。
发明领域
本发明涉及熔融可加工的、高度中和的乙烯和C3-C8的α,β烯键不饱和羧酸共聚物以及制备它们的工艺。本发明涉及超过90%被中和,尤其是那些接近或恰好100%被中和的共聚物。通过在中和到高水平之前将足量的特定的有机酸(或盐)加入共聚物来制备这些共聚物。
本发明尤其涉及熔融可加工的、高度中性(大于90%)的聚合物,它们含有(1)乙烯和C3-C8的α,β烯键不饱和羧酸共聚物,其结晶性已通过附加柔化单体或其它方式受到破坏,以及(2)由于其基本上或完全抑制乙烯结晶的能力而选择的足量的不挥发、不迁移剂如有机酸(或盐)。也可以使用除有机酸(或盐)之外的试剂。
本发明还涉及热塑性塑料,当模塑成球形时,该热塑性塑料的回复系数至少为0.785(通过以125英尺/秒的初始速度将球形热塑性塑料射向一面钢墙,该钢墙离测定初始速度和回弹速度的位置是3英尺,并通过将回弹速度除以初始速度来测定回复系数)以及Atti压缩不超过100。
这些共聚物适用于制备模塑产品如高尔夫球成分、防滑鞋的热塑性鞋底,和运动用品的弹性泡沫体。它们在生产单层、双层、三层以及多层高尔夫球方面尤其适用。本发明尤其涉及球形组分(核、中心层和单层球),当以125英尺/秒的速度测量时其回复系数至少为0.785以及Atti压缩为100或更小。
相关领域的描述
一般高级高尔夫球包括三层球、双层球和多层球。“三层”球一般有一个球形模塑的中心层、缠绕在中心外围的弹性线状物质以及一个热塑性或热固性的覆盖层。“双层”球一般有一个模塑核,用一种热塑性物质将其覆盖。“多层”球一般有一个球形模塑核和在核和覆盖层之间的一个或多个中间层或包裹层。
一般利用热固性橡胶如聚丁二烯橡胶来制备三层球的中心层和双层以及多层球的核。采用热固性橡胶,需要复杂的多步工艺来制备核和中心层,且边角料不可循环使用。通过用热塑性塑料取代热固性橡胶来解决这些困难的尝试只取得有限的成功。同时,制备高级单层球的尝试未获成功。见美国专利5,155,157、英国专利申请2,164,342A和WO92/12206。根据这些文献制备的球、核和中心层价格高且缺乏在高级球中有用的耐久性、柔软性(低Atti压缩)和弹性等性能。
长期以来已经发现在高尔夫球组分和其它应用中适用的一种热塑性塑料是α-烯烃共聚物的离聚物,尤其是乙烯和C3-8的α,β烯键不饱和羧酸。美国专利3,264,272(Rees)教授了从“直接”酸共聚物制备这种离聚物的方法。“直接”共聚物是通过将所有单体同时加入而聚合的聚合物,这和接枝共聚物不同,接枝共聚物中通常是通过随后进行的自由基反应将一种单体接枝到已经存在的聚合物上。在美国专利4,351,931中叙述了制备酸共聚物的工艺,该酸共聚物是离聚物的基础。
酸共聚物可以含有破坏聚合物的结晶性的第三种“柔化”单体。当α-烯烃是乙烯时,这些酸共聚物可以描述为E/X/Y,其中E是乙烯,X是α,β烯键不饱和羧酸,尤其是丙烯酸和甲基丙烯酸,以及Y是柔化共聚单体。优选柔化共聚单体是丙烯酸的C1-C8烷基酯或甲基丙烯酸酯。X和Y可以以宽范围的百分比存在,X一般最高约为聚合物的35(重量)%,以及Y一般最高约为聚合物的50(重量)%。
已知有多种可在酸共聚物中中和酸部分的阳离子。中和度已知在宽范围内变化。一般的阳离子包括锂、钠、钾、镁、钙、钡、铅、锡、锌、铝以及这些阳离子的组合。已知中和至90%或更高,包括最高为100%,但这样高的中和度导致熔融可加工性或其它性能如延伸性和韧性的损失。对高酸性的共聚物并且当用钡、铅和锡以外的阳离子来中和共聚物时尤其如此。
发明概述
本发明的热塑性组合物含有一种聚合物,当形成直径为1.50-1.54英寸的球时,当通过以125英尺/秒的初始速度将该球射向一面钢板,该钢板离测定初始速度和回弹速度的位置是3英尺,并通过将回弹速度除以初始速度来测定回复系数时,该聚合物具有一定回弹系数(COR),以及不超过100的Atti压缩。
本发明的热塑性组合物优选含有(a)(一种或多种)少于36个碳原子的脂肪族、单官能度有机酸;和(b)乙烯和C3-C8α,β烯键不饱和羧酸共聚物以及它们的离聚物,其中(a)和(b)中所有酸的超过90%,优选接近100%,更优选100%被中和。
热塑性组合物优选含有熔融可加工的、高度中和(超过90%、优选接近100%,更优选100%)的聚合物,该聚合物包括(1)乙烯和C3-C8α,β烯键不饱和羧酸共聚物,通过加入柔化单体或其它方法如高酸性来破坏它们的结晶性,和(2)由于其基本上或完全抑制任何残存的乙烯的结晶性的能力而选择的不挥发、不迁移试剂如有机酸(或盐)。也可使用除有机酸(或盐)之外的试剂。
已经发现,通过用足量的特定有机酸(或它们的盐)来改性酸共聚物或离聚物,在不损失可加工性或其它性能如延伸性和韧性情况下高度中和该酸共聚物是可能的。在本发明中使用的有机酸是脂肪族、单官能度、饱和或不饱和有机酸,尤其是那些少于36个碳原子的有机酸,尤其是那些不挥发和不迁移并且显示离子阵列增塑和抑制乙烯结晶性的性能的有机酸。
凭借足量有机酸的使用,制备离聚物的酸共聚物中超过90%,接近100%,优选100%的酸部分可以被中和而不损失可加工性和延伸性和韧性性能。
熔融可加工的、高度中和的酸共聚物离聚物可以由下述方法制备:
(a)将(1)乙烯和(一种或多种)C3-C8的α,β烯键不饱和羧酸共聚物或(一种或多种)它们的熔融可加工离聚物(离聚物不被中和到它们已经变得难以加工的水平,即不再是熔融可加工的了)和(2)一种或多种少于36个碳原子的脂肪族、单官能度、饱和或不饱和有机酸或它们的盐进行熔融混合,然后同时或随后地,
(b)加入足量的阳离子源来增加所有酸部分的中和水平(包括那些在酸共聚物中和在有机酸中的酸部分)至高于90%,优选接近100%,更优选至100%。
优选地,本发明的高度中和的热塑性塑料可以由如下方法制备:
(a)(1)乙烯和(一种或多种)C3-C8α,β烯键不饱和羧酸共聚物或(一种或多种)它们的熔融可加工离聚物,它们的结晶性已通过加入柔化单体或其它方法破坏,与(2)足量基本上能消除残存的乙烯的结晶性的不挥发、不迁移试剂熔融混合,继而同时或随后地
(b)加入足量的阳离子源来增加所有酸部分的中和水平(包括那些在酸共聚物中的酸部分,如果不挥发、不迁移试剂为有机酸,也包括有机酸中的酸部分)至高于90%,优选接近100%,更优选至100%。
发明详述
在本公开中,术语“共聚物”用来指含有两种或多种单体的聚合物。短语“不同单体的共聚物”是指其单元是从不同单体衍生来的共聚物。“基本上含有”是指给出的组分是必需的,而少量其它的组分可在它们不妨碍本发明的可操作性的范围内使用。术语“(甲基)丙烯酸”是指甲基丙烯酸和/或丙烯酸。同样的,术语“(甲基)丙烯酸酯”是指甲基丙烯酸酯和/或丙烯酸酯。
本说明书中指出的所有参考文献,包括背景技术描述中的那些和本案要求优先权的那些参考文献全部在此引入作为参考。酸共聚物
本发明中用来制备离聚物的酸共聚物优选是“直接”酸共聚物。它们优选是α烯烃,尤其是乙烯、C3-C8的α,β烯键不饱和羧酸,尤其是丙烯酸和甲基丙烯酸,共聚物。它们可以任选含有第三种柔化单体。所谓“柔化”,是指结晶性被破坏(使得聚合物更少结晶)。合适的“柔化”共聚单体是从丙烯酸烷基酯和甲基丙烯酸烷基酯中选取的单体,其中烷基合有1-8个碳原子。
当α烯烃是乙烯时,酸共聚物可以描述为E/X/Y共聚物,其中E是乙烯,X是α,β烯键不饱和羧酸,Y是柔化单体。X优选占聚合物的3-30(优选4-25,更优选5-20)(重量)%,Y优选占聚合物的0-30(替代地3-25或10-23)(重量)%。
由于单体-聚合物的相分离,高水平酸(X)的乙烯-酸共聚物难以在连续聚合器中制备。然而可以通过采用美国专利5,028,674描述的“共溶剂技术”或通过采用略高于可以制备低酸的共聚物时的压力来避免这些问题。
特定的酸共聚物包括乙烯/(甲基)丙烯酸共聚物。它们也包括乙烯/(甲基)丙烯酸/(甲基)丙烯酸正丁酯、乙烯/(甲基)丙烯酸/(甲基)丙烯酸异丁酯、乙烯/(甲基)丙烯酸/(甲基)丙烯酸甲酯、和乙烯/(甲基)丙烯酸/(甲基)丙烯酸乙酯三元共聚物。离聚物
按照上述以“通过在制备离聚物的领域中已知的方法制备酸共聚物(见相关领域的描述)”为标题而描述的酸共聚物来制备本发明中使用的未加改性的、熔融可加工的离聚物。它们包括部分中和的酸共聚物,尤其是乙烯/(甲基)丙烯酸共聚物。可以将未加改性的离聚物中和至任何水平,只要不生成不可加工(熔融不可加工),没有适用的物理性能的聚合物。优选地,通过一种碱金属或一种碱土金属阳离子中和酸共聚物中大约15-大约80%,优选大约50-大约75%的酸部分。对具有高酸性水平(例如超过15重量%)的酸共聚物,中和比例必须较低,才能保持熔融可加工性。
在制备未加改性离聚物中适用的阳离子是锂、钠、钾、镁、钙、或锌或这些离子的组合。有机酸和盐
本发明中使用的有机酸是脂肪族的、单官能度(饱和、不饱和、或多重不饱和)有机酸,尤其是那些具有少于36个碳原子的有机酸。也可以使用这些有机酸的盐。盐可以是各种各样的,尤其包括有机酸的钡、锂、钠、锌、铋、钾、锶、镁或钙盐。
虽然和酸共聚物或离聚物熔融混合时,有机酸(或盐)具有低挥发性可能适用,但将混合物中和至高水平,尤其是接近或正好100%时,已发现挥发性不具有限制性。在100%中和时(所有共聚物和有机酸中的酸被中和),挥发性根本成为问题。这样,也可以使用更低碳含量的有机酸。然而,优选有机酸(或盐)不挥发且不迁移。优选它们是有效增塑离子阵列和/或消除乙烯和C3-C8的α,β烯键不饱和羧酸共聚物或它们的离聚物中的乙烯结晶性的试剂。所谓不挥发,它是指它们在试剂和酸共聚物熔融混合的温度下不挥发。所谓不迁移,它是指试剂在普通贮存条件下(室温)不在聚合物表面泛霜。尤其适用的有机酸包括C4-少于C36(如C34)、C6-C26,尤其是C6-C18,尤其是C6-C12有机酸。本发明中尤其适用的有机酸包括己酸、辛酸、癸酸、月桂酸、硬脂酸、二十二烷酸、芥酸、油酸、和亚油酸。填料
本发明中任选的填料组分被选来增加上述组分的混合物的密度,该选择依赖于所需的高尔夫球的类型(如单层、双层、三层或中间层),这将在下文有更为详尽的说明。一般来讲,填料是密度大于4克/立方厘米3(gm/cc)的无机物,优选大于5gm/cc,且其用量占组合物总重的0-大约60(重量)%。适用的填料的例子包括氧化锌、硫酸钡、硅酸铅和碳化钨、氧化锡,也包括其它为人熟知的相应的盐和它们的氧化物。优选填料物质为非活性或几乎非活性以及不增加韧性或提高压缩,也不明显减小回复系数。其它组分
本发明的实施中适用的附加任选添加剂包括酸共聚物石蜡(如,联合石蜡AC143认为是乙烯/16-18%的数均分子量为2,040的丙烯酸共聚物),它有助于阻止乙烯共聚物中填料物质(如氧化锌)和酸部分的反应。其它任选添加剂包括TiO2,它用作增白剂;光学增亮剂;表面活性剂;加工助剂等等。柔性、高COR的热塑性塑料
本发明涉及一种柔性和弹性的(“柔性的、高COR热塑性塑料)热塑性聚合物。当形成直径为1.50-1.54英寸的球时,这种柔性、高COR热塑性塑料的回复系数至少0.785,通过以125英尺/秒的初始速度将该球射向一面钢板,该钢板离测定初始速度和回弹速度的位置是3英尺,并通过将回弹速度除以初始速度来测定回复系数,Atti压缩不超过100。本发明进一步涉及柔性、高COR热塑性塑料,其COR值为0.790、0.795、0.800、0.805、0.810、0.815、0.820、0.825、0.830、0.835以及更高,同时Atti压缩为95、90、85、80、75以及更低。
这些柔性、高COR热塑性塑料优选是(a)上述的酸共聚物或熔融可加工的离聚物和(b)上述一种或多种脂肪族、单官能度有机酸或它们的盐的熔融混合聚合物的组合物,其中(a)和(b)中所有酸超过90%被中和。优选地,(a)和(b)中所有酸接近100%或100%被阳离子所中和。优选地,用超过中和(a)和(b)中所有酸的100%所需数量的阳离子来中和(a)和(b)中的酸。
优选地,酸共聚物为E/X/Y共聚物,其中E是乙烯,X是α,β烯键不饱和羧酸,Y是一种柔化共聚单体。X优选用量为聚合物的3-30(优选4-25,更优选5-20)(重量)%,Y优选用量为聚合物的0-30(可选3-25或10-23)(重量)%。有机酸优选为一种在E/X/Y共聚物或离聚物中不挥发、不迁移且有效增塑离子阵列和/或抑制结晶性的酸。
优选通过加入柔化单体或其它方式来破坏酸共聚物的结晶性。破坏结晶性的其它方式包括当无柔化单体可用时使用高的酸性水平。例如,在E/X/Y共聚物中,当不用Y时,X可以是用量超过18(重量)%的甲基丙烯酸或用量超过15(重量)%的丙烯酸。优选地,有机酸被选来基本上或完全抑制乙烯的结晶性,并和结晶性被破坏的酸共聚物熔融混合,接着被高度中和(所有酸的90%或更多,接近100%,甚至100%)。回弹和压缩材料的选择
本发明实施中使用的回弹和压缩性的特定组合物很大程度上依赖于所需高尔夫球的类型(如,单层球、双层球、三层球或多层球),以及所获高尔夫球所需求的性能类型,正如下面所述。三层高尔夫球的优选实施方案
按照已广为人知的,如在美国专利4,846,910中所述的技术来生产三层球。根据本发明的目的,通过注射或压塑将上述的柔性、高COR热塑性塑料模塑成一个所需尺寸的球,以制备这些三层球的中心层,用足量的填料填充,以提供大约1.6gm/cc-1.9gm/cc的中心层密度,具体依赖于中心层的直径、缠绕层、覆盖层的厚度和组成,以制成满足PGA制定的重量限制(45g)要求的高尔夫球。双层高尔夫球的优选实施方案
根据广为人知的技术生产双层球,其中在中心核上注射或压塑而成覆盖层。根据本发明的目的,通过注射或压塑将上述的柔性、高COR热塑性塑料模塑成一个所需尺寸的球,以制备这些双层球的核,用足量的填料填充,以提供大约1.14gm/cc-1.2gm/cc的核密度,具体依赖于核层的直径和包覆层的厚度和组成,以制成满足PGA制定的重量限制(45g)要求的高尔夫球。多层高尔夫球的优选实施方案
根据广为人知的技术生产多层球,其中通过注射或压塑模塑用一层或多层中间层或包裹层和外层覆盖层覆盖注射或压塑模塑的核。通过注射或压塑将上述的柔性、高COR热塑性塑料模塑成一个所需尺寸或厚度的球或层,以制备这些多层球的核和/或包裹层,该热塑性塑料用足量的填料填充,以制成满足PGA制定的重量限制(45g)要求的高尔夫球。在核和包裹层中使用的填料数量可以从0-大约60(重量)%变化,具体依赖于组分的尺寸(厚度)和球中重量的要求位置,假设最终的球满足所需重量的限制。填料可以用核中而不在包裹层中使用,在包裹层而不在核中使用,或两者都用。虽然不拟限制可能的组合,但该实施方案包括:
1.一个含有与三层球中心层相同的组合物的核,而包裹层则由本领域公知的任何组合物制成,
2.一个含有与双层球或三层球中心层相同组合物的核,一个用本发明中的组合物制成的包裹层,加入填料或不加,以调整提供所需重量的高尔夫球,
3.一个用任何组合物(包括热固性组合物,如聚丁二烯橡胶)制成的核,它有一个用本发明中的组合物制成的包裹层,加入填料或不加,以保证所得的最终的高尔夫球的重量满足所需的限制。覆盖层
本发明包括含有上述柔性、高COR热塑性塑料的高尔夫球的覆盖层。可以通过对上述柔性、高COR热塑性塑料(有或没有填料、其它组分、以及其它热塑性塑料包括其它离聚物)进行注射或压塑模塑成型制备覆盖层,覆盖在双层高尔夫球的热塑性或热固性的核上,在包围在热塑性或热固性核的缠绕层上,或作为多层高尔夫球的最外层。单层高尔夫球的优选实施方案
可以通过广为人知的注射或压塑技术制备单层球。它们具有传统的波纹状并且可以用氨酯漆涂附或为了外观原因涂油漆,但是这种涂层和/或漆层不能影响球的性能特征。
通过注射或压塑将上述的柔性、高COR热塑性塑料模塑成一个所需尺寸的球,以制备本发明的单层球,用足量的填料进行填充,使得得到的高尔夫球满足PGA规定的重量限制(45g)。优选地,使用足够的填料使得球的密度为1.14gm/cc。制备高度中和的离聚物的工艺
本发明的熔融可加工的、高度中和的酸共聚物可以按如下方法生产
(a)将乙烯,α,β烯键不饱和的C3-C8羧酸共聚物或它们的离聚物,它们没有被中和到难以加工(不能熔融加工)的水平,和一种或多种脂肪族、单官能度、饱和或不饱和的少于36个碳原子的有机酸或该有机酸的盐熔融混合并同时或随后地,
(b)加入足量的阳离子源以增加所有酸部分(包括酸共聚物中和有机酸中的酸)的中和水平至超过90%,优选接近100%,更优选恰好100%。
该脂肪族、单官能度、饱和或不饱和有机酸优选少于36个碳原子,或按占乙烯α,β烯键不饱和的C3-C8羧酸共聚物或它们的离聚物的重量比计,有机酸的盐的用量在每100份(pph)大约5-大约150份(也可选大约25-大约80)。
已经发现按这种方式(同时或随后)中和酸共聚物和有机酸是唯一不用惰性稀释剂来中和共聚物,又不会导致可加工性和诸如韧性及伸长等性能损失到超过单独用该离聚物时熔融加工性和性能损失程度的途径。例如,可以中和酸共聚物到超过90%,优选到大约100%或恰好到100%的中和度,而在将酸共聚物中和到超过90%的同时不损失熔融可加工性。另外,中和到大约100%或到100%可减少当模塑混合物中和度小于100%时观察到的有机酸在模具排气孔处的沉积。
可以将酸共聚物或未改性、熔融可加工的离聚物核有机酸或盐按本领域公知的任何方式进行熔融混合。例如,可以制备组分的盐和pepper混合物,然后可以在一个挤出机中熔融混合该组分。
可以本领域公知的方法将仍可熔融混合、酸共聚物/有机酸-或-盐混合物中和或进一步中和。例如,可以用Werner&Pfleiderer双螺杆挤出机来同时中和酸共聚物和有机酸。
根据共聚物或三元共聚物的酸性水平,可以基于本说明书的公开来确定控制可加工性的有机酸的水平。有机酸的百分比必须高,以便在共聚物或三元共聚物主链中达到高酸性水平。例如下表(表1),表中对比了E/14-16%nBA/AA三元共聚物中不同酸性水平获得的熔融指数。只需要少量的低分子量有机酸便可达到与大量高分子量有机酸相同的效果。
制备高度中和、熔融可加工离聚物的工艺包括如下步骤
(a)(1)乙烯α,β烯键不饱和羧酸共聚物或它们的熔融可加工离聚物,其中酸共聚物的乙烯结晶性已被破坏;和(2)足量的用于基本上或完全抑制乙烯α,β烯键不饱和的羧酸共聚物或它们的熔融可加工的离聚物的剩余乙烯结晶性的不挥发、不迁移试剂,进行熔融混合,以及
(b)同时或随后加入足量的阳离子源来中和酸共聚物或它们的离聚物到超过90%(优选接近100%或至少100%)的所有酸部分,加入量以不挥发、不迁移剂含有酸部分,不挥发、不迁移试剂的酸部分为度。
优选不挥发、不迁移试剂的存在量是大约5-大约150(可选大约25-大约80)pph,以乙烯α,β烯键不饱和的C3-8羧酸共聚物或它们的离聚物的重量计。
优选地,阳离子源的用量超过中和酸共聚物或它们的离聚物中所有酸部分所需的数量,加入量以不挥发、不迁移时间含有酸部分,不挥发、不迁移试剂的酸部分为度。
优选地,该工艺使用乙烯α,β烯键不饱和羧酸共聚物或它们的熔融可加工离聚物,它是E/X/Y共聚物或E/X/Y共聚物的熔融可加工离聚物,其中E是乙烯,X是C3-C8的α,β烯键不饱和羧酸,Y为柔化剂,其中X占E/X/Y共聚物的大约4-25(重量)%,Y占E/X/Y共聚物的3-25(重量)%。
优选不挥发、不迁移试剂为有机酸或盐,更优选油酸。
表1
硬脂酸水平和%AA与熔融指数的对照
热塑性塑料 高度中和、熔融可加工的离聚物
酸水平 | 树脂基M.I. | 硬脂酸水平 | ||||
20% | 30% | 35% | 40% | 45% | ||
8.1%AA | 67.9 | 1.8 | 2 | 6 | ||
约8.3%AA | 62.5 | 1.08 | 1.13 | 2.25 | ||
10.1%AA | 66.8 | 0.62 | 1.55 | 2.22 | ||
约6.8%AA | 75 | 1.25 | 1.92 | 6.52 | ||
约4.9%AA | 86 | 4.9 | 9.7 | 23.2 |
本发明的最终热塑性组合物基本上含有(a)少于36个碳原子的脂肪族、单官能度有机酸;和(b)乙烯、α,β烯键不饱和羧酸共聚物和它们的离聚物,其中超过90%,优选接近100%,更优选100%的所有酸被中和。
本发明的最终高度中和、熔融可加工酸共聚物可以和其它组分熔融混合以制备最终产品。例如,可以将其和共同未决美国专利系列09/422,142中使用的组分熔融混合以制备单层、双层、三层核多层高尔夫球和在鞋类及其它运动球类如垒球中适用的发泡材料。在这种情况下和所得的高度中和、熔融可加工的酸共聚物共同使用的组分包括从共聚醚酯、共聚醚酰胺、弹性聚烯烃、苯乙烯二烯嵌段共聚物和热塑性聚氨酯中选择的热塑性聚合物组分以及填料。
实施例的测试标准
通过将具有高尔夫球尺寸的注射成型的干净的树脂球以由空气压力决定的速度的从气枪中射出测量回复系数(COR)。初始速度一般为125英尺/秒。该球碰撞一块钢板,该钢板离测量初始速度的位置为3英尺,经过一个速度监测设备回弹,该设备和初始速度测量的位置相同。用回弹速度除以初始速度就是COR。
PGA收缩定义为高尔夫球的抗形变能力,用Atti机测量。
根据ASTM D1708测量抗张性能(断裂强度、断裂伸长、屈服强度、和屈服伸长)。
测量回弹百分比的方法为:将球(或三层的中心层/两层核)从高度为100英寸的地方落下,并测量从一个坚固、刚性表面如厚钢板或石块的回弹。可接受的结果为65-85%。
实施例
表中括弧里的数字代表混合物中组分的重量百分比。
采用Werner&Pleiderer双螺杆挤出机,将4812g硬脂酸加入7218g的E/23nBA/9.6MAA聚合物中。向该混合物中加入足量的氢氧化镁以中和存在的酸的90%或95%以上。(见表1中的实施例1a和1b)。
将另外两种树脂和表2中引用的组合物与硬脂酸和氢氧化镁反应。然而,在这种情况下,加入足量的氢氧化镁中和存在的所有酸的100%。这些混合的阴离子离聚物实施例1c和1d列于表2。
表2
硬脂酸镁改性的镁离聚物
实例号 | 树脂组合物 | 阳离子类型 | 有机酸(%) | 中和百分比 | M.I.(g/10min) |
1a | E/23nBA/9.6MAA | Mg | 硬脂酸(40) | 90 | 5.2 |
1b | E/23nBA/9.6MAA | Mg | 硬脂酸(40) | 95 | 3.6 |
1c | E/15nBA/8.5AA | Mg | 硬脂酸(40) | >100 | 1.15 |
1d | E/16nBA/12AA | Mg | 硬脂酸(40) | >100 | 0.09 |
实施例1c的100%被中和的树脂的性能在下表3中列出。
表3
热塑性球
PGA压缩 | COR | 断裂强度(磅/英寸2) | 屈服强度(磅/英寸2) | 断裂伸长(%) | 屈服伸长(%) |
90 | 0.787 | 2802 | 2069 | 340 | 28 |
下例描述了为测试用的球的混合物的制备。表5中给出的制备混合物的挤出条件列于表4。
表4制备混合物(表5)的挤出条件
挤出速度(转/分) | 1区温度(℃) | 2-3区温度(℃) | 4-9区温度(℃) | 模头温度(℃) | 速率(1b/hr) | Vac.(英寸) |
100-300 | 75-100 | 125-150 | 140-240 | 200-230 | 15-25 | 28 |
表5
样品 | 树脂类型(%) | 酸类型(%) | 阳离子(中和百分比) | M.I.(g/10分钟) |
1A | A(60) | 油酸(40) | 镁(100) | 1.0 |
2B | A(60) | 油酸(40) | 镁(105)* | 0.9 |
3C | B(60) | 油酸(40) | 镁(100) | 0.9 |
4D | B(60) | 油酸(40) | 镁(105)* | 0.9 |
5E | B(60) | 硬脂酸(40) | 镁(100) | 0.85 |
A-乙烯,14.8%丙烯酸正丁酯,8.3%的丙烯酸
B-乙烯,14.9%丙烯酸正丁酯,10.1%的丙烯酸
*表示阳离子足以中和树脂和有机酸中105%的所有酸。
制备直径为1.53英寸的球,采用表7中所用数据,其模塑条件列于表6。
表6球的模塑条件
温度,(℃)
机后 183
机中 173
机前 173
挤出口 177
模具前端/后端 10
熔体 195
压力(Kg/cm2)
第一阶段注射 130
第二阶段注射 110
保压阶段 13
周期时间(秒)
注入 10
保压 480
增压 10
固化时间 15
螺杆退回 5.35
表7
样品 | Atti压缩 | COR,在125英尺/秒初速下 |
1A | 75 | 0.826 |
2B | 75 | 0.826 |
3C | 78 | 0.837 |
4D | 76 | 0.837 |
5E | 97 | 0.807 |
结果表明COR值明显高于0.785,而Atti压缩小于100。可以用高密度的填料如氧化锌填充这些树脂,并用聚醚酯柔化,该聚醚酯可以从E.I.杜邦公司和商标为Hytrel的公司获得,提供热塑性高尔夫球的部分。
Claims (27)
1.一种含有热塑性聚合物的组合物,该聚合物形成直径为1.50-1.54英寸的球时,回复系数至少为0.785,通过将初始速度为125英尺/秒的球射向一块钢板,该钢板离测定初始速度的位置3英尺,并用从钢板回弹的速度除以初始速度来测量回复系数,Atti压缩不超过100。
2.权利要求1的组合物,其中COR至少为0.800。
3.权利要求2的组合物,其中COR至少为0.810。
4.一种熔融可加工的热塑性组合物,它基本上由以下成分组成,(a)E/X/Y共聚物,其中E是乙烯,X是C3-C8α,β烯键不饱和羧酸,Y是柔化共聚单体,或E/X/Y共聚物的离聚物,其中X占E/X/Y共聚物的大约3-30(重量)%,Y占E/X/Y共聚物的0-大约30(重量)%;和(b)一种或多种脂肪族、单官能度的少于36个碳原子的有机酸或它们的盐,其中超过(a)和(b)所有酸的90%被中和。
5.权利要求4的组合物,其中有机酸或它们的盐不挥发、不迁移且有效地增塑离子阵列,并且/或抑制E/X/Y共聚物或离聚物中的结晶性。
6.权利要求5的组合物,其中X占E/X/Y共聚物的大约4-25(重量)%,Y占E/X/Y共聚物的大约3-25(重量)%。
7.权利要求6的组合物,其中X占E/X/Y共聚物的大约5-20(重量)%,Y占E/X/Y共聚物的大约10-23(重量)%。
8.权利要求5的组合物,其中X为用量超过18(重量)%的甲基丙烯酸,或是用量超过15(重量)%的丙烯酸,且不用Y。
9.权利要求6、7或8的组合物,其中所选的有机酸基本上或完全抑制乙烯的结晶性。
10.权利要求4的组合物,其中(a)和(b)中所有酸的大约100%被中和。
11.权利要求10的组合物,其中用超过中和(a)和(b)中100%酸所需阳离子的过量阳离子源来中和(a)和(b)中的酸。
12.权利要求4的组合物,其中有机酸为一种或多种C6-C26有机酸。
13.权利要求12的组合物,其中有机酸为一种或多种C6-C18有机酸。
14.权利要求13的组合物,其中有机酸为一种或多种C6-C12有机酸。
15.权利要求4的组合物,其中当形成直径为1.50-1.54英寸的球时,热塑性聚合物的回复系数至少为0.785,通过以125英尺/秒的初始速度将该球射向一块钢板,该钢板离测定初始速度的位置为3英尺,测量从钢板弹回的速度,用弹回速度除以初始速度来测量回复系数,Atti压缩不超过100。
16.制备高度中和、熔融可加工离聚物的工艺,包括如下步骤:
(a)将乙烯α,β烯键不饱和羧酸共聚物或它们的熔融可加工离聚物和有机酸或有机酸的盐熔融混合,和
(b)同时或随后,用足量的阳离子源以中和酸共聚物或它们的离聚物及有机酸或它们的盐中超过90%的酸部分。
17.权利要求16的工艺,其中加入足量的阳离子源以中和大约100%的酸部分。
18.权利要求17的工艺,其中阳离子源的用量超过中和酸共聚物或它们的离聚物和有机酸或它们的盐中的所有酸部分所需的用量。
19.制备高度中和、熔融可加工离聚物的工艺,包括如下步骤:
(a)将(1)乙烯α,β烯键不饱和羧酸共聚物或它们的熔融可加工离聚物,其中酸共聚物的乙烯结晶性已被破坏;和(2)足量的用于基本上或完全消除乙烯α,β烯键不饱和羧酸共聚物或它们的熔融可加工离聚物中的剩余乙烯结晶性的不挥发、不迁移试剂熔融混合,和
(b)同时或随后加入足量阳离子源以中和酸共聚物或它们的离聚物中超过90%的所有酸部分,用量以不挥发、不迁移试剂含有酸部分,不挥发、不迁移试剂的酸部分为度。
20.权利要求19的工艺,其中乙烯α,β烯键不饱和羧酸共聚物或它们的熔融可加工离聚物是E/X/Y共聚物或E/X/Y共聚物的熔融可加工离聚物,其中E是乙烯,X是C3-C8的α,β烯键不饱和羧酸,Y是柔化单体,其中X的用量占E/X/Y共聚物的大约4-25(重量)%,Y占E/X/Y共聚物的大约3-25(重量)%,其中不挥发、不迁移试剂为一种或多种少于36个碳原子的脂肪族、单官能度有机酸或它们的盐。
21.权利要求20的工艺,其中大约100%的酸部分被中和。
22.权利要求21的工艺,其中阳离子源用量超过中和所有酸部分所需的用量。
23.含有权利要求1、2或3的组合物的高尔夫球的覆盖层。
24.含有权利要求1、2或3的组合物的双层高尔夫球的核。
25.含有权利要求1、2或3的组合物的三层高尔夫球的中心层。
26.含有权利要求1、2或3的组合物的多层高尔夫球的核或包裹层。
27.含有权利要求1、2或3的组合物的单层高尔夫球。
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Also Published As
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EP1222226B1 (en) | 2010-07-14 |
US6653382B1 (en) | 2003-11-25 |
AU8029100A (en) | 2001-04-30 |
BR0015054B1 (pt) | 2011-06-14 |
JP2003512495A (ja) | 2003-04-02 |
WO2001029129A1 (en) | 2001-04-26 |
BR0015054A (pt) | 2002-07-02 |
CN1258563C (zh) | 2006-06-07 |
EP1222226A1 (en) | 2002-07-17 |
JP5199527B2 (ja) | 2013-05-15 |
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