CN101594831A - 纤维增强的复合材料 - Google Patents

纤维增强的复合材料 Download PDF

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CN101594831A
CN101594831A CNA2007800438419A CN200780043841A CN101594831A CN 101594831 A CN101594831 A CN 101594831A CN A2007800438419 A CNA2007800438419 A CN A2007800438419A CN 200780043841 A CN200780043841 A CN 200780043841A CN 101594831 A CN101594831 A CN 101594831A
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CN101594831B (zh
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J·罗斯
M·布朗
N·麦奥利
M·霍尔
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Smith and Nephew Inc
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Smith and Nephew Richards Inc
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Abstract

本发明涉及一种纤维增强的复合材料。在一种实施方式中，该复合材料包括PLLA纤维材料和具有与所述的纤维材料的化学成分组成不同的化学成分组成的基体材料，还公开了其它纤维增强的复合材料。

Description

纤维增强的复合材料
相关申请的交叉引用
本申请是申请日为2006年11月30日的美国专利申请号60/867,978的PCT国际申请，在此将其公开全部引入作为参考。
发明背景
发明领域
本公开涉及生物可吸收的复合材料，更特别是涉及一种用于制造生物可吸收的制品的纤维增强聚合物复合材料。
相关技术
由于金属制品的高强度，已经将其用于骨折固定。虽然这些产品表现很好，但是在这些产品能给病人带来问题之处也发生很多事件。在某些情形中，金属植入物的存在可导致植入物周围的软组织受刺激，在严重的情形下这需要除去植入物。去除金属制品的操作使病人有与经历主要医疗过程相关的风险并且使最初骨折愈合的总成本增加。使除去骨折固定硬件的需要基本上减少了的一种可能解决方法是使用生物可吸收器件来固定骨折。然而，当前可采用的生物可吸收材料和制品不具有适于骨折愈合所需的初始强度和保持该强度的组合。
当前的市售生物可吸收制品包括那些由聚合物、聚合物共混物和共聚物注射成型制造的产品。这些产品已经被用在颅上颌面植入物和非承重骨折固定植入物领域，例如针和螺钉，用于腕和踝应用和软组织如韧带和腱再附着到骨上。另外，还有某些利用了这些聚合物的压缩性能的可利用的脊状产品。包含这些材料的产品是易于加工的，但是受该材料机械性能的限制。这些材料的拉伸强度在大约50MPa-100MPa之间。取决于所选择的聚合物或共聚物，这类产品保留其大部分强度持续小于约12周。因此，这些材料不适用于骨折固定应用，除了简单的非承重针和螺钉之外。
其它市售的生物可吸收产品包括自增强产品，其由于在产品加工期间的聚合物取向而具有提高的强度。尽管这些产品的强度提高了，然而其弯曲强度还是仅在250MPa左右，这限制了将该骨折固定技术用于螺钉和针。
最近，利用聚羟基乙酸(PGA)纤维已经由纤维增强聚合物复合材料制得了器件。这些复合材料具有良好的初始强度，但是由于这些纤维迅速水解而强度迅速受损。已经利用PLLA纤维和PDLLA作为基体材料制得了器件。不幸的是，该基体迅速分解并导致该复合材料的强度迅速降低。其它尝试采用了包含PLLA作为增强纤维的共聚物，例如比例为82∶18的PLLA-共-PGA共聚物。然而，已经难于找到能够在该增强纤维不劣化或破坏下被加工成复合材料的适当聚合物基体材料。最近，已经制造出这样的复合材料，其中基体是一种其化学组成与纤维相同的聚合物，或者基体是一种共混物，该共混物的大部分是一种其化学组成与基体相同的聚合物。这些复合材料的初始弯曲强度为120-140MPa，在使用大约12周内该强度损失了大部分。
使聚合物基体的降解慢下来的尝试包括使复合材料改性以加大聚合物的疏水性。但是，这要么增大了聚合物基体的结晶度，从生物学的观点来看，这是不好的，要么如果加入疏水性的橡胶组分例如聚己内酯(PCL)，其使得聚合物太柔软。缓冲材料例如碳酸钙也被加入聚合物中以减慢降解速率和改善生物学性能例如骨传导性。然而，为了得到碳酸钙的有益效果，需要其以高含量存在，约为复合材料重量的30％。由于纤维聚合物复合材料含有至少50％体积的纤维，可预期含碳酸钙的基体将会不利地干扰聚合物基体和增强纤维之间的界面。这会导致纤维增强的复合材料实质上弱化或甚至在骨折完全愈合之前瓦解。
为了制造适宜的纤维增强的复合材料，对于纤维和基体材料具有某些要求。为了使骨折愈合，该纤维需要具有高的初始拉伸强度和保留大部分该强度的能力。为了具有高的初始强度，该纤维需要高度取向并且以复合材料体积的约40％存在。另外，该纤维还应该具有一些结晶度，因为这可赋予抵抗纤维中的取向松弛的稳定性。
为了使骨折愈合，基体材料还需要能够保留其大部分强度持续适当的时间，大约6-12周左右。为了达到此目的，基体应该具有足够高的初始分子量。当聚合物降解时，分子量减小并且该聚合物变得易碎并且丧失其机械性能。可以将添加剂例如碳酸钙或其它缓冲材料加入基体中来控制降解速率。缓冲材料的量应该为基体的约30％重量，而不会不利地干扰聚合物基体和增强纤维之间的界面。
另外，基体材料必须在低得足以不显著地影响纤维强度的温度下是可加工的，并且对纤维粘附得足够好而允许应力从基体转移到纤维。为了达到此目的，半结晶和无定形共聚物两者都可被采用。半结晶共聚物典型地由乳酸与一种或多种另外的单体的单元组成，该单体单元的作用是将共聚物基体的熔点降低到在固结步骤期间纤维强度不受影响的点。无定形的或非结晶的材料例如聚(D-乳酸)聚合物，适用于与纤维一起加工，因为它们在比较低的温度下软化。然而，这些材料不具有长的强度保留时间。通过向基体材料中引入缓冲材料例如碳酸钙可以改善这种强度保留性。在这种情形中，碳酸钙起两方面作用：缓冲剂作用和在加工期间降低聚合物分解的热敏感性。合起来看，碳酸钙的影响是两方面的：减慢聚合物分解速率和有助于在加工期间保持分子量，而不会不利地干扰聚合物基体和增强纤维之间的界面。
本公开将这些要求结合起来而制造具有高初始强度并且在使用寿命期间保留该强度的大部分的生物可吸收材料。
发明概述
本公开一方面涉及一种纤维增强的复合材料，其包括PLLA纤维材料例如连续的PLLA纤维材料以及基体材料，该基体材料没有与纤维材料相同的化学成分组成。在一种实施方式中，该复合材料还包括分散于基体材料中的降解控制剂。在另一实施方式中，该降解控制剂包括选自基本上由以下物质组成的组的缓冲材料：碳酸钙、碳酸氢钙、磷酸钙、磷酸三钙、磷酸二钙、碳酸镁和碳酸钠。在又一实施方式中，该降解控制剂包括常用盐。在一种实施方式中，该降解控制剂选自包括缓冲材料、常用盐及其组合的组。在进一步的实施方式中，该降解控制剂为基体材料的约0.1％-40％重量。在又一实施方式中，该复合材料还包括分散于纤维或基体材料中的促进剂。在又一实施方式中，所述PLLA纤维材料约为复合材料的50％体积。在一种实施方式中，生物可吸收的纤维材料的拉伸强度为约500MPa-2000MPa，并且分子量为约290,000克/摩尔-516,000克/摩尔。
在一种实施方式中，基体材料是生物可吸收的并且选自包括聚合物、共聚物和聚合物共混物的组。在另一实施方式中，当聚合物共混物被用作基体时，该混合物包括至少两种聚合物并且所述聚合物中的至少一种的化学成分组成与纤维的化学成分组成不同。在又一实施方式中，所述化学成分组成不同于纤维的化学成分组成的聚合物占聚合物共混物的至少50％。在又一实施方式中，化学成分组成不同于纤维的化学成分组成的聚合物占聚合物共混物的50％以上。在又一实施方式中，所述基体材料是生物可吸收的。
在又一实施方式中，复合材料具有至少为250MPa的初始拉伸强度并且保留该初始拉伸强度的至少75％持续至少8周。在一种实施方式中，复合材料包括约为200MPa的弯曲强度和至少为140MPa的剪切强度。
另一方面，本公开包括具有基体材料、玻璃纤维材料和降解控制剂的纤维增强的复合材料。在一种实施方式中，所述基体材料选自包括聚合物、共聚物和聚合物共混物的组。在一种实施方式中，基体材料是生物可吸收的。在另一实施方式中，玻璃纤维材料是生物可吸收的。在又一实施方式中，玻璃纤维材料包括在大约300MPa-1200MPa之间的拉伸强度。在又一实施方式中，玻璃纤维材料包括疏水性材料。在又一实施方式中，玻璃纤维材料为复合材料的约50％体积。
在一种实施方式中，将降解控制剂分散于基体材料中。在另一实施方式中，降解控制剂被涂覆在纤维材料表面上。在又一实施方式中，降解控制剂为基体材料的约0.1％-40％重量。在又一实施方式中，降解控制剂包括选自包括：碳酸钙、碳酸氢钙、磷酸钙、磷酸三钙、磷酸二钙、碳酸镁和碳酸钠的组的缓冲材料。在又一实施方式中，该降解控制剂包括常用盐。在一种实施方式中，该降解控制剂选自缓冲材料、常用盐及其组合。
在又一实施方式中，复合材料具有至少为250MPa的初始拉伸强度并且保留该初始拉伸强度持续至少8周。在一种实施方式中，复合材料包括约为250MPa-400MPa的初始弯曲强度。在另一实施方式中，复合材料包括约为20-30Gpa的初始弯曲模量。在又一实施方式中，复合材料保留初始质量的约98％持续至少2周。
又一方面，本公开包括具有基体材料、纤维材料和降解控制剂的纤维增强的复合材料。
又一方面，本公开包括具有基体材料和玻璃纤维材料的纤维增强的复合材料，其中玻璃纤维材料包括300MPa-1200MPa的拉伸强度。
又一方面，本公开包括具有PLLA纤维材料和基体材料的纤维增强的复合材料，其中纤维材料包括约290,000克/摩尔-516,000克/摩尔的分子量。
由以下提供的详细说明本公开的更多应用领域将变得显而易见。应当明白，该详细说明和具体实施例，虽然指出了本公开的优选实施方式，但仅仅是为了举例说明的目的而不是限制本公开的范围。
实施方式的详细说明
以下对优选实施方式的说明只是在本质上示范而决不是限制本公开、其应用或用途。
一方面，本公开涉及一种纤维增强的复合材料，其具有PLLA纤维材料和基体材料，该基体材料没有与纤维材料相同的化学成分组成。
将连续PLLA纤维挤出和拉伸以提供拉伸强度为约500MPa-2000MPa和分子量约为290,000g/mol-516,000g/mol的纤维。用于制造纤维的挤出和拉伸可以是本领域普通技术人员已知的任何挤塑和拉伸方法。PLLA纤维材料为复合材料的约50％体积并且是生物可吸收的。
然后制造基体材料，它是生物可吸收的，并且选自聚合物、共聚物和聚合物共混物。对于本公开的目的，不具有与纤维材料相同的化学成分组成的基体材料被定义如下。如果基体材料是聚合物，那么该聚合物不可以是纯聚交酯材料。如果基体材料是共聚物，那么至少一种单体物质不是内酯单体。如果基体材料是聚合物共混物，那么至少一种聚合物具有与纤维的化学成分组成不同的化学成分组成。具有与纤维的化学成分组成不同的化学成分组成的聚合物占聚合物共混物的至少50％或更多。另一方面，具有与纤维材料相同的化学成分组成的基体材料也在本公开的范围内，其被定义如下。如果基体材料是聚合物，那么该聚合物是纯聚交酯材料。如果基体材料是共聚物，那么两种单体物质都是内酯单体。如果基体材料是聚合物共混物，那么两种聚合物都是纯聚交酯材料。
复合材料还可包括降解控制剂。为了本公开的目的，降解控制剂可包括缓冲材料、常用盐及其组合。缓冲材料选自包括(但不限于)碳酸钙、碳酸氢钙、磷酸钙、磷酸三钙、磷酸二钙、碳酸镁和碳酸钠的组。常用盐是水溶性的并且可以是有机或无机的。另外，该盐可基于(而不限于)以下之一：I族金属，包括(但不限于)锂、钠和钾；II族金属，包括(但不限于)铍、镁、钙、锶和钡；过渡金属，包括(但不限于)铜、锌、银、金、铁和钛；III族金属，包括(但不限于)铝和硼。此外，该盐可以包括(而不限于)碳酸盐、碳酸氢盐、磷酸盐、磷酸氢盐、硅酸盐、多磷酸盐和聚硅酸盐。最后，该盐可以是单一成分、化合物或其混合物。
降解控制剂被分散于基体材料中，并且被用作缓冲剂以使复合材料的降解减慢。降解控制剂为基体材料的约0.1％-40％重量。复合材料可进一步包括分散于基体材料或纤维材料中的促进剂，例如月桂酸叔丁酯或富马酸二叔丁酯。本领域普通技术人员已知的其它促进剂也可被采用。这些促进剂的使用加速了纤维或基体的分解速率。
复合材料具有至少为250MPa的初始拉伸强度并且保留该初始拉伸强度的至少75％持续至少8周。为了本公开的此目的，初始拉伸强度是指复合材料在分解之前的拉伸强度。另外，复合材料具有约为200MPa的弯曲强度以及至少为140MPa的剪切强度。
另一方面，本公开涉及一种包括基体材料、玻璃纤维材料和降解控制剂的纤维增强的复合材料。
基体材料可以是任何可生物降解的聚合物、聚合物共混物、共聚物、或本领域技术人员已知的其它可生物降解材料。可生物降解的聚合物例子包括α-聚羟基酸、聚乙交酯(PGA)、聚(L-丙交酯)、聚(D，L-丙交酯)、聚(ε-己内酯)、聚(碳酸三亚甲基酯)、聚(氧化乙烯)(PEO)、聚(β-羟基丁酸)(PHB)、聚(β-羟基戊酸)(PHVA)、聚(对二氧杂环己酮)(PDS)、聚(原酸酯)、酪氨酸衍生的聚碳酸酯、多肽、聚氨酯及其组合。
玻璃纤维材料是生物可吸收的并且占复合材料的约50％体积。可以采用本领域普通技术人员已知的任何挤塑和拉伸方法将玻璃纤维材料挤出和拉伸。该纤维包括约为300MPa-1200MPa的拉伸强度。另外，纤维材料可包括疏水性材料以使玻璃纤维材料的降解慢下来。疏水性材料可以是玻璃纤维材料组合物的组分或被涂覆在玻璃纤维材料的表面上。疏水性材料的例子包括(而不限于)聚己内酯、聚(对二甲苯)(例如聚对亚苯基二甲基)、聚交酯的异构体和共聚物、多肽、陶瓷材料(即羟磷灰石和任何形式的磷酸钙)以及可能使水渗入纤维慢下来的任何其它有机或无机的疏水性材料。为了本公开的此目的，玻璃纤维包括约50摩尔％氧化钾(P2O5)、约30摩尔％氧化钙(CaO)、约15摩尔％氧化钠(Na2O)和5摩尔％氧化铁(Fe2O3)。但是，可采用具有不同的组成的玻璃纤维。
所述降解控制剂可以是与上述降解控制剂的类型相同的降解控制剂，并且可以被分散于基体材料中或被涂覆在纤维材料的表面上。该降解控制剂起的作用是作为控制复合材料和/或玻璃纤维降解的手段。特别是，关于玻璃纤维，认为常用盐实质上减少了离子从纤维中释放。当降解控制剂被分散于基体材料中时，该降解控制剂占基体材料的约0.1％-40％重量。
所述复合材料具有至少为250MPa的初始拉伸强度并且能够保留该初始拉伸强度持续至少8周。另外，所述复合材料包括约为250MPa-400MPa的初始弯曲强度。而且，复合材料在其被置于体内条件下保留其初始质量的约98％持续至少2周。
如上所述两种复合材料的增强纤维，优选其机械性能在生理环境(水性，37℃)下测试时没有受到实质性的损害。优选该纤维在用于溶解基体聚合物的溶剂中是不溶解的。另外，两种复合材料的降解控制剂必须是一种与在聚合物纤维或基体或玻璃纤维分解期间产生的酸副产物反应的物质，其包括(但不限于)乳酸、乙醇酸、己酸和不同形式的磷酸。当降解控制剂呈微粒形式时，该粒子可具有许多尺寸，其范围为约1mm-10nm，以及具有许多几何形状，例如针状、立方体、小板、纤维、球形及本领域普通技术人员已知的其它几何形状。重要的(但不是必需的)是，粒子具有能提高该粒子的机械性能的形状。
生物制剂例如细胞、生长因子、抗生素、抗菌剂或其它这类因子可被添加到复合材料的一种或多种组分中以促进骨折愈合。
由以下实施例可得到更多的细节。
实施例1
通过取具有标称固有粘度为3.8的PLLA颗粒并将该粒料挤塑成纤维来首先制备PLLA纤维，采用配备有齿轮泵和2mm喷丝模具的单螺杆挤出机。该挤出机还具有用于空气冷却的设备。在线轴上分批处理所挤出的纤维用于下一加工步骤。随后，在高温下逐渐拉伸该纤维以产生大约为100微米的最终直径和约为8-15的拉伸比。拉伸纤维的最终分子量为约290,000g/mol-1-516,000gmol-1。所得纤维的平均拉伸强度大于约800MPa。
然后利用85∶15的PDLLA和PGA共聚物并且添加重量为35％的碳酸钙(CaCO3)作为基体材料来制备复合材料。然后将拉伸的聚(L-丙交酯)纤维缠绕在保持固定距离间隔开的平行杆的支架周围。对于每个样品，将纤维围绕支架缠绕75次，在每种复合材料中产生150条纤维。将基体以溶剂的10％wt/vol溶解于溶剂乙酸甲酯中。然后将溶剂/聚合物共混物涂覆到纤维上。然后将复合材料置于真空烘箱中在40℃持续12小时以除去溶剂。
然后将复合材料置于圆筒形模具中并加热到165℃。采用该温度来熔融基体材料以允许其流动并且将复合材料固结在一起。一旦达到热平衡，就将微小的张力施加到纤维上以使其在模具中成直线排列。然后将模具完全闭合以使纤维和基体团结。然后将闭合的模具保持在165℃持续至多5分钟，然后将其从加热的压机中取出并置于冷的金属块之间来将复合材料冷却到室温以允许张力从纤维中释放。
将复合材料样品于37℃在磷酸盐缓冲溶液(PBS)中老化。该样品的平均直径为大约1.7mm。将复合材料从老化溶液中取出、干燥，并且利用三点弯曲试验方法进行测试。如表1中所示，测试了样品的初始拉伸强度及其6、10、12和16周后的拉伸强度，与初始拉伸强度相比，在随后的几个星期期间复合材料的拉伸强度仍然很高。
表1
  星期   拉伸强度/MPa
  0   325
  6   319
  10   338
  12   291
  16   315
实施例2
在基体中有或没有混入CaCO3，并且采用一系列不同的基体材料，采用实施例1所述的方法来制备复合材料。在三点弯曲中测试所得复合材料的弯曲强度。针直径为2mm并且采用16∶1的跨度与直径比来测试该针。结果在表2中给出。显然含有降解控制剂的复合材料的机械性能没有因该材料的存在而显著地受到损害。
表2
  基体材料   复合材料的弯曲强度/MPa
  PLLA-共-PGA(85∶15)   342
  PLLA-共-PGA(82∶18)   299
  PLLA-共-PGA(82∶18)+30wt％CaCO3   311
  PDLA-共-PGA(85∶15)+35wt％CaCO3   323
实施例3
采用实施例1中所述的方法来制备复合材料，其包括聚L-乳酸(PLLA)纤维以及聚L-乳酸(PLLA)和聚羟基乙酸(PGA)的共聚物基体(PLGA 85∶15)。该复合材料不包括碳酸钙或其它降解控制剂。在37℃时在PBS中老化之后，通过三点弯曲试验测试所得针的弯曲和剪切性能。结果示于表3中。
表3
  周   弯曲强度/MPa   剪切强度/MPa
  0   251   192
  6   261   187
  12   172   190
  18   185   173
  24   87   158
实施例4
将40g聚(D，L-丙交酯-共-乙交酯)共聚物溶解于360ml CHCl3中以制备透明溶液以及将填充有聚(D，L-丙交酯-乙交酯)共聚物的61.54g碳酸钙(CaCO3)溶解于360ml CHCl3中以制备CaCO3颗粒于聚合物溶液中的悬浮液。然后将性能示于表4中且称重为4.56g-7.32g的1米长玻璃绞丝浸入溶液中并且悬挂在通风橱中以使溶剂蒸发。将所得的涂覆纤维带在80℃和1毫巴以下真空干燥到质量恒定。干燥的绞丝的重量和组成示于表5中。
表4
  纤维   A   B   C
  样品数   n＝15   n＝16   n＝11
  直径(μm)   18±5   36±6   24±5
  断裂拉伸强度(MPa)   1200±320   560±190   313±280
  拉伸弦线模量(GPa)(0.1％-0.3％应变)   101±18   82±24   39±15
表5
将涂覆的纤维带切成120mm长并且在160℃下压缩成型以制造标称测量值为10x 3x 120mm的复合材料杆。精确测量该杆并且称重来计算其组成。用三点弯曲试验方法来测试该复合材料的抗弯机械性能。该复合材料的长度/距离比为32并且试验速度为4.74mm/min。由3个测量值和1个样品失效的强度/应变来确定模量。组成和机械性能结果示于表6中。该表显示玻璃纤维复合材料具有与表2中聚合物纤维复合材料大体上相似的弯曲强度。为了本公开目的，模量是表示物质具有一种特性例如弹性的程度的量。
表6
  基体聚合物   纤维(％v/v)   模量(GPa)   强度(MPa)   断裂应变(％)
  填充的聚(D，L-丙交酯-共-乙交酯)共聚物   60.6   26.6±1.1   297.4   1.1
  聚(D，L-丙交酯-共-乙交酯)共聚物   61.6   25.9±0.3   297.1   1.2
实施例5
制备了10％w/w85∶15聚(D，L-丙交酯-共-乙交酯)共聚物和35％w/w(聚合物重量的)CaCO3在CH2Cl2中的溶液。将称重为1.5-7g的约50cm长的玻璃纤维(50mol％P2O5、30-40mol％CaO、5-15mol％Na2O、5mol％Fe2O3)称重、浸渍于聚合物溶液中并且在通风橱中挂起来干燥整夜。然后将该纤维在80℃下真空干燥并再称重。将复合材料带切成12mm长并使其随机打乱。
在型腔测量值为120x 3x 10mm的铝模具中将复合材料压缩成型。该模具衬有PTFE浸渍玻璃布带以使产品能够更容易地被取出。模塑成型是在160℃和100kN压力下进行的。将模具预热并然后在用一只手或两只手一次性地将布带装填在模具中。一旦将模具装满，就施加压力持续几秒，然后再打开模具，进一步加入布带。将此重复直至不能迫使更多的布带进入模具。然后在压力下将模具冷却到室温。修理复合材料杆，然后用基体填充层来封闭端部。该纤维的重量和组成被示于表7中。
表7
Figure A20078004384100161
测试全部样品来评估弯曲硬度并测试到其失效。在三点弯曲试验装置中进行试验，试验跨度为90mm，并且测量各样品的厚度和宽度。对于模量测量，利用100N压力传感器在横梁位移值为4.74mm/min下进行弯曲。利用10kN压力传感器测量强度。组成和机械性能结果被示于表8中。
表8
  复合材料类型   弯曲强度(MPa)   弯曲模量(GPa)
  15％Na2O   272.2±31.0   26.8±1.7
  5％Na2O   334.6±22.5   27.3±1.9
实施例6
在有或没有CaCO3填料混入基体的情况下，将如实施例5中那样制备的玻璃纤维复合材料分别浸渍于含有300ml磷酸盐缓冲盐水(PBS)并放置在37℃恒温箱中的瓶子中。14天后取出样品进行分析，记录其干燥质量。含CaCO3的样品保留了其初始干燥质量的98％，而那些没有CaCO3的样品仅保留了其初始干燥质量的63％。
本公开的聚合物纤维复合材料包括高强度聚乳酸纤维以及适于与该纤维一起工作的基体材料，该基体允许在纤维和基体之间有良好的界面强度，这使得该复合材料机械强度高并且分解速率下降。还公开了具有一定浓度的缓冲材料的聚合物和玻璃纤维复合材料，已经显示出该缓冲材料不会不利地干扰在聚合物基体和纤维材料之间的界面。更确切地说，试验结果显示缓冲材料工作给复合材料提供了在长时间期间保留其初始强度的大部分的能力，这是由于减慢了聚合物基体的分解速率，并且在玻璃纤维复合材料中，减慢了玻璃纤维的分解速率。
在有或没有降解控制剂下，含有基体材料以及上述玻璃和聚合物纤维混合物的复合材料也在本公开范围内。基体以及玻璃和聚合物纤维可以是与上述基体和聚合物/玻璃纤维相同类型的并且是通过相同方法制造的。另外，降解控制剂可以是如上所述相同类型的。此外，制造该复合材料的加工条件可以与制造上述聚合物纤维复合材料的加工条件相同。
在不偏离本公开范围内，由于如上所述参考相应的举例说明，可对示范性实施方式进行各种改变，其意图是包含在前述说明书并且示于附图中的全部内容都应该被认为是举例说明性的而不是限制性的。因此，本公开的宽度和范围应该不限于任何上述示范性实施方式，而是应该仅根据以下所附权利要求及其等同物来限定。

Claims (44)

1.一种纤维增强的复合材料，其包括：
PLLA纤维材料；以及
基体材料，其具有与所述纤维材料不同的化学成分组成。
2.权利要求1中所述的复合材料，其还包括分散于所述的基体材料中的降解控制剂。
3.权利要求1中所述的复合材料，其还包括分散于所述的基体材料中的促进剂。
4.权利要求1中所述的复合材料，其还包括分散于所述PLLA纤维材料中的促进剂。
5.权利要求2中所述的复合材料，其中所述降解控制剂是基本上由选自以下物质组成的组的缓冲材料：碳酸钙、碳酸氢钙、磷酸钙、磷酸二钙、磷酸三钙、碳酸镁和碳酸钠。
6.权利要求2中所述的复合材料，其中所述降解控制剂是常用盐。
7.权利要求2中所述的复合材料，其中所述降解控制剂占所述基体材料的约0.1％-40％重量。
8.权利要求1中所述的复合材料，其中所述PLLA纤维材料包括连续的PLLA纤维材料。
9.权利要求1中所述的复合材料，其中所述PLLA纤维材料占所述复合材料的约50％体积。
10.权利要求1中所述的复合材料，其中所述纤维材料包括约500MPa-2000MPa的拉伸强度。
11.权利要求1中所述的复合材料，其中所述纤维材料包括约800MPa的拉伸强度。
12.权利要求1中所述的复合材料，其中所述纤维材料包括约290,000g/mol-516,000g/mol的分子量。
13.权利要求1中所述的复合材料，其中所述纤维材料是生物可吸收的。
14.权利要求1中所述的复合材料，其中所述基体材料选自基本上由聚合物、共聚物和聚合物共混物组成的组。
15.权利要求14中所述的复合材料，其中所述聚合物共混物包括至少两种聚合物，其中所述共混物中的至少一种聚合物具有与所述纤维的化学成分组成不同的化学成分组成。
16.权利要求15中所述的复合材料，其中所述的具有与所述纤维的化学成分组成不同的化学成分组成的聚合物占所述聚合物共混物的至少50％。
17.权利要求16中所述的复合材料，其中所述的具有与所述纤维的化学成分组成不同的化学成分组成的所述聚合物占所述聚合物共混物的50％以上。
18.权利要求1中所述的复合材料，其中所述基体材料是生物可吸收的。
19.权利要求1中所述的复合材料，其中所述复合材料具有至少为250MPa的初始拉伸强度。
20.权利要求19中所述的复合材料，其中所述复合材料保留其初始拉伸强度的至少75％持续至少8周。
21.权利要求1中所述的复合材料，其中所述复合材料具有约为200MPa的弯曲强度。
22.权利要求1中所述的复合材料，其中所述复合材料具有至少为约140MPa的剪切强度。
23.一种纤维增强的复合材料，其包括：
基体材料；
玻璃纤维材料；以及
降解控制剂。
24.权利要求23中所述的复合材料，其中所述基体材料选自基本上由聚合物、共聚物和聚合物共混物组成的组。
25.权利要求23中所述的复合材料，其中所述基体材料是生物可吸收的。
26.权利要求23中所述的复合材料，其中所述纤维材料包括生物可吸收的玻璃纤维材料。
27.权利要求23中所述的复合材料，其中所述玻璃纤维材料包括约300MPa-1200MPa的拉伸强度。
28.权利要求23中所述的复合材料，其中所述玻璃纤维材料包括疏水性材料。
29.权利要求23中所述的复合材料，其中所述纤维材料占所述复合材料的约50％体积。
30.权利要求23中所述的复合材料，其中所述降解控制剂被分散于所述基体材料中。
31.权利要求23中所述的复合材料，其中所述降解控制剂被涂覆在所述纤维材料的表面上。
32.权利要求23中所述的复合材料，其中所述降解控制剂占所述基体材料的约0.1％-40％重量。
33.权利要求23中所述的复合材料，其中所述降解控制剂包括选自基本上由以下物质组成的组的缓冲材料：碳酸钙、碳酸氢钙、磷酸钙、磷酸二钙、磷酸三钙、碳酸镁和碳酸钠。
34.权利要求33中所述的复合材料，其中所述降解控制剂包括常用盐。
35.权利要求23中所述的复合材料，其中所述复合材料具有至少为250MPa的初始拉伸强度。
36.权利要求35中所述的复合材料，其中所述复合材料保留其初始拉伸强度持续8至少8周。
37.权利要求23中所述的复合材料，其中所述复合材料具有约250MPa-400MPa的初始弯曲强度。
38.权利要求23中所述的复合材料，其中所述复合材料具有约20-30GPa的初始弯曲模量。
39.权利要求23中所述的复合材料，其中所述复合材料保留其初始质量的约98％持续至少2周。
40.一种纤维增强的复合材料，其包括：
基体材料；
纤维材料；以及
降解控制剂。
41.一种纤维增强的复合材料，其包括：
基体材料；以及
玻璃纤维材料，该玻璃纤维材料包括约300MPa-1200MPa的拉伸强度。
42.权利要求2中所述的复合材料，其中所述降解控制剂选自基本上由缓冲材料、常用盐及其组合组成的组。
43.权利要求23中所述的复合材料，其中所述降解控制剂选自基本上由缓冲材料、常用盐及其组合组成的组。
44.一种纤维增强的复合材料，其包括：
PLLA纤维材料，该纤维材料包括约290,000g/mol-516,000g/mol的分子量，以及
基体材料。
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