CN106103031B - 形状记忆产品和制造它们的方法 - Google Patents

形状记忆产品和制造它们的方法 Download PDF

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CN106103031B
CN106103031B CN201480077407.2A CN201480077407A CN106103031B CN 106103031 B CN106103031 B CN 106103031B CN 201480077407 A CN201480077407 A CN 201480077407A CN 106103031 B CN106103031 B CN 106103031B
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foaming agent
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CN106103031A (zh
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S.库鲁普
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TECH ELECTRONICS BRITISH Ltd
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Abstract

通过将熔融混合的能交联的聚合物组合物注射成型而制造能热收缩的形状记忆产品，所述组合物优选包括聚乙烯和乙烯‑乙酸乙烯酯(EVA)共聚物。所述组合物还包含微包封的发泡剂和交联剂，且选择温度和压力条件使得组合物的发泡和膨胀不是在注射成型机中、而是在模具本身中发生。

Description

形状记忆产品和制造它们的方法
技术领域
本发明涉及形状记忆产品，例如作为其中微包封的(microencapsulated)起泡剂(发泡剂，blowing agent)分布在聚合物或聚合物共混物基体中的类型的隔热材料(保温材料，insulating material)使用的形状记忆产品。
背景技术
重量轻的能热收缩的产品在许多工业、尤其是其中减轻重量是主要考虑因素的航空航天和汽车工业中正呈现出日益增长的重要性。制造能热恢复的产品的一种方式是使用包括如下的熔融组合物(熔体组合物，melt composition)：基础聚合物例如乙烯乙酸乙烯酯共聚物和由被多个聚合物壳包封的至少一种热活化的化合物(chemical compound)制得的起泡剂。所述熔融组合物还可包括交联促进剂或其它添加剂。所述起泡剂具有活化温度，且通过在制造过程期间加热而活化。US3615972A公开了包封在能膨胀的热塑性微球中的热活化的液体起泡剂。
发明内容
本发明提供制造能热收缩的产品的方法，其包括这些步骤：
(i)通过熔融混合制备聚合物组合物，该聚合物组合物包含均匀分散在其中的能交联的聚合物、交联剂和微包封的发泡剂(foaming agent)，所述发泡剂具有比熔融混合温度高的峰活化温度，以及
(ii)将所述组合物在使得由发泡剂引起的组合物的膨胀和随后成型产物的交联发生在模具内的温度和压力条件下注射成型。
除了发泡剂和交联剂之外，所述聚合物组合物还可包括任选的填料例如抗氧化剂、热稳定剂、着色剂、阻燃剂等。
所述组合物的基础聚合物材料优选地是基于烯烃的，并且对其进行选择使得其将容易地熔融、经受住注射成型的热和压力而不降解、且与所述起泡剂均匀地混合。
优选的聚烯烃包括：聚乙烯，其可为从非常低到高密度的任何合适密度的聚乙烯(中密度是优选的)、茂金属聚合的乙烯；包含C4-C10烯烃的乙烯共聚物；聚乙烯与乙酸乙烯酯、乙酸烷基酯、丙烯酸、马来酸酐或羧酸的共聚物和三元共聚物；聚丙烯；乙烯丙烯二烯橡胶(EPDM)；苯乙烯丁二烯橡胶、和与聚烯烃的橡胶共混物。
常常合意的是将具有较高水平结晶度的聚合物与具有较低水平结晶度的聚合物混合以实现特定的能热恢复的性质。优选的基础聚合物包括中密度聚乙烯和乙烯/乙酸乙烯酯共聚物(EVA)。
所述基础聚合物优选地以所述熔融组合物的50重量％-90重量％、更优选地以所述熔融组合物的60重量％-75重量％存在。
在本发明的一些优选实施方式中，聚合物基础物包括30-70重量％的聚乙烯和10-25重量％的EVA，更优选地40-60重量％的聚乙烯和10-20重量％的EVA，基于总的组合物。
本发明采用处于多个聚合物壳包封热活化的化合物的形式的起泡剂。这些包封物(胶囊，capsule)常称为微球。所选择的化合物优选地在室温下为液体，且具有相对低的沸点、即小于50℃。选择具体的化合物和聚合物壳材料使得聚合物壳在注射成型的苛刻条件下始终保持完整，更具体地，选择聚合物壳材料使得壳不会在混合过程中使用的热和压力下降解或熔融，且不会在注射成型过程的施加力的期间破裂。所述壳此外还具有高的化学耐受性且与聚合物基体相容。
所述微球还具有这样的活化温度，在该活化温度，包封的液体开始沸腾且转变为气体。在该活化温度，所述聚合物壳足够软而开始膨胀以容许体积随着化合物进入气相而增大，同时仍然有效地包封所述化合物。微球的该膨胀在基础聚合物中形成空隙而生成发泡的材料。通常所述活化温度包括容纳产品的特定批次中的微球尺寸差异的范围。此外，常常限定包封的起泡剂的最低膨胀温度(或温度范围)、即包封剂(encapsulant)开始膨胀时的温度，以及最高膨胀温度(或温度范围)、即包封剂已经完成膨胀时的温度。所述活化温度通常稍微低于所述最高膨胀温度。
所述聚合物壳可包括但不限于如下的聚合物和共聚物：氯乙烯、偏二氯乙烯、丙烯腈、甲基丙烯腈、苯乙烯、或其组合。优选地，所述聚合物壳包封低沸点的基于烃的液体例如异戊烷或异丁烷。
在本发明的优选实施方式中，未膨胀的聚合物壳优选地具有范围在3μm-60μm、更优选6μm-40μm的直径。未膨胀的包封的起泡剂的密度通常小于25kg/m3。未膨胀的包封的起泡剂优选地以熔融组合物的0.5％-3重量％、更优选地以熔融组合物的约1％-2％的量使用，尽管所使用的起泡剂的精确量随如下而变化：聚合物的类型、起泡剂的类型、和任选的填料的存在。
一种优选的包封的起泡剂为可得自Akzo Nobel的ExpancelTM聚合物微球。通常，这样的微球具有6μm-40μm的未膨胀直径和20μm-150μm的膨胀直径。优选的包封的热活化的起泡剂包括ExpancelTM091-DU-80或ExpancelTM92-DU-120、或ExpancelTM950MB80(母料形式)，其具有包括丙烯腈和甲基丙烯腈的共聚物的聚合物壳且全都包封异戊烷。
然而，为了生成均匀稳定的泡沫，选择注射成型温度和压力使得起泡剂微球直到聚合物混合物被注入模具中才开始膨胀。优选地，将选择起泡剂使得它的活化温度高于混合温度区中的温度、但低于模具中的温度。因此优选的是选择最低膨胀温度高于基础聚合物的熔融温度的起泡剂，使得在基础聚合物材料熔融的同时膨胀不发生。更优选地，所选择的起泡剂具有比熔融步骤的期望混合温度高的最低膨胀温度。
注射成型压力优选地在10-20MPa、更优选地在12-17MPa的范围内，且适合为约15MPa。
为了生产能热恢复的成型产物，使聚合物材料交联。交联给予聚合物其当前形状的“记忆”，且给予完成的聚合物成型部分在加热时收缩或以其它方式改变形状的能力。交联还提高发泡的聚合物的结构刚性，且确保泡沫在膨胀或热收缩时不减压或“变平(goflat)”。交联可通过辐射或化学手段实现，且聚合物混合物可包括交联剂或促进剂以增大离散的聚合物链之间的交联量。存在两种总的交联促进剂类型–化学交联促进剂和辐射交联促进剂。可使用这些交联促进剂类型的一种或两者。
优选的化学交联剂包括过氧化物，优选地有机过氧化物，例如2,5-双(叔丁基过氧基)-2,5-二甲基己烷。化学交联剂的优选含量为0.1-1.0重量％，基于总的组合物。
当暴露于辐射，例如来自高能电子束的辐射时，辐射交联促进剂充当聚合物交联的催化剂。辐射交联促进剂可从常规地用以促进聚合物交联的那些中选择，包括氰尿酸三烯丙基酯(TAC)、异氰尿酸三烯丙基酯(TAIC)、偏苯三酸三烯丙基酯、均苯三酸三烯丙基酯、均苯四酸四烯丙基酯、1,1,3,-三甲基-5-羧基-3-(4-羧基苯基)茚的二烯丙基酯、三羟甲基丙烷偏苯三酸酯(TMPTM)、季戊四醇三甲基丙烯酸酯、三(2-丙烯酰氧基乙基)异氰尿酸酯、三(2-甲基丙烯酰氧基乙基)偏苯三酸酯等、和其组合。一种优选的辐射交联促进剂是可作为SartomerTMSR350从Sartomer Company商购得到的TMPTM。另一种是TAC。辐射交联促进剂的优选含量为0.2-1.5重量％，基于总的组合物。
还可以将为发泡产品提供有效的阻燃性的量添加阻燃剂。合适的阻燃剂典型地包括多溴代的芳族化合物，例如与无机材料如三氧化二锑组合的十溴代联苯。其它可能的阻燃剂包括氧化铝三水合物和基于磷的阻燃剂。还可以常规的量采用其它填料，例如抗氧化剂、粘附促进剂、防紫外线剂、增塑剂、着色剂、热稳定剂和其它添加剂。如本领域的技术人员已知的，这样的添加剂可基于产品的最终用途进行选择。阻燃剂的总含量优选地在15-30重量％的范围内，基于总的组合物。
熔融组合物中存在的任选的填料(其在本说明书中包括交联促进剂和阻燃剂两者、以及以上提及的其它填料和添加剂)的量取决于基础聚合物和包封的起泡剂的类型和量、以及期望的物理性质。通常，填料的量为熔融组合物的至多35重量％，优选地为熔融组合物的至多20重量％，特别地为熔融组合物的至多10重量％，例如为熔融组合物的0-19.9重量％。
根据本发明的能发泡的聚合物的注射成型过程与本领域的技术人员已知的类似。首先将基础聚合物与起泡剂和其它能发泡的聚合物组合物成分(element)混合。混合通过本领域的技术人员已知的任何方法进行；优选地，混合通过班伯里(Banbury)型混合机发生。还可成功地采用双螺杆混合装置。混合发生在这样的升高的温度下：其被选择成足够高的使得基础聚合物将在混合期间熔融，但其不高到足以使聚合物混合物的其它组分(例如起泡剂或任何交联促进剂)活化。因此，混合步骤在这样的温度下发生：其高于所选择的基础聚合物的熔融温度，但低于起泡剂的最低活化温度。
然后将处于熔融状态的经混合的聚合物共混物注入如本领域中已知的模具中。聚合物共混物在熔融和混合之后但在注射之前的温度可独立于注射时和注射点的温度设定。优选地，混合后、注射前的温度被设定在这样的温度：其等于或高于混合温度，但低于聚合物共混物中的组分的最低活化温度。模具的温度优选地设定为适当高于至少所述起泡剂的最低活化温度，即高至少10℃。通过等待直至刚要注射之前达到使所述起泡剂活化的温度，已经发现生成更稳定均匀的泡沫。在活化时，起泡剂的聚合物包封物内部的液体改变相态至气态，且所述包封物膨胀而生成气囊。从而所述熔融组合物优选地形成为期望的形状，且近似同时发泡。
注射成型温度优选地在120-160℃、更优选130-150℃的范围内。模具温度优选地在170-210℃、更优选180-200℃的范围内。
一旦成型物体(体，body)已经经历了发泡，起泡剂微球就处于充分膨胀的状态，且基础聚合物处于熔融、即高度粘稠的液体样状态。随着所述物体刚在成型之后开始冷却，聚合物开始在膨胀的微球周围凝固。然后所述微球以膨胀的状态冻结(冷冻)，生成泡沫中的空隙。
然后成型物体经历后加工，其通常包括一个涉及暴露于热的步骤。在进一步的步骤中，使发泡的聚合物物体交联。取决于所使用的交联过程的类型，将所述物体辐照和/或加热至适当的温度以使化学交联促进剂活化。辐照通过本领域中已知的任何方法例如高能电子束辐照发生。使泡沫中的聚合物股料(strand)交联的目的是给予成型部分以产品当前形状的“记忆”以及在高于基础树脂熔点时的结构稳定性。
附图说明
现在将参照附图详细描述本发明的优选实施方式，在所述附图中：
图1是显示具有不同添加水平的微包封的发泡剂的本发明的能发泡的组合物的比重的变化的图，和
图2是依照本发明的能发泡的物体在膨胀前的显微照片，和
图3是显示图2的能发泡的物体在膨胀之后的显微照片。
具体实施方式
实施例
在下表1中列出了依照本发明使用包封的起泡剂的能发泡的组合物的三个示例性配方、以及未使用起泡剂的对比例。
表1
使用具有六个区段的注射成型机将表1中的四种组合物在135℃的温度熔融混合，并在15MPa下注入模具中，所述六个区段的前五个区段加热至135±10℃且最后一个加热至145±10℃。测得的组合物温度从第一区段中的134℃升至最后一个区段中的145℃。
将所述模具加热至190±5℃，由此本发明组合物的膨胀发生在模具中。
然后对膨胀的组合物进行化学或辐射交联以得到最终产品。在表2中列出了这些的物理性质。
表2
基于以上结果，包封的起泡剂的优选含量为实施例2的1.5重量％，其得到最有利的比重与物理性质之间的平衡(热收缩产品的关键特征)。然而，该量可根据发泡的聚合物的期望比重而变化。附图的图1显示了产品的比重可下降，从没有发泡剂添加时的1.13近似线性地至具有2重量％发泡剂添加时的0.85。
图2显示其中分布有1.5重量％起泡剂微包封物的依照本发明的聚合物的能膨胀的物体的部分的显微照片。这些作为小黑点显示出来。
图3显示在190℃膨胀之后的图2的能膨胀的聚合物物体。

Claims (9)

1.制造能热收缩的产品的方法，其包括如下步骤：
(i)通过熔融混合制备聚合物组合物，该聚合物组合物包含聚乙烯能交联的聚合物、交联剂和均匀分散在其中的微包封的发泡剂，所述发泡剂具有比熔融混合温度高的峰活化温度，以及
(ii)将所述组合物在使得由发泡剂引起的组合物的膨胀和随后成型产物的交联发生在模具内的温度和压力条件下注射成型；
其中所述聚合物组合物包括30-70重量％的聚乙烯且进一步包括10-25重量％的乙烯-乙酸乙烯酯共聚物(EVA)，基于总的组合物；并且
所述交联剂包括有机过氧化物化合物。
2.根据权利要求1所述的方法，其中注射成型温度在120-160℃的范围内。
3.根据权利要求1或权利要求2所述的方法，其中模具温度在170-210℃的范围内。
4.根据权利要求1或权利要求2所述的方法，其中注射成型压力在10-20MPa的范围内。
5.根据权利要求1或权利要求2所述的方法，其中所述基于聚烯烃的组合物包括40-60重量％的聚乙烯和10-20重量％的EVA，基于总的组合物。
6.根据权利要求1或权利要求2所述的方法，其中所述能交联的聚合物组合物包括辐射交联促进剂，且对所述成型产物进行辐射交联。
7.根据权利要求1或权利要求2所述的方法，其中所述能交联的聚合物组合物进一步包括阻燃剂。
8.根据权利要求1的方法，其包括0.5-3重量％的微包封的发泡剂和0.1-1重量％的有机过氧化物化合物，且进一步包括15-30重量％的阻燃剂，所述百分比基于总的组合物。
9.能热收缩的发泡的形状记忆产品，其包括包含以下组分的化学交联的注射成型发泡物体：
所述百分比基于总的组合物。
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