CN1128541A - 塑料制品及其制备方法 - Google Patents

塑料制品及其制备方法 Download PDF

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CN1128541A
CN1128541A CN94192980A CN94192980A CN1128541A CN 1128541 A CN1128541 A CN 1128541A CN 94192980 A CN94192980 A CN 94192980A CN 94192980 A CN94192980 A CN 94192980A CN 1128541 A CN1128541 A CN 1128541A
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plastics
pebbs
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J·佩特拉吉斯
W·霍格
T·林内
M·阿芬纳
J·G·M·纽坎普
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Koninklijke DSM NV
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Abstract

本发明涉及一种塑料制品，其特征在于它由几种泡沫热塑性弹性体(TPE′s)，如TE(EM-X-PP)及PEBBS和/或PBBS和/或TE(PEBBS+PP)和/或TE(PBBS+PP)组成。它进一步包括基于TPE′s和TPE-O′s的混合物的塑料制品，本发明还涉及制备这些制品的方法。

Description

塑料制品及其制备方法
本发明涉及具有类似泡沫橡胶性质的泡沫塑料制品及该塑料制品的制备方法。
已知的用作密封型材的塑料制品由金属衬底型材和PVC护套组成。在PVC护套上粘合一泡沫型材。虽然这类型材已使用了许多年，但仍有缺点并且已不能满足当今技术要求。人们认为已知型材的缺点在于PVC和泡沫橡胶不能同时挤出，这意味着必须用一条单独压出生产线制备衬底型材而单独用另一压出生产线制备泡沫型材，造成相当高的成本，另一缺点是为使各个型材粘合在一起所需的消耗(即花费的大量时间和金钱)，同时达到的附着力不完全可靠。常规型材的再一缺点是使用的橡胶不可能染色。最后，已知的型材因使用不同的原材料和粘合剂，不能循环利用，这被认为是非常严重的缺点，因为目前正努力寻找重复使用原材料的途径。
本发明的目的就在于提供一种具有类似泡沫橡胶性质的泡沫塑料制品和该制品的制备方法，由此避免了上述缺点。
具体地，此目的因泡沫塑料制品包含几种热塑性弹性体(TPEs)而实现。此目的特别因热塑性弹性体为TE(EM-X-PP)[聚丙烯(PP)-弹性体(EM)与动态(现场)交联弹性体组分的共混物]及PEBBS[苯乙烯-乙烯/丁烯-苯乙烯ABA嵌段共聚物]和/或PBBS[苯乙烯-丁二烯-苯乙烯-ABA嵌段共聚物]的混合物而实现。使用TE(EM-X-PP)及PEBBS和/或TE(PEBBS＋PP)作为热塑性弹性体具有优点，同时已发现使用约4份肖氏(A)硬度为40的TE(EM-X-PP)及1份肖氏(A)硬度为30的PEBBS和/或TE(PEBBS＋PP)或约3份肖氏(A)硬度为60的TE(EM-X-PP)及2份肖氏(A)硬度为30的PEBBS和/或TE(PEBBS＋PP)最为有利。
本发明的制品基本不含氯，对环境无害，并且不含对健康有害的物质。本发明的新材料组合物可确保完全可循环利用。根据本发明，可制得肖氏(A)硬度为约25至85及肖氏(D)硬度为约30至45的新制品，并且其制备不成问题。本发明的另一优点是高耐光性、耐紫外线(UV)性、耐臭氧性和良好的压缩变形，且当加热至70～100℃时，也具有这样的性质。
当要满足的要求较低时，泡沫塑料制品也可由下列热塑性弹性体组成，即：TE(EM-X-PP)和/或TE(EM＋PP)及PBBS和/或TE(PBBS＋PP)。
本发明的目的也可通过包含热塑性弹性体(TPEs)和一种或多种热塑性烯烃(TPE-O)的泡沫塑料制品来达到。正如人们知道的，TPE′s是至少部分交联的而TPE-O′s是非交联的。优选使用的材料组合物是(例如)TE(EM-X-PP)和PEBBS和/或TE(PEBBS＋PP)及TE(EM＋PP)或TE(EM-X-PP)、PBBS和/或TE(PBBS＋PP)及TE(EM＋PP)。在一系列实际测试中，包含约4份肖氏(A)硬度为80的TE(EM-X-PP)、1份肖氏(A)硬度为30的PEBBS和/或TE(PEBBS＋PP)(或PBBS和/或TE(PBBS＋PP))及3份肖氏(D)硬度为30的TE(EM＋PP)的塑料制品证明是特别有利的。
作为TE(EM-X-PP)和TE(EM＋PP)中的弹性体，可使用任何合适的橡胶，此橡胶可以是(动态)交联的。作为参考可以提及(卤化)丁基共聚物和三元共聚物橡胶、天然橡胶、NBR，优选乙烯-丙烯共聚物橡胶(EPM)，更优选乙烯-丙烯-二烯三元共聚物橡胶(EPDM)。
对于本发明塑料制品，在该塑料制品的制备过程中使用了发泡剂，优选化学发泡剂，同时还可加入颜料。
在一个优选实施方案中，本发明的塑料制品具有挤出型材条的形状，并且型材条可具有至少一个相对硬的部分和至少一个相对软的部分，该至少一个相对硬的部分与至少一个相对软的部分通过共挤出牢固连接。型材条的至少一个相对软的部分采用密封唇缘或密封管的形状是有利的。
在本发明的另一优选实施方案中，塑料制品为注射模塑件。在这种情况下，也可以通过注射模塑实现软质至硬质或硬质至软质的粘合。
对于本发明制备塑料制品的方洗可使用常规的塑料加工设备，将包含TE(EM-X-PP)和/或TE(EM＋PP)组分、PEBBS和/或TE(PEBBS＋PP)组分或PBBS和/或TE(PBBS＋PP)组分及化学发泡剂的混合物加入该设备中。发泡剂的量对于每100份聚合物组分通常为0.5～2.5份(重量)。在本发明的塑料制品中，含热塑性弹性体的PEBBS或PBBS的量一般为热塑性弹性体总量的1～75％(重量)。
制备TE(EM-X-PP)可以与制备塑料制品分开进行，但也可以在制备本发明的塑料制品过程中进行。在TE(EX-X-PP)中橡胶的交联程度至少应为70％，优选大于85％(通过在沸腾二甲苯中萃取测量)。
本发明的材料组合物可以通过挤出和注射模塑，以令人满意的质量制备具有弹性体性能的塑料制品，而这被认为是出乎意料的，因为试图用TPE组分与(化学)发泡剂或用TPE-O组分与(化学)发泡剂产生绝对无用的结果。发现的缺陷包括如下：不均匀泡沫结构、挤出物不可控制的膨胀、表面龟裂、发泡程度不够、非常低的挤出速度、挤出物发脆、机械性能明显降低、拉伸强度和伸长率降低、表面粗糙和发灰色、当挤出物离开设备时破碎及在表面上形成气泡和疙瘩。
前面提出的目的可优选通过本发明方法、使用由TE(EPDM-X-PP)组分、PEBSS和/或PBBS和/或TE(PEBBS＋PP)或TE(PBBS＋PP)组分及(化学)发泡剂组成的混合物来实现。
最后，制备本发明塑料制品的优选方法在于使用已进行混合后的基于TE(EM-X-PP)、PEBBS和/或TE(PEBBS＋PP)或PBBS和/或TE(PBBS＋PP)和任选的TE(EM＋PP)组分的聚合物材料及化学发泡剂，其中混合必须在温度低于发泡剂的活化温度下进行。按此方式，可达到极高的物料均匀性。
本发明方法可通过加入颜料并将此混合物或混合料挤出成型材条或注射模塑成制品而完成。塑料制品还可与金属衬底型材结合。
采用本发明的方法，由发泡TPE/TPE-O共混物可以以低的生产成本以优异的质量制得或制备适合于内外使用(尤其用于车辆)的挤出和/或注射模塑制品。TPE/TPE-O泡沫共混物的特殊性质和组成还使该共混物可以与非泡沫材料通过共挤出、注射模塑和压塑(在25A至45D肖氏硬度范围内及密度为500至900kg/m3下进行)而结合使用。此外，本发明方法开辟了染色的可能性、类似于在此肖氏(A)硬度范围内的泡沫橡胶的光滑、闭孔表面和性质。特别是各种共混物基本不含氯因而对环境有益，同时这些共混物可不受限制地循环使用。
可使用的发泡剂在本领域中是已知的；它们包括可蒸发物质如水或脂族烃类，或可分解物质(例如：放热和/或吸热发泡剂，如基于改性偶氮二酰胺的发泡剂)。还可参考US-A-4918111，第3列，27行以下给出的信息。
根据本发明，由于相容性TPE/TPE-O′s的混合物和加入特定的(化学)发泡剂，使得可以生产具有下列性能和加工可能性的共混物：-    无PVC(氯)-    对环境有益-    无对健康有害的物质-    可循环利用以生产类似制品-    肖氏硬度(A)25～85-    肖氏硬度(D)30～45-    可挤出具有光滑和闭孔的表面-    化学性质可与橡胶混合物比拟-    根据说明书的机械和物理性能-    可挤出和注射模塑-    可通过排出口注射模塑-    可以泡沫制品的形式挤出-    可以常规设备和模具上挤出-    可与TPE’s和/或TPE-O’s共挤出-    均匀泡沫结构(多微孔)-    密度500～900kg/m3
此塑料制品优选呈现具有多微孔和均匀泡沫结构的闭孔和光滑表面。
在本发明进一步的实施方案中，生产挤出制品的特点在于，通过设置于挤出模具内或挤出模具外甚至不与模具接触的切割单元，在流动方向按要求切割熔体。按此方式，在一次生产过程中可得到在切割面具有闭孔和光滑表面的一个或多个挤出制品。
在本发明另一实施方案中，得到类似整理织物(textile-likefinish)的制品表面，使其具有抗刮伤性和耐磨性。
前面使用的术语都摘自由Dipl.Ing.Ekkehard Gorski，München出版的报告‘Nomenclature and testing’(会议日期1992年10月6-7日，Mainfrankensle，Veitshcheim，附录25-29页)。
本发明可由下列实施例说明，而这些实施例并不限制本发明。
实施例I：涉及制备具有类似橡胶的性质的型材条：
将80份具有肖氏(A)硬度为40的TE(EPDM-X-PP)(粒料)、20份具有肖氏(A)硬度为30的TE(PEBBS＋PP)(粒料)和2份偶氮二酰胺作为化学发泡剂及任选加入的着色颜料一起混合(或混料)，将其加入挤出机中并在操作温度170～210℃下挤出。
结果：微孔、均匀分布、闭孔表面、光滑表面(silky mat)、肖氏(A)硬度＝25，泡沫。
实施例II：涉及生产具有泡沫橡胶性质的注射模塑制品：
将60份肖氏(A)硬度为60的TE(EPDM-X-PP)(粒料)、40份肖氏(A)硬度为30的TE(PEBBS＋PP)(粒料)和0.5至2.5％的偶氮二酰胺作为化学发泡剂一起混合并在190～240℃温度下注射模塑为制品。
结果：微孔、均匀分布、闭孔表面、良好手感、肖氏(A)硬度＝30，泡沫。

Claims (22)

1.具有类似泡沫橡胶性质的泡沫塑料制品，其特征在于它包含几种热塑性弹性体(TPE′s)。
2.根据权利要求1的塑料制品，其特征在于热塑性弹性体包含TE(EM-X-PP)与PEBBS和/或PBBS的混合物。
3.根据权利要求1的塑料制品，其特征在于热塑性弹性体包含TE(EM-X-PP)与TE(PEBBS＋PP)和/或TE(PBBS＋PP)的混合物。
4.根据权利要求1至2中任意一项的塑料制品，其特征在于TE(EM-X-PP)中的弹性体是EPM或EPDM。
5.根据权利要求1至4中任意一项的塑料制品，其特征在于它包含约4份肖氏(A)硬度为40的TE(EM-X-PP)和1份肖氏(A)硬度为30的PEBBS和/或TE(PEBBS＋PP)或约3份肖氏(A)硬度为60的TE(EM-X-PP)和2份肖氏(A)硬度为30的PEBBS和/或TE(PEBBS＋PP)。
6.根据权利要求1至5中任意一项的塑料制品，其特征在于它包含热塑性弹性体(TPE′s)和一种或多种热塑性烯烃(TPE-O′s)的混合物。
7.根据权利要求6的塑料制品，其特征在于它包含热塑性弹性体，即基于聚丙烯(PP)的TE(EM-X-PP)及PEBBS和/或TE(PEBBS＋PP)，以及热塑性烯烃(TPE-O′s)。
8.根据权利要求6的塑料制品，其特征在于它包含热塑性弹性体，即基于PP的TE(EM-X-PP)及PBBS和/或TE(PBBS＋PP)，以及热塑性烯烃(TPE-O′s)。
9.根据权利要求6至8中任意一项的塑料制品，其特征在于它包含约4份肖氏(A)硬度为80的TE(EM-X-PP)、1份肖氏(A)硬度为40的PEBBS和/或TE(PEBBS＋PP)(或PBBS和/或TE(PBBS＋PP))及3份肖氏(D)硬度为35的TPE-O。
10.根据权利要求1至9中任意一项的塑料制品，其特征在于将化学发泡剂用于制备中。
11.根据权利要求1至10中任意一项的塑料制品，其特征在于它包括着色颜料。
12.根据权利要求1至11中任意一项的塑料制品，其特征在于它具有挤出型材条形状。
13.根据权利要求12的塑料制品，其特征在于型材条具有至少一个相对硬的部分和至少一个相对软的部分，此至少一个相对硬的部分与至少一个相对软的部分通过共挤出牢固连接。
14.根据权利要求12或13的塑料制品，其特征在于型材条的至少一个相对软的部分为密封唇缘或密封管形状。
15.根据权利要求1至11中任意一项的塑料制品，其特征在于它是注射模塑的。
16.根据权利要求1至14中任意一项的塑料制品，其特征在于它显示具有多微孔和均匀泡沫结构的闭孔和光滑表面。
17.生产根据权利要求1至16中任意一项的塑料制品的方法，其特征在于在常规塑料加工设备中制备包含TE(EM-X-PP)组分、PEBBS和/或TE(PEBBS＋PP)组分或PBBS和/或TE(PBBS＋PP)组分及化学发泡剂的混合物。
18.生产根据权利要求1至16中任意一项的塑料制品的方法，其特征在于先将聚合物材料和化学发泡剂在温度低于发泡剂活化温度下混合。
19.根据权利要求17至18中任意一项的方法，其特征在于通过设置于挤出模具内或挤出模具外甚至不与模具接触的切割单元，在流动方向按需要切割熔体。
20.根据权利要求17至19中任意一项的方法，其特征在于制得的制品表面类似整理织物，由此使该制品具有抗刮伤性和耐磨性。
21.由权利要求20的方法制得的制品。
22.用于制备根据权利要求1～16和21中任意一项的塑料制品的组合物。
CN94192980A 1993-08-05 1994-08-05 塑料制品及其制备方法 Pending CN1128541A (zh)

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US5824400A (en) 1998-10-20
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