CN1077025C - 含可粘着在可交联烯烃橡胶上的基于聚酰胺聚合物的材料 - Google Patents
含可粘着在可交联烯烃橡胶上的基于聚酰胺聚合物的材料 Download PDFInfo
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Abstract
本发明涉及一种材料,它含有:
-聚合物A,该聚合物又含有:
1)至少一种选自于聚酰胺、聚酰胺合金、具有聚酰胺嵌段和聚醚嵌段共聚物的产品,
2)至少一种选自于聚乙烯、乙烯共聚物、聚丙烯、丙烯共聚物的产品,这些产品被不饱和二羧酸或其酸酐接枝,
-聚合物A基本上是在无粘合剂的情况下粘着在硫化橡胶EPDM或EPM上的。
Description
本发明涉及一种材料,它含有:
-聚合物A,该聚合物含有:
1)至少一种选自于聚酰胺、聚酰胺合金、具有聚酰胺嵌段和聚醚嵌段共聚物的产品。
2)至少一种选自于聚乙烯、乙烯共聚物、聚丙烯、丙烯共聚物的产品。这些产品被不饱和羧酸、不饱和二羧酸或其酸酐接枝。
-聚合物A基本上是在无粘合剂的情况下粘着在硫化橡胶EPDM或EPM上的。
本发明例如涉及的是一些以聚酰胺为基的薄膜复盖的EPDM接头(衬垫),聚酰胺基本上是无粘合剂时粘着在EPDM上的。
以聚酰胺为基的薄膜含有(i)聚酰胺或具有聚酰胺嵌段和聚醚嵌段的嵌段共聚物,和(ii)由马来酸酐接枝并可能含有聚酰胺接枝的聚乙烯或聚丙烯。以聚酰胺为基的薄膜也可作粘合剂,并且它本身被另一种薄膜复盖,因此相继有EPDM、即以聚酰胺为基的薄膜,其它薄膜。
US5154979描述了由两种不相容的聚合物共注入所得到的物品。为了沿着分开两种聚合物的连接线达到良好粘着,就在其中一种聚合物中加入一种接枝聚烯烃。
有一些实施例描述了聚酰胺、由马来酸酐接枝的聚丙烯和玻璃纤维的混合体,它们粘着在SEBS(苯乙烯-乙烯/丁烯-苯乙烯嵌段共聚物)上或粘着在Santoprène(充填了橡胶EPDM的聚丙烯)上。
DE3914011叙述了具有聚酰胺或聚酰胺和聚烯烃混合物内层的管,其内层由可以是EPDM的橡胶复盖。必需在这两层之间加一种粘合剂,以便使整体坚固并耐久。然后这些层又复盖了加强件部分最后再用橡胶复盖。
EP266982叙述了复盖有聚酰胺、聚氨基甲酸乙酯或聚酯的热塑性弹性体。
热塑性弹性体是由可交联烯烃橡胶(EPDM)、聚烯烃(聚丙烯)和不饱和酸、环氧化物或不饱和烃基单体反应得到的。这些产品作为车窗玻璃导轨(滑槽)是有效的。
FR2322166描述了用等离子体处理EPDM来改善粘着。
FR2274670叙述了将聚酰胺固定在EPDM上的粘合剂。
现在发现了一种制备复盖有聚酰胺或以聚酰胺为基的共聚物的硫化EPDM的最简单的方法。在聚酰胺或以聚酰胺为基的共聚物中加入一种由马来酸酐接枝的聚烯烃足是以能达到粘着作用,比如分离只能在聚酰胺或EPDM薄膜断裂时发生。
因此,本发明是一种含聚合物A的材料,该聚合物A又含有:
1)至少一种选自于聚酰胺、聚酰胺合金、具有聚酰胺嵌段和聚醚嵌段共聚物的产品,
2)至少一种选自于聚乙烯、乙烯共聚物、聚丙烯、丙烯共聚物的产品,这些产品由不饱和羧酸、不饱和二羧酸或其酸酐接枝。
-聚合物A基本上是在无粘合剂的情况下粘着在硫化橡胶EPDM或EPM上的。
它们可以由诸如己二酸之类的二羧酸与诸如六亚甲基二胺之类的二胺反应得到。它们也可由诸如己内酰胺或ω-十二碳内酰胺之类的内酰胺缩合,或诸如氨基十一烷酸之类的α-ω氨基酸缩合得到。作为聚酰胺(PA)实例,可以列举PA6、PA6,6、PA11、PA12、PA6,4、PA6,10、PA6,12。这些产品本身都是已知的。
符合A1的聚酰胺合金可以是例如上述的聚酰胺与诸如聚乙烯、聚丙烯之类的聚烯烃,或诸如乙烯与α烯烃、乙烯及(甲基)丙烯酸烷基酯,或乙烯与饱和羧酸乙烯酯共聚物的合金。这些产品本身是已知的。
具有聚酰胺嵌段及聚醚嵌段的聚合物是由具有可反应端的聚酰胺链区与具有可反应端的聚醚链区彼此共缩聚而得到的,例如其中有:
1)二胺链端的聚酰胺链区与二羧酸链端的聚氧化烯链区(共缩聚)
2)二羧酸链端的聚酰胺链区与二胺链端的聚氧化烯链区,它们是通过氰乙基化和氢化人们称之为聚醚二醇的脂族α-ω二羟基化聚氧化烯链区而得到的。
3)二羧酸链端的聚酰胺链区与聚醚二醇,在这种特定的情况下,所得到的产品是聚醚酯酰胺。
二羧酸链端的聚酰胺链区可来自于,例如在链的限制剂二羧酸存在下由内酰胺的α-ω氨基羧酸或二羧酸和二胺的缩合。更有利地是,聚酰胺嵌段是聚酰胺12或聚酰胺6。
聚酰胺链区的数均分子量Mn为300-15000,优选为600-5000。聚醚链区的数均分子量Mn为100-6000,优选为200-3000。
具有聚酰胺嵌段与聚醚嵌段的聚合物还可含有无规分布的结构单元。这些聚合物可以由聚醚与聚酰胺嵌段前身同时反应而制得。
例如,在少量的水存在下,让聚醚二醇、内酰胺、(或α-ω氨基酸)和链的限制剂二酸进行反应。得到一种主要有聚醚嵌段、长度不一的聚酰胺嵌段的聚合物,但也得到许多随机进行反应的不同反应物,这些反应物在聚合链上统计分布。
具有聚酰胺嵌段与聚醚嵌段的这些聚合物,它们来自于前面制备的聚酰胺和聚醚链区的共缩聚,或者一步反应,这些聚合物的肖氏硬度D为20-75,有利地为30-70,而特性粘度为在起始浓度0.8克/100毫升、于250℃时的间甲酚中所测量的0.8-2.5。
当聚醚嵌段由聚乙二醇、聚氧亚丙基二醇或聚氧化四亚甲基二醇衍生时,或者它们原样使用,与羧酸端的聚酰胺嵌段共缩聚,或者将其胺化以便转化成二胺聚醚,再与羧酸端的聚酰胺嵌段缩合。还可以将它们与聚酰胺前身和链的限制剂混合以便制备具有统计分布结构单元的有聚酰胺嵌段与聚醚嵌段的聚合物。
在US4331786、US4115475、US4195015、US4839441、US4864014、US4230838和US4332920中描述了具有聚酰胺嵌段和聚醚嵌段的聚合物。
聚醚可以是例如聚乙二醇(PEG)、聚丙二醇(PPG)、或聚四亚甲基二醇(PTMG)。后者也称之聚四氢呋喃(PTHF)。
或四亚甲基二醇(-O-(CH2)4-)衍生的结构单元的不同结构单元时,也不超出本发明的范围。
优选地,具有聚酰胺嵌段和聚醚嵌段的聚合物含有仅一类聚酰胺嵌段和仅一类聚醚嵌段。人们最好使用具有PA-12嵌段和PTMG嵌段的聚合物,和具有PA-6嵌段和PTMG嵌段的聚合物。
更有利地是,具有聚酰胺嵌段和聚醚嵌段的聚合物是聚酰胺在重量上为主要组分的这种聚合物,即以嵌段形式的聚酰胺的量与在其链中可能以统计分布的量为具有聚酰胺嵌段和聚醚嵌段的聚合物的50%(重量)或50%(重量)以上。
关于乙烯共聚物中聚合物A的部分A2,可以列举例如乙烯-α烯烃共聚物或乙烯与至少一种选自于(甲基)丙烯酸烷基酯或饱和羧酸乙烯酯中的结构单元的共聚物。
关于产品A2,作为酸酐可以列举柠康酸酐、衣康酸酐、四氢化邻苯二甲酸酐、2-甲基马来酸酐、2,3-二甲基马来酸酐和马来酸酐。
可以以熔融态或按溶剂介质形式在聚合物上接枝酸酐。接枝率(即以接枝的聚合物计接枝的重量)可以为0.05-5%。
A1与A2的比例可以从30份A2为70份A1到70份A2为30分A1。
根据本发明的比较有利的实施方式,产品A2还可用能与酸、二酸或酸酐反应的聚酰胺或单官能聚酰胺低聚物接枝。优选地,使用与产品A1中相同的聚酰胺结构单元。
f为3-11,
g是5-80,
R5是氢或最多为20个碳原子的烷基,
R6是最多为20个碳原子的烷基或烯烃基、环脂族基、芳基或上述基团的组合。
这种聚酰胺单胺化低聚物可以通过具有下述化学式的氨基酸缩聚得到:或者通过具有下述化学式的内酰胺加聚得到:式中f是具有前面给出的意义,但需在具有下述化学式的单官能聚合限制剂存在下进行:式中R5和R6具有前面给出的意义。
合成本发明单胺化低聚物的优选氨基酸或内酰胺单体选自于己内酰胺,11-氨基十一烷酸或十二烷内酰胺。
优选的单官能聚合限制剂是月桂胺和油胺。
上面定义的缩聚可按照通常已知的方法进行,例如温度一般为200-300C,在真空或惰性气氛下,搅拌反应混合物。
低聚物的平均链长度是由可缩聚单体或内酰胺与单官能聚合限制剂之间的起始摩尔比所决定的。
为了计算平均链长度,通常都考虑到每一个低聚物链为一个链限制剂分子。
在接枝(共)聚合物上加聚酰胺的单胺化低聚物是通过低聚物胺官能团与至少一种接枝(共)聚合物的酸酐或酸官能团反应而进行的。这样就产生了酰胺或酰亚胺链。
最好是在熔融状态下将低聚物加到接枝(共)聚合物上。还可以在挤压机中于温度一般为230-250℃下将低聚物与(共)聚合物拌合。熔化物料在挤压机中的平均停留时间可以是15秒至5分钟,优选是1-3分钟。
采用选择性提取游离聚酰胺的低聚物,即设有反应生成最后接枝共聚物的这些低聚物,可以评价在接枝(共)聚合物上加低聚物的情况。
橡胶EPDM是乙烯、丙烯与二烯的共聚物,二烯不饱和位点可用硫硫化。二烯或者是未共轭的直链二烯烃,或者是环二烯或双环二烯。作为二烯实例,可以列举1,4-己二烯,环戊二烯或亚乙基降冰片烯,二烯的量例如可以是1-10%(重量)的EPDM。橡胶EPM是乙烯丙烯共聚物。
在EPM或EPDM中添加诸如SBR和NBR之类的橡胶时,只要EPDM或EPM仍是主要组分则没有超出本发明的范围。
本发明的材料可以是复盖聚合物A膜的硫化橡胶EPDM或EPM薄板。这种材料也可以是由复盖硫化橡胶EPDM或EPM的可变形金属芯构成的接头(衬垫)或型材,聚合物A薄膜可部分或全部复盖EPDM或EPM。这些型材例如是汽车车门接头衬垫,可变形的金属芯能将本发明的材料扣住或柠在汽车车身上。
本发明的材料还可以呈管状,是用硫化EPDM或EPM构成的,在其外层和/或内层包涂聚合物A薄膜。
可以通过将聚合物A薄膜压延或共挤压在硫化橡胶EPDM或EPM上生产出本发明的材料。还可以在硫化之前将EPDM或EPM与聚合物A薄膜共挤压,然后硫化该橡胶,只要聚合物A承受住硫化温度。这种方案只是聚合物A的熔点高于EPDM或EPM硫化温度(例如高含量聚酰胺的混合物)才有可能。
在硫化橡胶EPDM与聚合物A之间加粘合剂的情况不超出本发明的范围。
根据本发明的另外一种实施方式,可以用另一种聚合物B复盖本发明的材料,在这种情况下,更确切地说,聚合物A薄膜是一种粘合剂。
这种聚合物B是一种与聚合物A最好相容的聚合物或聚合混合物。
B可以选自于聚酰胺、聚酰胺合金、具有聚酰胺嵌段和聚醚嵌段的共聚物。
优选地,B与A1为同样产品。
例如,本发明的材料是一种型材,它可以含有包涂了硫化橡胶EPDM或EPM的可变形金属芯,其橡胶上涂有聚合物A粘合剂,而粘合剂上是聚合物B薄膜。
例如,粘合剂的厚度为10-50μm,聚合物B薄膜厚度为50-250μm。
实施例1
在单轴挤压机中,其轴速度调节到150转/分,将50份酰胺嵌段聚醚(A1)与50份接枝聚丙烯PA11(A2)混合。
挤压温度为225-250℃,挤压机的流量固定在20公斤/小时。
在挤压模出口,得到的组合物(I)呈灯芯草状,其平均粒度约为3mn。
所使用的酰胺嵌段聚醚是由66%PA12链区(Mn=2000)和33%PTMG链区(Mn=1000)组成,它由ELFATOCHEM公司以商品名PEBAX销售。
通过用25%(质量)PA11低聚物(Mn=2800)使马来酸化的PP接枝而得到的PPgPA11。
以经典方式采用炭黑、石蜡油和用硫的硫化系统配制成所使用的EPDM,是EXXON的VISTALON6630。
或者采用复制模型,或者采用重复挤压(reprise d′extrusion)可以制作EPDM/(I)复合材料,在这里我们将描述在压缩模里制作复制模型的过程,已知挤压试验得到了相同的粘着值。
a)制备橡胶相坯:用冲头将粗坯切成100×40×4mm大小,再在180℃硫化5分钟。
b)制备混合物(I)粗坯:用模压制得厚约1mm的薄膜,再用冲头将其膜切成100×40×1mm大小。
c)在压缩模中,在硫化EPDM表面不加压地将其混合物(I)升到200℃(熔化态)达3分钟。施加很小的压力达2分钟以保证粗坯成形。然后用循环水冷却其复合材料。
这种复合材料可以按照使用的要求再涂一层PEBAX、聚酰胺或以聚酰胺为基的合金。
在24小时后根据标准NFT 46008测定脱落强度(La force dePelage)。在硫化弹性体与混合物(I)之间设置无粘合剂的区域,在弹性体复制模型之前利用置于混合物(I)之上的铝胶带进行脱落。
实施例2
在与实施例1相同的条件下,把由60份酰胺嵌段聚醚(A1)和40份接枝聚丙烯PA12(A2)组成的组合物的II混合。
使用的酰胺嵌段聚醚是由66%PA12链区(Mn=2000)和33%PTMG链区(Mn=1000)组成,它由ELFATOCHEM公司以商品名PEBAX售。
用25%(质量)PA12低聚物(Mn=2800)使马来酸化的PP接枝而得到PPg PA12。
然后,在与复合材料I所描述的同样条件下,进行制作复合材料II。
实施例3
在与I相同样条件下,把由40份酰胺嵌段聚醚(A1)和60份接枝聚丙烯PA6(A2)构成的组合物(III)混合。
所用的酰胺嵌段聚醚是由66%PA6链区(Mn=1300)和33%PTMG链区(Mn=650)组成,由ELFATOCHEM以商品名PEBAX销售。
通过用25%(质量)PA6低聚物(Mn=2800)使马来酸化的PP接枝而得到PPgPA6。
然后,在与复合材料I描述的同样条件下进行制作复合材料Ⅲ。
实施例 I II II
脱落强度, 1.90 2.10 2.00
DaN/cm
断裂观察 粘着 粘着 粘着
Claims (5)
1.一种材料,它含有:
-聚合物A,该聚合物又含有:
聚合物A1)至少一种选自于聚酰胺、聚酰胺合金、具有聚酰胺嵌段和聚醚嵌段共聚物的产品,
聚合物A2)至少一种选自于聚乙烯、乙烯共聚物、聚丙烯、丙烯共聚物的产品,这些产品被不饱和羧酸、不饱和二羧酸或其酸酐接枝,
-聚合物A是在无粘合剂的情况下粘着在硫化橡胶EPDM或EPM上的。
2.根据权利要求1所述的材料,其特征在于,聚合物A2被马来酸酐接枝。
3.根据权利要求1或2所述的材料,其特征在于,聚合物A2还被聚酰胺低聚物接枝。
4.根据权利要求1或2所述的材料,其特征在于,它是一种由包涂硫化橡胶EPDM或EPM的可变形金属芯构成的型材,全部或部分橡胶包涂有一种聚合物A薄膜。
5.根据权利要求1或2所述的材料,其特征在于,聚合物A薄膜包涂有与聚合物A相容的聚合物B。
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FR2611727B1 (fr) | 1987-02-26 | 1989-06-16 | Atochem | Polyesteramides et polyetheresteramides - leur procede de fabrication |
JPH0222050A (ja) * | 1987-12-28 | 1990-01-24 | Tokai Rubber Ind Ltd | 冷媒輸送用ホース |
GB8810610D0 (en) * | 1988-05-05 | 1988-06-08 | Exxon Chemical Patents Inc | Coated rubber |
ATE156172T1 (de) * | 1990-06-01 | 1997-08-15 | Atochem Elf Sa | Zusammensetzungen thermoplastischer elastomere auf der basis von polyamiden und modifizierten polyolefinen, geformte oder extrudierte körper, filme und verbundmaterialien hergestellt aus diesen |
JP3166382B2 (ja) * | 1993-02-26 | 2001-05-14 | 東海ゴム工業株式会社 | 自動車燃料配管用ホース |
-
1994
- 1994-07-19 FR FR9408905A patent/FR2722793B1/fr not_active Expired - Fee Related
-
1995
- 1995-07-07 EP EP95401644A patent/EP0693367B1/fr not_active Expired - Lifetime
- 1995-07-07 DE DE69517560T patent/DE69517560T2/de not_active Expired - Fee Related
- 1995-07-17 CA CA002154051A patent/CA2154051C/fr not_active Expired - Fee Related
- 1995-07-19 KR KR1019950021222A patent/KR0165160B1/ko not_active IP Right Cessation
- 1995-07-19 CN CN95115255A patent/CN1077025C/zh not_active Expired - Fee Related
- 1995-07-19 JP JP7182998A patent/JP2721137B2/ja not_active Expired - Lifetime
-
1997
- 1997-12-15 US US08/990,589 patent/US5962146A/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4950436A (en) * | 1988-04-25 | 1990-08-21 | The Yokohama Rubber Co., Ltd. | Process for producing hoses of high impermeability to gas and vapor |
EP0393409A1 (de) * | 1989-04-10 | 1990-10-24 | Ems-Inventa Ag | Formmassen aus unverträglichen Polymeren und ihre Verwendung |
Also Published As
Publication number | Publication date |
---|---|
CA2154051A1 (fr) | 1996-01-20 |
DE69517560T2 (de) | 2001-02-08 |
DE69517560D1 (de) | 2000-07-27 |
CN1125739A (zh) | 1996-07-03 |
KR960004480A (ko) | 1996-02-23 |
FR2722793B1 (fr) | 1996-11-29 |
CA2154051C (fr) | 2001-07-03 |
US5962146A (en) | 1999-10-05 |
JPH0881626A (ja) | 1996-03-26 |
KR0165160B1 (ko) | 1999-03-20 |
FR2722793A1 (fr) | 1996-01-26 |
EP0693367B1 (fr) | 2000-06-21 |
JP2721137B2 (ja) | 1998-03-04 |
EP0693367A1 (fr) | 1996-01-24 |
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