CN1103076A - 弹性聚丙烯与非烯烃类热塑性塑料的共混物 - Google Patents
弹性聚丙烯与非烯烃类热塑性塑料的共混物 Download PDFInfo
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Abstract
本发明提供弹性聚丙烯与非烯烃类热塑性塑料
的共混物。
Description
本发明涉及弹性聚丙烯（ELPP）与非烯烃类热塑性塑料的共混物。
等规聚丙烯（IPP）与如聚酰胺、聚酯、聚苯乙烯或聚碳酸酯的非烯烃类热塑性塑料的共混物是已知的。例如，EP-A-244，601或EP-B-261，748公开了IPP与聚酰胺的共混物。这些共混物的突出优点是：一方面，根据用该共混物制得的最终制件需要的性能曲线，可以综合每个共混物组分的有利性能;另一方面，普通的、更经济的聚丙烯的使用使整个系统的成本降低。因此，例如可将聚丙烯的固有性能-低吸湿性、便于加工性能和良好机械性能-与所用非烯烃类热塑性塑料的性能如防氧透过性能、耐热形变性能和耐划伤性能结合起来。
非烯烃类热塑性塑料与等规聚丙烯的共混物的缺点是其刚性太高，这在许多应用中是不希望的，例如用于薄膜、管材和波纹板等时。一个方法是使用弹性系统，如基于乙烯和丙烯（EPR）或基于乙烯、丙烯和二烯（EPDM）的无定形共聚物。但是，由于EPR分子量太高、EPDM具有交联结构，无定形共聚物与它们的共混物的缺点是其粘度较高。
因此，本发明的主要目的是提供一种共混物，它一方面可加工成低刚性、即低弹性模量的最终产品，另一方面又可制成低粘度的易流动熔体。
共混物中的聚丙烯组分是弹性聚丙烯时可达到上述目的。
因而，本发明涉及一种共混物，它含有：
a）5%-80%重量、优选10%-60%重量弹性聚丙烯（ELPP），
b）20%-95%重量、优选40%-90%重量非烯烃类热塑性塑料，
c）0-10%重量相容剂，
以及非强制性的其它常规添加剂、填料或增强材料。
根据所需要的性能，这种共混物还可含有其它聚烯烃，例如基于乙烯、丙烯、丁烯、戊烯、己烯或它们的混合物的聚合物，如聚乙烯，或等规立构、间规立构或无规立构丙烯均聚物或共聚物。
用于本发明共混物的弹性聚丙烯特别是那些公开于如US4，335，225、US4，522，982和US5，188，768中的聚丙烯。它们包括均聚物和共聚物。共聚物在分子中除含有丙烯单元外，还含有如乙烯、丁烯、戊烯或己烯单元的其它烯烃单元。它们在链结构中主要是有规立构嵌段排列，例如由交替存在于聚合物链中的等规丙烯序列和间规丙烯序列的嵌段构成。它们例如可根据US4，355，255，通过使用特殊催化剂的聚合反应来制备，催化剂由有机Ti、Zr或Hf化合物与如Al2O3、TiO2、SiO2或MgO的金属氧化物反应或混合制备。另外，也可以用类似于US4，522，982的方法，借助于与铝噁烷组合的金属茂催化剂来制备弹性聚丙烯，或者用类似于US5，118，768的方法，在特殊电子给体存在下使用基于醇镁和四氯化钛的催化剂来制备。
使用ELPP时，粘度的量度-根据ISO1133/DIN53735在230℃/2.17kg下的熔流指数（MFI）为约0.1-50g/10min。优选使用MFI大于1的ELPP。具有较高MFI、即低粘度的ELPP或可从反应器产物直接得到，或例如用有机过氧化物的化学降解得到。
在很多应用中，使用由不饱和接枝单体接枝改性的ELPP证明是有优势的。也可以使用接枝ELPP和未接枝ELPP的混合物。接枝ELPP的接枝程度、即接枝单体的含量为约0.1%-30%重量。适宜接枝单体例如是：不饱和一元和/或二元羧酸，它们的酸酐，它们与C1-C10脂肪醇和二元醇的酯以及它们的缩水甘油酯，乙烯基醇的酯，乙烯基芳烃，或这些单体的混合物，以及这些单体与C2-C10烯烃的混合物。选自马来酸、丙烯酸或甲基丙烯酸或它们的衍生物和选自乙烯基芳烃的接枝单体是特别优选的，如马来酸酐（MAA）、甲基丙烯酸缩水甘油酯（GMA）或苯乙烯。
如在EP-A-280，454或US4，260，690中所述的对IPP的接枝方法，接枝反应可用自由基接枝共聚合方法进行，用烯属不饱和接枝单体对ELPP的接枝例如可以溶液中优选在芳烃中、在50-200℃优选80-150℃进行，或者在熔融态优选在挤出机中、在170-300℃优选200-250℃进行。在聚合物中优选用自由基引发剂如过氧化物或偶氮化合物、和/或如γ-或电子辐射的高能辐射来产生自由基。
适宜非烯烃类热塑性塑料是可用热塑方法加工的所有塑料，例如聚酰胺、聚酯、聚碳酸酯、聚苯乙烯、聚（甲基）丙烯酸酯、聚氨酯、聚甲醛、聚环氧乙烷和聚苯醚。优选非烯烃类热塑性塑料是聚酰胺、聚酯、聚碳酸酯和聚苯乙烯。
适宜相容剂是可用于共混物的所有已知相容剂，例如：不饱和羧酸或其衍生物，如酯、酰卤、酸酐或酰胺，用不饱和羧酸或其衍生物或用乙烯基芳烃接枝的弹性体或聚烯烃。相容剂是商业上可得到的，例如用马来酐接枝的苯乙烯-乙烯/丁烯-苯乙烯（SEBS）三嵌段共聚物（Kraton（R），壳牌公司产品）。优选接枝改性的弹性体或聚丙烯用作相容剂。特别优选接枝改性的弹性聚丙烯。例如马来酸酐、甲基丙烯酸缩水甘油酯或苯乙烯用作接枝单体。
本发明共混物另外还可含有常规添加剂，如加工和长期稳定剂、成核剂、增强材料和填料。优选填料是滑石、白垩和高岭土。因此，本发明共混物例如最好含有2%-50%重量、优选10%-40%重量滑石或者1%-40%重量如玻璃纤维或碳纤维的增强纤维。
本发明共混物的显著特点是，加工时具有良好流动性，而且制成的产品具有较低刚性。它们例如可用于制备薄膜或通过挤出或注塑制备模塑品。
可在180-300℃、在混合机、捏合机或挤出机中将下列组分混合和均化来制备本发明共混物：
a）5%-80%重量弹性聚丙烯（ELPP），
b）20%-95%重量非烯烃类热塑性塑料，
c）0-10%重量相容剂
和非强制性的其它常规添加剂、填料或增强材料。
通过下列实施例来说明可制备本发明共混物的方法。
A.弹性聚丙烯的制备
实施例1
1.1.催化剂的制备
在20℃，在高纯氮下的惰气瓶中，将44.22g灰褐色四（2-甲基-2-苯基-丙基）锆（TNZ;Tm＝66℃，Du Pont）溶于620ml正己烷〔该正己烷已用Cu催化剂（在70℃、BASF催化剂R3-11）除氧、用4A或10A分子筛除水和极性杂质〕中。大部分不溶物沉降15分钟后，将得到的悬浮体经一玻璃料过滤进入一冷却至-40℃的搅拌惰气瓶中〔完全加热至高于150℃并用高纯氮（O2含量低于2ppm）冲压〕。过滤结束后（约需140分钟），在-40℃将瓶中内容物继续搅拌15分钟，使TNZ尽可能定量沉淀。TNZ沉淀后，在升高的N2压力下用滤烛将上清溶液过滤至另一冷却的惰气瓶中。用15分钟在约5-10℃将留下的TNZ溶于另外350ml正己烷中，冷却至-34℃后，使其再次沉淀。
TNZ沉淀物沉降以后，在升高的N2压力下用玻璃滤烛再次将上清溶液过滤至装有第一次母液的冷却惰气瓶中。然后用经液氮冷却的串联冷阱连接的真空油泵抽真空（低于1×10-2mbar），将TNZ干燥。纯化后的TNZ的熔点为68℃，呈乳白色。收集的母液浓缩至200ml，并通过冷至至-40℃将仍溶于其中的TNZ沉淀。经滤烛加压过滤后，将这些TNZ重新溶于100ml己烷中，再次在-40℃沉淀，按上述方法过滤和真空干燥。这纯化方法的总产率为82.2%。所有的操作在高纯氮下进行。
将266.7g调理过的Al2O3（DEGUSSA的氧化铝C，在约800-1000℃、在N2流中调理，在23℃、在相对湿度为50%下贮存16小时，然后在400℃、在N2流中重新干燥，使羟基表面浓度为约1mmol/g氧化铝C）加入6升4颈惰气瓶中，并加入5035ml正己烷（已用BASF R3-11和4A或10A分子筛纯化过）。将悬浮体在300转/分钟搅拌约1小时。在20℃将上述制备的TNZ（不含从母液中得到的产品）溶于465ml正己烷（上述纯化过的）中，然后马上用50分钟在不断搅拌下将该TNZ溶液滴加入Al2O3悬浮液中，加入几毫升TNZ溶液后，Al2O3悬浮液的粘度明显减小。TNZ溶液加完后，将搅拌速度降至120转/分钟，在避光下将该混合物继续搅拌12.5小时。为便于过滤，使得到的催化剂固体沉降1小时，最后经一玻璃料加压过滤分出溶液（时间3小时）。然后在搅拌下，抽真空至低于1×10-2mbar（油扩散泵，通过两个串联的用液氮冷却的冷阱连接）将催化剂固体干燥至恒重292g（时间约5小时）。所有操作在高纯氮下进行。得到的TNZ/Al2O3催色剂呈米浅棕色，是可自由流动粒料，它有形成约1mm直径的小珠的趋势。Zr含量为1.66%重量。
1.2.聚合
充丙烯/抽真空循环三次以后，向已完全加热至160℃、0.1mbar下且装有Wall-flush surface-polished搅拌器、恒温控制套和温度、转数和力矩鉴测装置的20升夹套反应器中充入7.3kg25℃的丙烯。搅拌器转速升至400转/分以后，用300ml的液体丙烯（约20℃）将10.02g步骤1.1.制备的催化剂冲洗入反应器中，2分钟后，转速降至260转/分。然后用约10分钟将丙烯温度升至60℃，并在此温度下保持120分钟（从加入催化剂后计时）。然后搅拌器转速降至200转/分，用3分钟借助于升高的氮气压力向反应器中加入1880g预热至约50℃的丙酮。搅拌器转速升至400转/分计约2分钟后，降至100转/分，用20分钟在60-46℃将未反应的丙烯急速馏掉。留下的ELPP（弹性聚丙烯）/丙酮浆液是可搅拌的，可经过1-英寸底部出料口从反应器中出料。
滤出ELPP并在50℃、氮气流中干燥以后，得到1.88Kg颗粒状/碎料非粘性ELPP，其熔点（Tm）为148.1℃（用Du Pont示差扫描量热计910/20（Thermal Analyst2100）测量），对应于平衡的Zr含量为89ppm、Al2O3含量为0.49%重量。根据ISO1133/DIN53735、在230℃/2.16kg下，ELPP的MFI（熔流指数）低于0.01g/10分钟。
1.3.化学降解
根据1.2.制得的弹性聚丙烯冷却至低于0℃以后，在轮碾机上研磨至粒度低于3mm。然后混入占聚丙烯量0.2%重量的二（2-叔丁过氧基异丙基）苯（Perkadox14SFI，Akzo），将该混合物在220℃的18mm Brabender单螺杆挤出机上熔融，并以1Kg/小时的出料速率经一圆形口模挤出成为3mm直径的线料。在挤出机中的停留时间为约1分钟。在水浴中固化后，将线料切粒。在这个操作中，弹性聚丙烯降解至MFI为25g/10分钟。根据ISO1133/DIN53735、在230℃/2.16Kg测量MFI。
1.4.接枝
1.4.1.用马来酸酐接枝
在用油浴加热的装有回流冷凝器、氮气进管、气密性搅拌器和滴液漏斗的2升搅拌容器中，在氮气流中、在120℃、不断搅拌下，将50g根据1.3.的弹性PP（MFI：25）溶于1，250ml二甲苯（异构体混合物）中，然后加入60g马来酸酐（MAA）。用60分钟在130℃向上述溶液中滴加溶于100ml二甲苯中的40g过氧化苯甲酰。将该溶液继续搅拌60分钟，并在冷却至80℃后加入2.5升丙酮。抽滤滤出沉淀出来的接枝共聚物，在2.5升丙酮中洗涤，再次抽滤，并在80℃真空干燥8小时。IR光谱测定的MAA接枝度为1.2%重量（基于总量）。
1.4.2.用甲基丙烯酸缩水甘油酯接枝
用60g甲基丙烯酸缩水甘油酯（GMA）代替MAA，按照实施例1.4.1.进行接枝。
1.4.3.用苯乙烯接枝
用60g苯乙烯代替MMA，按照实施例1.4.1.进行接枝。
B.共混物的制备
作用下列原料制备共混物：
弹性聚丙烯（ELPP）：
ELPP1 根据实施例1.3.制备
ELPP2 根据实施例1.4.1.制备
ELPP3 根据实施例1.4.2.制备
ELPP4 根据实施例1.4.3.制备
非烯烃类热塑性塑料：
PA 聚酰胺6，Miramid SH3，Leuna
PC 聚碳酸酯，Lexan PK1340，General Electrics
PS 聚苯乙烯，PS165H，BASF
PET 聚对苯二甲酸乙二醇酯，Polyclear G，Hoechst
对比聚烯烃：
IPP：等规立构聚丙烯均聚物，230℃/2.16Kg的MFI＝10g/10分钟，Daplen KS10，PCD Polymere
EPR：乙烯/丙烯树脂，Mooney粘度：65（ML（1+4）121℃），Dutral CO038，Enimont产品
相容剂：
VV1 根据实施例1.4.1.MAA接枝的ELPP
VV2 根据实施例1.4.2.GMA接枝的ELPP
VV3 根据实施例1.4.3.苯乙烯接枝的ELPP
VV4 SEBS共聚物，Kraton G1652，Shell
VV5 MAA接枝的SEBS共聚物，Kraton FG1901X，Shell
实施例2
在带有捏合室和气动填料装置的Brabender Plasticorder中，将20g（50%重量）PA、48g（45%重量）根据实施例1.3.的弹性聚丙烯（ELPP1）和2g（5%重量）相容剂VV5的混合物在260℃捏合6分钟。为测量弹性模量和流变性能，将捏合后的共混物在Battenfeld液压机上在230℃压成2mm厚的薄板。使用80×10×2mm测试样品，根据DIN53452/57的三点弯曲试验测量弹性模量。用贮存和损失模量（在Rheometrics RDS Ⅱ流变仪上、锥板装置，在230℃测量）、借助于Cox-Merz关系式（W.P.Cox，E.Merz，J.Pol.Sci.28（1958）619）来计算剪切速度为10-1和100rad/s时的粘度。弹性模量和粘度值列于表1中。
实施例3-9和对比例V1-V6
使用表1所示原料，按照实施例2的捏合方法制备共混物。实施例V1-V6是非本发明的对比例，其中使用IPP（V1-V4）或弹性体（V5和V6）代替ELPP，作为共混物的烯烃类聚合物组分。
使用PET作为共混物非烯烃类组分（实施例8、9和V4）时，首先单独将PET在加热至270℃的捏合室中熔融2分钟，然后加入剩下的其它组分，并进一步捏合5分钟。同样地，制备含PET测试薄板时的压片温度也是270℃。
共混物的弹性模量和粘度值列于表1。表1中数据表明，本发明含ELPP共混物（实施例2-9）的刚性、即弹性模量大大低于相应的含IPP共混物（比较例V1-V4）的，与含有弹性体（V5和V6）的相似弹性共混物相比，本发明共混物粘度大大降低。
实施例10-13
用表1中所示原料，按照实施例2的捏合方法制备共混物。使用PET作为共混物的非烯烃类聚合物组分时，半捏合温度和压片温度升至270℃。
弹性模量数值以及所用的非烯烃类聚合物组分列于表1中。在所有情况下，都能使刚性大大降低。
Claims (10)
1、含有下列组分的共混物：
a)5%-80%重量弹性聚丙烯(ELPP)，
b)20%-95%重量非烯烃类热塑性塑料，
c)0-10%重量相容剂，
以及非强制性的其它常规添加剂、填料或增强材料。
2、根据权利要求1的共混物，它含有：
a）10%-60%重量弹性聚丙烯（ELPP），
b）40%-90%重量非烯烃类热塑性塑料，
c）0-10%重量相容剂，
以及非强制性的其它常规添加剂、填料或增强材料。
3、根据权利要求1的共混物，其中，该ELPP是用不饱和接枝单体接枝改性过的。
4、根据权利要求1的共混物，其中，该ELPP是接枝ELPP与未接枝ELPP的混合物。
5、根据权利要求1的共混物，其中，该弹性聚丙烯在230℃/2.16kg的熔流指数（MFI）大于1。
6、根据权利要求1的共混物，其中，该非烯烃类热塑性塑料是聚酰胺、聚苯乙烯、聚碳酸酯或聚酯。
7、根据权利要求1的共混物，其中，该相容剂是接枝改性的弹性体或聚丙烯。
8、根据权利要求7的共混物，其中，该相容剂是接枝改性的弹性聚丙烯。
9、根据权利要求1的共混物，其中，该填料是滑石、白垩或高岭土。
10、根据权利要求1的共混物的制备方法，其中在混合机、捏合机或挤出机中在180-300℃将下列组分混合和均化：
a）5%-80%重量弹性聚丙烯（ELPP），
b）20%-95%重量烯烃类热塑性塑料，
c）0-10%重量相容剂，
以及非强制性的其它常规添加剂、填料或增强材料。
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| AT0148593A AT403695B (de) | 1993-07-26 | 1993-07-26 | Blends aus elastomeren polypropylenen und nichtolefinischen thermoplasten |
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| DE4330341A DE4330341A1 (de) | 1993-07-26 | 1993-09-08 | Blends aus elastomeren Polypropylenen und nichtolefinischen Thermoplasten |
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| AT (2) | AT403695B (zh) |
| CZ (1) | CZ179394A3 (zh) |
| DE (2) | DE4330341A1 (zh) |
| ES (1) | ES2110662T3 (zh) |
| FI (1) | FI943491A (zh) |
| HU (1) | HU212461B (zh) |
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| WO2015131583A1 (zh) * | 2014-03-06 | 2015-09-11 | 常熟市江顺塑料制品有限公司 | 一种超薄覆盖塑料薄膜 |
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-
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- 1993-07-26 AT AT0148593A patent/AT403695B/de not_active IP Right Cessation
- 1993-09-08 DE DE4330341A patent/DE4330341A1/de not_active Withdrawn
-
1994
- 1994-07-13 DE DE59404933T patent/DE59404933D1/de not_active Expired - Fee Related
- 1994-07-13 AT AT94110857T patent/ATE161868T1/de not_active IP Right Cessation
- 1994-07-13 ES ES94110857T patent/ES2110662T3/es not_active Expired - Lifetime
- 1994-07-13 EP EP94110857A patent/EP0640650B1/de not_active Expired - Lifetime
- 1994-07-25 JP JP6172824A patent/JPH07145274A/ja not_active Withdrawn
- 1994-07-25 FI FI943491A patent/FI943491A/fi unknown
- 1994-07-25 NO NO942770A patent/NO308079B1/no not_active IP Right Cessation
- 1994-07-25 HU HU9402189A patent/HU212461B/hu not_active IP Right Cessation
- 1994-07-25 RU RU94026253A patent/RU2141492C1/ru active
- 1994-07-25 SK SK897-94A patent/SK280956B6/sk unknown
- 1994-07-25 CN CN94108022A patent/CN1103076A/zh active Pending
- 1994-07-26 CZ CZ941793A patent/CZ179394A3/cs unknown
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040773A (zh) * | 2010-12-07 | 2011-05-04 | 惠州市沃特新材料有限公司 | 一种塑料合金、其制备方法和应用 |
| CN102040773B (zh) * | 2010-12-07 | 2012-11-21 | 惠州市沃特新材料有限公司 | 一种塑料合金、其制备方法和应用 |
| CN103342885A (zh) * | 2013-07-05 | 2013-10-09 | 深圳市奥晶科技有限公司 | 一种玻璃纤维增韧聚碳酸酯/聚丙烯合金材料及其制备方法 |
| WO2015131583A1 (zh) * | 2014-03-06 | 2015-09-11 | 常熟市江顺塑料制品有限公司 | 一种超薄覆盖塑料薄膜 |
| CN105647104A (zh) * | 2016-04-18 | 2016-06-08 | 重庆理工大学 | 一种聚甲醛合金及其制备方法 |
| CN116396593A (zh) * | 2023-04-11 | 2023-07-07 | 金发科技股份有限公司 | 一种热塑性聚酯复合材料及其制备方法和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2110662T3 (es) | 1998-02-16 |
| EP0640650B1 (de) | 1998-01-07 |
| SK89794A3 (en) | 1995-02-08 |
| NO942770L (no) | 1995-01-27 |
| HUT69012A (en) | 1995-08-28 |
| HU212461B (en) | 1996-07-29 |
| AT403695B (de) | 1998-04-27 |
| SK280956B6 (sk) | 2000-10-09 |
| HU9402189D0 (en) | 1994-09-28 |
| ATE161868T1 (de) | 1998-01-15 |
| CZ179394A3 (en) | 1995-02-15 |
| DE59404933D1 (de) | 1998-02-12 |
| ATA148593A (de) | 1997-09-15 |
| NO942770D0 (no) | 1994-07-25 |
| NO308079B1 (no) | 2000-07-17 |
| RU2141492C1 (ru) | 1999-11-20 |
| DE4330341A1 (de) | 1995-03-09 |
| FI943491A (fi) | 1995-01-27 |
| JPH07145274A (ja) | 1995-06-06 |
| EP0640650A1 (de) | 1995-03-01 |
| FI943491A0 (fi) | 1994-07-25 |
| RU94026253A (ru) | 1996-05-27 |
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