CN1665866A - 开孔聚丙烯泡沫颗粒 - Google Patents
开孔聚丙烯泡沫颗粒 Download PDFInfo
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Abstract
本发明涉及含有大于40%的开孔的丙烯聚合物泡沫颗粒。这些颗粒通过用挥发性发泡剂将含有1-40重量%开孔剂的丙烯聚合物微粒浸渍在水悬浮液中,然后发泡来生产。
Description
本发明涉及基于丙烯聚合物的开孔泡沫珠。
由丙烯聚合物生产的泡沫制件越来越广泛地用于汽车内部制件,作为包装材料和作为消费品。它们通过相应泡沫珠的后膨胀和烧结来获得。这些泡沫珠又通过公知的方法获得(例如EP-A 95109),其中用挥发性发泡剂在压力容器中将聚丙烯颗粒浸渍在水悬浮液中,然后将该混合物解压缩。以此方式生产的泡沫珠在DSC热图谱中显示所谓的双峰,即至少有一个处于比所用丙烯聚合物的熔点峰更高温度下的高温峰(参见例如EP-A415744)。它们的特点是特别好的加工性能和机械性能,例如耐热变形性。这种泡沫珠通常具有闭孔;例如,根据EP-A 95109的泡沫珠具有至少65%的闭孔。这在大多数应用中也是希望的。
EP-A 1016690描述了由丙烯聚合物制备的泡沫珠,其包含水作为发泡剂和0.05-10重量%的亲水性聚合物,例如聚酰胺、聚酯或聚乙烯醇。但是,它们包含至少85%的闭孔,即不是开孔的。
开孔塑料泡沫通常比闭孔泡沫塑料具有更高的弹性,和具有隔音作用,这是有利的,例如用于汽车内饰和一些包装材料中。WO00/15700描述了开孔聚烯烃泡沫材料,其具有良好的吸音性能。它们是通过聚烯烃熔体与挥发性有机发泡剂一起挤出获得的板、膜或管。在这种泡沫材料的挤出中,仅仅可能生产具有简单几何形状的模制品。另外,这些泡沫材料没有上述在DSC热图谱中的双峰,所以例如它们的耐热变形性对于一些应用而言是不足的。
本发明的目的是提供基于丙烯聚合物的开孔泡沫珠,其特别显示良好的机械性能和能进一步以各种方式加工。
我们发现该目的通过开孔泡沫珠来达到,该开孔泡沫珠具有1-10mm的平均珠尺寸和基于丙烯聚合物的5-200g/l的堆积密度,和具有大于40%比例的开孔(根据DIN ISO 4590)。
一种生产这种开孔泡沫珠的优选方法包括用挥发性发泡剂在压力容器中在高温下将丙烯聚合物珠粒浸渍在水悬浮液中,然后将该混合物解压缩。丙烯聚合物珠包含1-40重量%的开孔剂,例如极性的水不溶性热塑体、水溶性的聚合物或针状无机固体。
为了本发明的目的,丙烯聚合物是:
a.丙烯均聚物,
b.丙烯与最多15重量%的乙烯和/或1-丁烯的无规共聚物,优选丙烯与0.5-6重量%的乙烯或与0.5-12重量%1-丁烯的共聚物,或者丙烯、0.5-6重量%乙烯和0.5-6重量%1-丁烯的三元共聚物,
c.a.或b.与0.1-75重量%、优选3-50重量%的聚烯烃弹性体的混合物,例如乙烯-丙烯嵌段共聚物。
用齐格勒催化剂或用茂金属催化剂生产的丙烯聚合物是合适的。
丙烯聚合物的结晶熔点(DSC峰最大值)是120-170℃。通过DSC方法测定的熔融焓优选是50-110J/g,根据DIN 53735测定的熔体流动指数(MFI)(230℃,2.16kp)是2-25g/10分钟。
根据本发明的开孔泡沫珠是从颗粒生产,优选这些颗粒具有0.2-10mm的平均直径,特别是0.5-5mm。这些颗粒通常是圆柱形或球形的微粒,通过将丙烯聚合物与混合的开孔剂和其它添加剂一起挤出并将该混合物强制通过挤出机来获得,如果需要的话可以将该混合物冷却,和将该混合物造粒。
必要的是这些微粒含有1-40重量%、优选5-35重量%的开孔剂。优选的开孔剂是极性的水不溶性热塑体,优选聚酰胺(PA)或聚甲醛(POM);水溶性聚合物,优选聚乙烯吡咯烷酮(PVP),聚乙酸乙烯酯和聚氧化乙烯;还可以是针状无机固体,优选具有0.25-5mm长度的雕玻璃。另外,微粒可以含有常规添加剂,例如抗氧化剂、稳定剂、阻燃剂、蜡、颜料、染料和特别是成核剂,例如滑石、石墨粉、热解硅酸、沸石、膨润土和聚烯烃蜡。
微粒分散在搅拌型反应器中的悬浮介质中。优选的悬浮介质是水。在这种情况下,必须加入悬浮助剂以保证微粒在悬浮介质中的均匀分布。合适的悬浮助剂是水不溶性无机稳定剂,例如磷酸三钙、焦磷酸镁和碳酸钙;还有聚乙烯醇和表面活性剂,例如芳基磺酸盐和脂肪醇氧基化物。它们的用量是0.05-5重量%,基于微粒计。挥发性发泡剂向悬浮介质中的添加量是2-50重量%,优选5-30重量%,基于微粒计。发泡剂可以在反应器内容物的加热之前、期间或之后加入。合适的发泡剂是沸点为-5至150℃的有机化合物,例如烷烃、酮和醚,以及无机气体,例如氮气和二氧化碳。特别优选C4-C6烃。
在浸渍期间,温度应该在大约丙烯聚合物的软化点附近。该温度可以是从比熔点(结晶熔点)低40℃至比该熔点高15℃。优选的浸渍温度是120-160℃。根据发泡剂的类型和用量以及根据温度,在反应器内的压力通常大于2巴,但不超过40巴。浸渍时间应该通常是0.5-10小时,在此之后,反应器快速解压。在该操作期间,被发泡剂浸渍的丙烯聚合物珠膨胀。由于开孔剂的作用,在该过程中形成根据本发明的开孔泡沫珠。在解压和从反应器排出之后,将泡沫珠从悬浮介质中分离出来并洗涤。如果使用水溶性开孔剂,将该开孔剂同时基本上洗掉。在水不溶性开孔剂的情况下,这些开孔剂保留在泡沫珠中。
根据本发明的开孔泡沫珠具有特别好的机械性能,如果它们在DSC熔融谱中具有至少一个比所用丙烯聚合物的熔融峰更高温度的高温峰的话。这些泡沫珠的平均珠尺寸是1-10mm,优选2-8mm;它们的堆积密度可以是5-200g/l,优选10-100g/l。它们的特征在于开孔的比例(根据DIN ISO4590)大于40%,优选大于50%和特别是大于75%。在理想的情况下,基本上所有的孔都是开放的,也就是说,泡沫结构仅仅由泡孔网组成。平均泡孔直径优选是0.01-0.5mm,特别是0.05-0.3mm。
泡沫模制品可以从根据本发明的泡沫珠按照公知的包括后膨胀和烧结的方法生产。
在下面实施例中的份(P)是按重量计。
实施例
P表示重量份。
原料:
PP1:Novolen 3200MC;来自Basell GmbH的聚丙烯
POM1:Ultraform N 2320(BASFAG)
PA1:Ultramid B3(BASF AG)
PS1:标准聚苯乙烯,Mw=195000g/mol,MVR=10cm3/10分钟(BASFAG)
PVP1:聚乙烯吡咯烷酮,Kollidon K 30,来自BASFAG
玻璃:雕玻璃3786
Wax1:Luwax AF 31;聚乙烯(Mn=3000),来自BASF AG
滑石:HP 325
s-Pentane:工业级戊烷异构体混合物
正-/异-丁烷:工业级丁烷异构体混合物
Antiblock1:CaCO3;
Antiblock2:磷酸三钙;
Surf1:脂肪醇氧基化物
Surf2:芳基磺酸盐
颗粒的生产:
为了生产颗粒,将原料混合,加入挤出机和转化成微粒(d:0.8-1.2mm;I:1.8-3mm)。
Gran1(G1):100P的PP1、20P的POM1、1P的滑石、0.5P的Wax1
Gran2(G2):100P的PP1、34P的POM1、2.8P的滑石、0.5P的Wax1
Gran3(G3):100P的PP1、25P的玻璃、0.5P的Wax1
Gran4(G4):100P的PP1、20P的PA1、1P的滑石、0.5P的Wax1
Gran5(G5):100P的PP1、25P的PVP1、1.25P的滑石、0.6P的Wax1
Gran6(G6):100P的PP1、20P的滑石、0.5P的Wax1
Gran7(G7):100P的PP1、20P的PS1、1P的滑石、0.5P的Wax1
颗粒的发泡
表中显示了在这些泡沫珠上测定的堆积密度和开孔比例。开孔比例按照DIN ISO 4590对泡沫珠检测得到。
实施例1-4
在每种情况下,将100P的颗粒、6.7P的Antiblock1、0.13P的Surf1、230P的水和表中所示量的正-/异-丁烷加入密闭的搅拌釜中。该釜然后在约55分钟内加热到表中显示的浸渍温度(IMT),当达到该温度后,通过将内容物解压到环境压力而将颗粒发泡。
实施例5-10
在每种情况下,将100P的颗粒、8.75P的Antiblock2、0.33P的Surf2、234P的水和表中所示量的正-/异-丁烷加入密闭的搅拌釜中。该釜然后在约55分钟内加热到表中显示的浸渍温度(IMT),当达到该温度后,通过将内容物解压到环境压力而将颗粒发泡。
表
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | 实施例7 | 实施例8 | 实施例9 | 实施例10 | |
颗粒 | G1 | G1 | G1 | G1 | G2 | G3 | G4 | G5 | G6 | G7 |
IMT[℃] | 129.0 | 129.0 | 128.7 | 127.6 | 128.0 | 127.5 | 130.0 | 129.0 | 130.0 | 136.0 |
发泡剂[P] | 24 | 20 | 20 | 20 | 24 | 24 | 35 | 24 | 35 | 16 |
堆积密度[g/l] | 18 | 31 | 30 | 37 | 15 | 11 | 14 | 9 | 15 | 13 |
开孔[%] | 43 | 42 | 51 | 65 | 80 | 59 | 79 | 65 | 10 | 9 |
[P]=重量份/100重量份PP微粒
实施例9-10是对比例。
Claims (11)
1、开孔泡沫珠,具有1-10mm的平均珠尺寸和基于丙烯聚合物的5-200g/l的堆积密度,和具有大于40%比例的开孔(根据DIN ISO 4590)。
2、根据权利要求1的开孔泡沫珠,其中丙烯聚合物是丙烯的均聚物或者丙烯与最多15重量%的乙烯和/或1-丁烯的共聚物。
3、根据权利要求1的开孔泡沫珠,其在DSC热图谱中具有至少一个在比所用丙烯聚合物的熔融峰温度更高温度下的高温峰。
4、根据权利要求1的开孔泡沫珠,其中平均泡孔直径是0.01-0.5mm。
5、根据权利要求1的开孔泡沫珠,其具有1-40重量%的开孔剂含量。
6、一种生产根据权利要求1的开孔泡沫珠的方法,其中用挥发性发泡剂在压力容器中在高温下将丙烯聚合物泡沫珠浸渍在悬浮液中,然后将该混合物解压,其中丙烯聚合物珠含有1-40重量%的开孔剂。
7、根据权利要求6的方法,其中发泡剂是沸点为-5至150℃的有机化合物,优选C4-C6烃,或是无机气体。
8、根据权利要求6的方法,其中开孔剂是极性的水不溶性热塑体,优选聚酰胺或聚甲醛。
9、根据权利要求6的方法,其中开孔剂是针状无机固体,优选长度为0.25-5mm的雕玻璃。
10、根据权利要求6的方法,其中开孔剂是水溶性聚合物,优选聚乙烯吡咯烷酮、聚乙酸乙烯酯或聚氧化乙烯。
11、通过将权利要求1的泡沫珠进行后膨胀和烧结而生产的开孔泡沫模制品。
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DE10230583.8 | 2002-07-05 | ||
DE10230583A DE10230583A1 (de) | 2002-07-05 | 2002-07-05 | Offenzellige Polypropylen-Partikelschäume |
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EP (1) | EP1521799B1 (zh) |
JP (1) | JP4128177B2 (zh) |
KR (1) | KR100988407B1 (zh) |
CN (1) | CN100528944C (zh) |
AU (1) | AU2003250861A1 (zh) |
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WO (1) | WO2004005383A1 (zh) |
Cited By (4)
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CN101531770B (zh) * | 2008-05-15 | 2011-11-23 | 上海高分子功能材料研究所 | 开孔发泡聚烯烃的制备与应用 |
CN109415529A (zh) * | 2016-06-23 | 2019-03-01 | 巴斯夫欧洲公司 | 制备由具有聚酰胺链段的热塑性弹性体制成的泡沫颗粒的方法 |
CN113045827A (zh) * | 2020-12-17 | 2021-06-29 | 株式会社Jsp | 聚丙烯系树脂发泡颗粒以及发泡颗粒成形体 |
CN113754954A (zh) * | 2021-08-24 | 2021-12-07 | 无锡敬仁电子材料科技有限公司 | 一种兼具高通孔率和高闭孔率的发泡聚合物吸波材料及其制备方法 |
Families Citing this family (11)
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TW200517426A (en) | 2003-08-25 | 2005-06-01 | Dow Global Technologies Inc | Aqueous dispersion, its production method, and its use |
DE10360398A1 (de) * | 2003-12-19 | 2005-07-14 | Basf Ag | Schaumstoffformteile aus offenzelligem EPP |
DE102004002367A1 (de) * | 2004-01-15 | 2005-08-11 | Basf Ag | Expandierte Polyolefinpartikel enthaltend spezielle Keimbildner |
US8357727B2 (en) | 2004-02-27 | 2013-01-22 | Dow Global Technologies Llc | Durable foam of olefin polymers, methods of making foam and articles prepared from same |
US7361694B2 (en) | 2004-02-27 | 2008-04-22 | Dow Global Technologies Inc. | Durable foam of olefin polymers, methods of making foam and articles prepared from same |
DE102005055076A1 (de) * | 2005-11-16 | 2007-05-24 | Basf Ag | Verfahren zur Herstellung von Polyolefin-Schaumpartikeln mit hoher Schüttdichte und enger Schüttdichtenverteilung |
DE102006000363A1 (de) | 2006-07-21 | 2008-01-24 | Hilti Ag | Befestigungselement |
BRPI0603479A (pt) * | 2006-08-14 | 2008-04-01 | Maria Isabel Pinto Koleski | espuma de polipropileno expandida |
CN105849167B (zh) * | 2013-12-27 | 2020-04-14 | 株式会社钟化 | 聚烯烃系树脂发泡粒子及聚烯烃系树脂模内发泡成型体 |
KR102141993B1 (ko) | 2018-11-26 | 2020-08-06 | 롯데케미칼 주식회사 | Voc 방출이 저감된 사출용 폴리프로필렌계 수지 조성물 |
US11780981B2 (en) * | 2018-12-06 | 2023-10-10 | Exxonmobil Chemical Patents Inc. | Foam beads and method of making the same |
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AU2044597A (en) * | 1996-04-05 | 1997-10-29 | Kaneka Corporation | Hydrous polyolefin resin composition, preexpanded particles produced therefrom, process for producing the same, and expanded moldings |
DE19638039A1 (de) * | 1996-09-18 | 1998-03-19 | Basf Ag | Verfahren zur Herstellung von expandierten Polyolefin-Partikeln |
GB2324798B (en) * | 1997-05-01 | 1999-08-18 | Ici Plc | Open celled cellular polyurethane products |
SG77671A1 (en) * | 1998-03-23 | 2001-01-16 | Jsp Corp | Foamed and expanded beads of polypropylene resin for molding |
DE19921386A1 (de) * | 1999-05-10 | 2000-11-16 | Basf Ag | Offenzellig Partikelschaumstoffe |
DE19950420A1 (de) | 1999-10-20 | 2001-04-26 | Basf Ag | Partikelförmige, expandierbare Olefinpolymerisate |
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2002
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- 2003-06-30 WO PCT/EP2003/006895 patent/WO2004005383A1/de active Application Filing
- 2003-06-30 KR KR1020057000106A patent/KR100988407B1/ko active IP Right Grant
- 2003-06-30 PL PL374820A patent/PL206014B1/pl unknown
- 2003-06-30 EP EP03762546.4A patent/EP1521799B1/de not_active Expired - Lifetime
- 2003-06-30 JP JP2004518621A patent/JP4128177B2/ja not_active Expired - Fee Related
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101531770B (zh) * | 2008-05-15 | 2011-11-23 | 上海高分子功能材料研究所 | 开孔发泡聚烯烃的制备与应用 |
CN109415529A (zh) * | 2016-06-23 | 2019-03-01 | 巴斯夫欧洲公司 | 制备由具有聚酰胺链段的热塑性弹性体制成的泡沫颗粒的方法 |
CN109415529B (zh) * | 2016-06-23 | 2022-08-30 | 巴斯夫欧洲公司 | 制备由具有聚酰胺链段的热塑性弹性体制成的泡沫颗粒的方法 |
CN113045827A (zh) * | 2020-12-17 | 2021-06-29 | 株式会社Jsp | 聚丙烯系树脂发泡颗粒以及发泡颗粒成形体 |
CN113754954A (zh) * | 2021-08-24 | 2021-12-07 | 无锡敬仁电子材料科技有限公司 | 一种兼具高通孔率和高闭孔率的发泡聚合物吸波材料及其制备方法 |
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Publication number | Publication date |
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EP1521799A1 (de) | 2005-04-13 |
AU2003250861A1 (en) | 2004-01-23 |
WO2004005383A1 (de) | 2004-01-15 |
KR100988407B1 (ko) | 2010-10-18 |
PL206014B1 (pl) | 2010-06-30 |
PL374820A1 (en) | 2005-10-31 |
EP1521799B1 (de) | 2019-04-10 |
CN100528944C (zh) | 2009-08-19 |
JP2006509051A (ja) | 2006-03-16 |
US20050236728A1 (en) | 2005-10-27 |
KR20050025580A (ko) | 2005-03-14 |
DE10230583A1 (de) | 2004-01-15 |
JP4128177B2 (ja) | 2008-07-30 |
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