CN1218487A - 可发泡的聚苯乙烯珠粒 - Google Patents
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Abstract
本发明涉及含有发泡剂的可发泡的聚苯乙烯珠粒,珠粒用0.01—0.5%(重量)疏水剂涂布,该疏水剂在25℃以上熔化,其平均粒度小于100微米。可将该珠粒加工成水吸附容量低的泡沫塑料模塑制品。
Description
本发明涉及含有发泡剂的可发泡聚苯乙烯(EPS)珠粒,由它们可制成水吸附容量低和/或水渗透率低的模塑制品。
在聚苯乙烯泡沫塑料的许多应用中,例如用作屋顶保温材料、墙壁材料和鱼箱等时,泡沫塑料模塑制品都与水接触,因此存在水分渗透到泡沫塑料内部的危险,从而使保温作用下降。
迄今为止,通常通过将塑料薄膜或表面涂料涂布到制成的模塑制品上来防止或降低聚苯乙烯泡沫塑料制成的厚板和模塑制品的水吸附量。但是,这就需要另外的步骤;此外,在复杂形状制品的情况下,这一覆盖层不能处处均匀。
减少水侵入到聚苯乙烯泡沫塑料制成的模塑制品中的另一方法是使EPS珠粒之间的空间尽可能地小。这一点可通过提高用于膨胀的蒸汽的压力和温度来达到。但是,它的缺点是使模塑制品的生产时间延长,而且如果升温,能耗也增加。
本发明的一个目的是提供可用简单方法且不新增步骤来生产水吸附容量低的模塑的聚苯乙烯泡沫塑料。
我们已发现,这一目的可通过使用含有发泡剂并涂有疏水剂的EPS珠粒来达到。因此,本发明提供了含有发泡剂、并用0.01-0.5%(重量)疏水剂涂布的可发泡聚苯乙烯(EPS)珠粒,该疏水剂在10℃以上熔化,其平均粒度小于100微米。本发明还提供相应的经涂布和发泡的聚苯乙烯珠粒。
为缩短冷却时间,通常用硬脂酸酯例如甘油单硬脂酸酯或硬脂酸锌涂布EPS珠粒。但是,这些硬脂酸酯不是起疏水剂的作用。还已知在模塑制品生产过程中,为了缩短冷却时间,将液体石蜡油涂布到EPS珠粒上,但这会使可发泡性下降。
EPS珠粒可用已知的传统方法生产。为此,将单体苯乙烯(如果需要还将其他烯属不饱和共聚单体)、催化剂、助剂和添加剂悬浮在水中并聚合,通常这一过程在悬浮稳定剂存在下进行。将生成的聚苯乙烯珠粒分出,洗涤和干燥。发泡剂可在聚合过程中加入,或在随后的步骤中加到聚苯乙烯中。适合的发泡剂为C4-C8烃类,优选戊烷。
根据本发明,EPS珠粒用0.01-0.5%、优选0.1-0.3%(重量)疏水剂涂布,每一情况都按固体含量计,该疏水剂在10℃以上熔化,其粒度小于100微米、优选小于10微米。如果粒度太大,则难以制成稳定的乳液。
优选的疏水剂为在碳链中有10-30个碳原子的石蜡烃,优选其熔点为10-70℃、特别是25-60℃。这样的石蜡烃以以下的商业产品提供:BASF的RAMASITKGT、PERSISTOL E和PERSISTOLHP,Henkel的AVERSIN HY-N和Sandoz的CEROL ZN。
另一类适合的疏水剂包括N-羟甲基胺与脂肪酸衍生物(例如脂肪酸酰胺、胺或醇)反应的树脂状产物,例如在US-A2927090或GB-A475170中公开的。其熔点通常为50-90℃。这类树脂例如以以下商业产品提供:BASF的PERSISTOL HP和Hoechst的ARCOPHOBEFM。
最后,聚(甲基)丙烯酸氟烷基酯例如聚丙烯酸全氟辛基酯也是适用的。后一物质以以下商业产品提供:BASF的PERSISTOL O和Pfersee的OLEOPHOBOL C。
本发明EPS珠粒优选用疏水剂的含水乳液涂布来制备。这种乳液含有10-80%、优选15-50%(重量)固体疏水剂。此外,该含水乳液还优选含有传统乳化剂,例如乙氧基化的油基胺,其用量为0.5-5%(重量),以及含有增溶剂和其他传统添加剂。
疏水剂的含水乳液优选在EPS珠粒处理和干燥后立刻涂布到EPS珠粒上,宜与其他传统的涂布剂一起涂布,例如抗粘合剂(例如硬脂酸金属盐和细分散的二氧化硅)以及缩短脱模时间的试剂(例如甘油酯和羟基羧酸酯)。疏水剂也可吸附到多孔固体中,例如细分散的二氧化硅中,其量优选为5-50%(重量),然后用它进行涂布。因为有疏水剂的涂层可提高泡沫塑料的可燃性,所以在某些情况下,优选与疏水剂一起涂布阻燃剂,例如含溴化合物,如六溴环十二烷;基于EPS计,阻燃剂的用量为0.01-0.5%(重量)。原则上,将含水乳液涂布到预发泡的PES珠粒上也是可能的。在这两种情况下,涂布通过喷涂或优选在传统的转鼓混合器中转鼓涂布来实现。
最后,疏水剂也可在苯乙烯在含水悬浮液中聚合生产EPS珠粒的过程中加入。
EPS珠粒用疏水剂处理后,将该珠粒干燥。这一干燥通常在室温下或稍微升温下用空气进行,但是在未发泡的珠粒处理中,这一温度必需低于其软化点,以防止不希望的发泡和发泡剂跑掉。通常,EPS珠粒的平均粒度为0.1-2毫米,特别是0.3-1.0毫米。
同样,含有发泡剂的EPS珠粒发泡制成泡沫塑料通常用现有技术已知的方法进行,首先用蒸汽在开模或闭模预发泡器中预发泡。然后将预发泡的珠粒在气体可透过模具中用蒸汽熔化制成模塑制品或厚板。经发泡的聚苯乙烯珠粒的平均粒度通常为1-10毫米、特别是2-8毫米。
关于传统的聚合、浸渍和发泡方法的更详细内容例如在《塑料手册(Kunststoff handbuch)》,第5卷,聚苯乙烯,R.Vieweg和G.Daumiller编辑,Carl-Hanser-Verlag,Munich,1969中给出。
令人吃惊的是,本发明用疏水剂的处理方法对苯乙烯聚合物的机械性能和加工性能没有任何不良影响。脱模时间也未延长。
疏水剂通常用于片状材料例如纺织品、皮革或纸张上作为防水剂。意想不到的是,用于可发泡的珠粒并发泡和固化制成模塑制品后,它们可使后者不渗水,而且意想不到的是,涂层不会阻碍发泡的珠粒的熔结。
本发明发泡的聚苯乙烯珠粒可优选用于生产经常暴露到水中的模塑制品,例如屋顶保温材料或四周保温板,用于救生器材或对水敏感的填料,例如鱼箱。
在实施例中,份数和百分数都以重量计。
按DIN 53 433测量水吸附量,用以下方法测定水渗透性:将直径100毫米的管子连到厚100毫米的泡沫塑料板上,管中装上100毫米高的水柱。
24小时后,观测泡沫塑料板下是否有水。以毫米水柱为单位测量水面下降程度。实验前,将泡沫塑料板在干燥箱中,在60℃下调制24小时。然后用硅橡胶将管子连上。
实施例1
将25千克EPS(珠粒尺寸0.4-0.7毫米,戊烷含量6.1%)在容积为40升的浆式混合机中与表1所示的涂料组合物在25℃下剧烈混合10分钟。然后将涂布的珠粒在未加压的发泡机(Rauscher体系)中预发泡,12小时后将其加工成模塑板(密度20千克/米3)。
表1列出涂料的组成和板的性能。实验1不是按本发明进行的。
表1
实验 | 涂料%,基于EPS计 | 水吸附量% | 水渗透性mm |
1 | 0.25 GMS0.12 Aerosil R 9720.13 硬脂酸锌 | 5.8 | 28 |
2 | 0.25 GMS0.12 Aerosil R 9720.13 硬脂酸锌0.25 Persistol HP | 0.21 | 2 |
3 | 0.15 GMS0.075 Aerosil R 9720.075硬脂酸锌0.2 Persistol HP | 0.30 | 2 |
4 | 0.25 GMS0.12 Aerosil R 9720.13 硬脂酸锌0.25 Ramasit KGT | 0.20 | 0.5 |
5 | 0.15 GMS0.075 Aerosil R 9720.075硬脂酸锌0.2 Ramasit KGT | 0.19 | 1 |
6 | 0.15 GMS0.12 Aerosil R 9720.13 硬脂酸锌0.1 Persistol HP | 0.9 | 5 |
GMS=工业级甘油单硬脂酸酯
Aerosil R 972=细分散二氧化硅(DEGUSSA)
Persistol HP=BASF的疏水剂,含有22.8%石蜡(熔点52-54℃)和9.6%由N-羟甲基密胺和硬脂酰胺制得的树脂(熔点70℃)的含水乳液
Ramasit KGT=BASF的疏水剂,含16.6%石蜡(熔点52-54℃)的含水乳液
实施例2
步骤如实施例1中的步骤,但疏水剂不用含水乳液,而是吸附在细分散的二氧化硅中(表2)。
表2
实验 | 涂料%,基于EPS计 | 水渗透性 |
1 | 0.05石蜡0.10 Aerosil R 9720.34 GTS0.11 硬脂酸锌 | 不渗透 |
2 | 0.012树脂 N/S0.10 Aerosil R 9720.36 GTS0.125 硬脂酸锌 | 不渗透 |
树脂N/S为N-羟甲基胺与硬脂酰胺的反应产物。GTS表示甘油三硬脂酸酯
实施例3
步骤如实施例1中的步骤,但将不同量的六溴环十二烷(HBCD)加到涂料中作为阻燃剂。结果列入表3;按DIN 4201的着火试验B2,测量一直到火焰熄灭的燃烧时间。
表3
实验 | 涂料%,基于EPS计 | 水渗透性 | 燃烧时间,秒 |
1 | 0.32 GTS0.1 Aerosil R 9720.08 硬脂酸锌 | 可渗透 | 4.8 |
2 | 0.32 GTS0.1 Aerosil R 9720.08 硬脂酸锌0.1 Persistol HP | 不渗透 | 6.5 |
3 | 0.32 GTS0.1 Aerosil R 9720.03 硬脂酸锌0.1 Persistol HP0.05 HBCD | 不渗透 | 4.6 |
4 | 0.32 GTS0.1 Aerosil R 9720.1 Persistol HP0.08 HBCD | 不渗透 | 4.4 |
实施例4
实验1
将124克平均粒度为0.9毫米的可发泡的聚苯乙烯珠粒在Rauscher型未加压的发泡机中预发泡2分钟,使密度达到35克/升。中间贮存24小时后,将预发泡的珠粒在含有17%Persistol O(BASF AG)的含水乳液的浴中浸泡15分钟,该乳液的pH值已用乙酸调节到4。
然后用冷空气将珠粒干燥,转移到厚5厘米、直径25厘米的模具中,并用蒸汽熔结制成模塑制品。模塑制品的氟含量为0.22克/100克。
为了测定水吸附容量,将直径10厘米、高10厘米的水柱作用在模塑制品上。24小时后,水面下降2毫米。
实验2(对比)
步骤如实验1中的步骤,但不用Persistiol O含水乳液进行处理。
为了测定水吸附容量,将直径10厘米、高10厘米的水柱作用在模塑制品上。24小时后,水面下降40毫米。
Persistol O为BASF提供的一种疏水剂,它含有聚丙烯酸全氟辛基酯。
Claims (16)
1.含有发泡剂的可发泡聚苯乙烯(EPS)珠粒,它用0.01-0.5%(重量)疏水剂涂布,后者在10℃以上熔化,其平均粒度小于100微米。
2.根据权利要求1的可发泡聚苯乙烯珠粒,其中疏水剂为碳链中有10-30个碳原子的石蜡烃。
3.根据权利要求1的可发泡聚苯乙烯珠粒,其中疏水剂为N-羟甲基胺和脂肪酸衍生物的反应产物。
4.根据权利要求1的可发泡聚苯乙烯珠粒,其中疏水剂为聚(甲基)丙烯酸全氟烷基酯。
5.根据权利要求1的可发泡聚苯乙烯珠粒,其中珠粒用疏水剂的含水乳液涂布。
6.一种制备权利要求1的可发泡聚苯乙烯珠粒的方法,该方法包括用含有10-80%(重量)疏水剂的含水乳液处理可发泡的聚苯乙烯珠粒。
7.根据权利要求6的方法,其中含水乳液还含有乳化剂和/或增溶剂。
8.根据权利要求6的方法,其中除了疏水剂外,还将阻燃剂和/或抗结块剂和/或缩短脱模时间的试剂涂到EPS珠粒上。
9.根据权利要求6的方法,其中用喷涂或转鼓涂布方法进行所述处理。
10.根据权利要求6的方法,其中将疏水剂的含水乳液吸附在细分散的二氧化硅上,并用生成的粉末混合物涂布可发泡的聚苯乙烯珠粒。
11.一种制备权利要求1的可发泡聚苯乙烯珠粒的方法,其中将疏水剂吸附到细分散的二氧化硅上,并用它涂布EPS珠粒。
12.一种制备权利要求1的可发泡聚苯乙烯珠粒的方法,该方法包括在苯乙烯在含水悬浮液中聚合生产EPS珠粒的过程中加入疏水剂。
13.用0.01-0.5%(重量)权利要求1中所述的疏水剂涂布的、发泡的聚苯乙烯珠粒。
14.一种生产发泡的聚苯乙烯珠粒的方法,该方法包括使权利要求1的涂布的EPS珠粒发泡。
15.一种生产发泡的聚苯乙烯珠粒的方法,该方法包括用0.01-0.5%(重量)权利要求1中所述的疏水剂涂布发泡的聚苯乙烯珠粒。
16.权利要求13的发泡的聚苯乙烯珠粒用于生产屋顶保温材料、四周保温板、救生器材或水敏感包装材料的应用。
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DE19619397A DE19619397A1 (de) | 1996-05-14 | 1996-05-14 | Expandierbare Polystyrolpartikel |
DE19619397.4 | 1996-05-14 |
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CN1218487A true CN1218487A (zh) | 1999-06-02 |
CN1070207C CN1070207C (zh) | 2001-08-29 |
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CN97194631A Expired - Fee Related CN1070207C (zh) | 1996-05-14 | 1997-05-07 | 可发泡的聚苯乙烯珠粒 |
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US (1) | US5985943A (zh) |
EP (1) | EP0898593B1 (zh) |
JP (1) | JP3886154B2 (zh) |
CN (1) | CN1070207C (zh) |
AT (1) | ATE213260T1 (zh) |
AU (1) | AU2894497A (zh) |
CA (1) | CA2255591C (zh) |
DE (2) | DE19619397A1 (zh) |
ES (1) | ES2172787T3 (zh) |
NO (1) | NO313639B1 (zh) |
WO (1) | WO1997043334A1 (zh) |
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-
1996
- 1996-05-14 DE DE19619397A patent/DE19619397A1/de not_active Withdrawn
-
1997
- 1997-05-07 ES ES97923024T patent/ES2172787T3/es not_active Expired - Lifetime
- 1997-05-07 AT AT97923024T patent/ATE213260T1/de not_active IP Right Cessation
- 1997-05-07 CA CA002255591A patent/CA2255591C/en not_active Expired - Fee Related
- 1997-05-07 JP JP54048897A patent/JP3886154B2/ja not_active Expired - Fee Related
- 1997-05-07 WO PCT/EP1997/002362 patent/WO1997043334A1/de active IP Right Grant
- 1997-05-07 US US09/147,246 patent/US5985943A/en not_active Expired - Fee Related
- 1997-05-07 CN CN97194631A patent/CN1070207C/zh not_active Expired - Fee Related
- 1997-05-07 AU AU28944/97A patent/AU2894497A/en not_active Abandoned
- 1997-05-07 DE DE59706390T patent/DE59706390D1/de not_active Expired - Lifetime
- 1997-05-07 EP EP97923024A patent/EP0898593B1/de not_active Expired - Lifetime
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- 1998-11-13 NO NO19985295A patent/NO313639B1/no not_active Application Discontinuation
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105143324A (zh) * | 2013-03-15 | 2015-12-09 | 耐克创新有限合伙公司 | 用于提高与超临界流体的相容性的改性热塑性弹性体 |
CN105143324B (zh) * | 2013-03-15 | 2018-02-06 | 耐克创新有限合伙公司 | 用于提高与超临界流体的相容性的改性热塑性弹性体 |
CN107603043A (zh) * | 2017-08-31 | 2018-01-19 | 苏州仲勉装饰有限公司 | 一种聚苯乙烯泡沫塑料板的制备方法 |
Also Published As
Publication number | Publication date |
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EP0898593A1 (de) | 1999-03-03 |
DE59706390D1 (de) | 2002-03-21 |
NO313639B1 (no) | 2002-11-04 |
CN1070207C (zh) | 2001-08-29 |
DE19619397A1 (de) | 1997-11-20 |
NO985295L (no) | 1998-11-13 |
EP0898593B1 (de) | 2002-02-13 |
JP2000510182A (ja) | 2000-08-08 |
WO1997043334A1 (de) | 1997-11-20 |
CA2255591A1 (en) | 1997-11-20 |
JP3886154B2 (ja) | 2007-02-28 |
AU2894497A (en) | 1997-12-05 |
ES2172787T3 (es) | 2002-10-01 |
CA2255591C (en) | 2006-07-11 |
ATE213260T1 (de) | 2002-02-15 |
NO985295D0 (no) | 1998-11-13 |
US5985943A (en) | 1999-11-16 |
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