CN101778890B - 用于可发性苯乙烯聚合物颗粒的涂料制剂 - Google Patents
用于可发性苯乙烯聚合物颗粒的涂料制剂 Download PDFInfo
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- C08J9/22—After-treatment of expandable particles; Forming foamed products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2325/04—Homopolymers or copolymers of styrene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
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Abstract
本发明涉及一种用于可发性苯乙烯聚合物颗粒的涂料组合物，其包含：(A)10至90重量％的熔点在60至65℃范围内的三硬脂基酯，(B)10至90重量％的熔点在70至95℃范围内的羟基C16-C18油酸的三酸甘油酯：还涉及具有至少一个由所述涂料组合物制剂构成的涂层的可发性苯乙烯聚合物颗粒。
Description
技术领域
本发明涉及一种可发性苯乙烯聚合物颗粒的涂料制剂。
背景技术
为顺利地运输可发性聚苯乙烯(EPS)，并降低预先发泡的聚苯乙烯泡沫颗粒的静电带电水平，通常用抗静电剂涂覆EPS颗粒。从颗粒材料的表面磨损或冲掉涂料组合物通常产生令人不满意的抗静电性质。另外，带抗静电剂的涂层还可导致颗粒材料结块和较差的流动特性。
EP-A 470 455描述了带有由季铵盐和微粒二氧化硅形成的涂层的珠状抗静电可发性苯乙烯聚合物，其特征是具有良好的流动特性。
DE 195 41 725 C1描述了具有降低的吸水能力的可发性苯乙烯珠状聚合物，其具有一涂层，该涂层除了甘油三硬脂酸酯、硬脂酸锌、和甘油单硬脂酸酯以外还包含以涂层重量为基准计5至50重量％的疏水硅酸盐。
DE 195 30 548 A1描述了具有降低的吸水能力的可发性苯乙烯珠状聚合物，其具有一涂层，该涂层除了以涂层重量为基准计10至90重量％的椰子油或石蜡油以外还有利地包含一种基于疏水硅酸盐的抗结块剂。
此外，GB 1,581,237还描述了使用蓖麻蜡(氢化蓖麻油，HCO)作为可发性聚苯乙烯的涂料组合物，以提高预先发泡的EPS颗粒烧结后泡沫模制品的可变形性和质量。
发明内容
只有在板制备或泡沫制备过程中可接受明显更长的脱模时间，特别是更长降压时间，用所述涂料组合物制剂才通常可取得良好机械性质，特别是挠曲强度和耐压强度。
因此本发明的一个目标是消除提及的缺陷并寻找到一种用于可发性苯乙烯聚合物颗粒的涂料组合物制剂，所述涂料组合物在预先发泡过 程中表现出较低的颗粒材料结决趋势、且允许以较低静电带电水平快速加工预先发泡的颗粒材料，形成具有良好的机械性质的泡沫模制品。
因此，已发现一种用于可发性苯乙烯聚合物颗粒的涂料组合物制剂，其包含
(A)10至90重量％的熔点在60至65℃范围内的三硬脂基酯，
(B)10至90重量％的熔点在70至95℃范围内的羟基C16-C18油酸的三酸甘油酯。
所述涂料还可包含抗静电剂和/或涂料助剂，或可施用于使用其他涂料组合物的其他涂料。
用于可发性颗粒苯乙烯聚合物的一种优选的涂料组合物制剂基本由以下物质组成，
(A)20至80重量％的熔点在60至65℃范围内的三硬脂基酯，
(B)15至60重量％，特别是20至45重量％的熔点在70至95℃范围内的羟基C16-C18油酸的三酸甘油酯，
(C)5至30重量％的亲水或疏水硅酸盐或硬脂酸锌，
(D)0至40重量％，特别是10至50重量％的C16-C18脂肪酸的甘油单酯，
(E)0至10重量％的季铵盐、锍盐或亚乙基二硬脂基二酰胺，其中组分(A)至(E)总计为100重量％。
组分(A)和(B)是天然产物，其通常包含少量杂质，且更具体地也可包含其他酸的一酸甘油酯、二酸甘油酯和三酸甘油酯。
优选所述涂料组合物制剂包含三硬脂酸甘油酯(GTS)或柠檬酸三硬脂基酯(CTS)作为三硬脂基酯(A)。
优选将单羟基C16-C18链烷酸的三酸甘油酯，特别是氢化蓖麻油(HCO，蓖麻蜡)用作羟基C16-C18油酸的三酸甘油酯(B)。
优选将甘油单硬脂酸酯(GMS)用作C16-C18脂肪酸的甘油单酯(D)。
本发明还提供了具有至少一个由上述涂料组合物制剂构成的涂层的可发性苯乙烯聚合物颗粒。
优选的可发性苯乙烯聚合物颗粒具有：
(I)一个第一涂层，其由基于所述可发性苯乙烯聚合物计0.1至2重量％的至少一种选自甘油单硬脂酸酯、甘油二硬脂酸酯、硬脂酸锌、 季铵盐、锍盐和亚乙基二酰胺的化合物构成，和
(II)一个第二涂层，其由基于所述可发性苯乙烯聚合物计0.1至2重量％的一种本发明的上述涂料制剂构成。
所述涂料也可在涂覆步骤中施用于原料。
所述可发性苯乙烯聚合物颗粒优选由包含发泡剂的苯乙烯聚合物组成，实例有聚苯乙烯(PS)，苯乙烯共聚物如苯乙烯-丙烯腈(SAN)、苯乙烯-丁二烯嵌段共聚物，和它们的混合物。
可发性苯乙烯聚合物颗粒是一种例如可通过使用热空气或蒸汽形成以得到膨胀的苯乙烯聚合物颗粒的材料。其通常包含基于所述苯乙烯聚合物计2至10重量％，优选3至7重量％的量的化学或物理发泡剂。
优选的物理发泡剂有气体，如氮气或二氧化碳，或者为含有2至7个碳原子的脂族烃、醇、酮、醚、或卤代烃。特别优选使用异丁烷、正丁烷、异戊烷、正戊烷、新戊烷、己烷、或它们的混合物。
此外，所述可发性苯乙烯聚合物颗粒还可包含有效量的常规助剂，如染料，颜料，填充剂，IR吸收剂例如炭黑、铝、或石墨，稳定剂，阻燃剂如六溴环十二烷(HBCD)，阻燃助剂如过氧化二异丙苯，成核剂，或润滑剂。
本发明的可发性苯乙烯聚合物颗粒可以根据制备方法成为球状或珠状或圆柱状的，其平均颗粒直径通常在0.05至5mm，特别是0.3至2.5mm的范围内，如果合适，可使用筛分方法将其分为不同的部分。
根据膨胀程度的变化，膨胀的苯乙烯聚合物颗粒的平均颗粒直径在1至10mm，特别是2至6mm的范围内，且其密度在10至200kg/m3的范围内。
所述可发性苯乙烯聚合物颗粒例如可通过在容器中用发泡剂压力浸渍热塑性聚合物颗粒获得，通过在发泡剂存在下的悬浮聚合获得，或通过在挤出机或静电混合器中熔融浸渍然后在水下加压粒化获得。
膨胀的苯乙烯聚合物颗粒可通过在压力预先发泡器中例如使用热空气或蒸汽使可发性苯乙烯聚合物颗粒发泡获得，通过在容器中用发泡剂压力浸渍苯乙烯聚合物颗粒然后降压获得，或者通过熔融挤出包含发泡剂的熔体、发泡、然后粒化获得。通常用本发明的涂料组合物涂覆的可发性苯乙烯聚合物与常规涂料相比可在相当的预先发泡条件下发泡 至更低的体积密度。单次预先发泡的体积密度通常在10至20kg/m3的范围内，优选在15至18kg/m3的范围内。
所述可发性或已发的苯乙烯聚合物颗粒的涂覆可在发泡过程之前或之后进行，例如通过在桨式混合机 中施用本发明的涂料制剂，或通过用一种溶液接触(例如通过浸渍或喷涂)所述颗粒苯乙烯聚合物的表面。在通过挤出包含发泡剂的熔体进行制备的情况下，也可以以水溶液或水悬浮液的形式将所述涂料组合物制剂加入水下粒化器的水回路中。
本发明的可发性苯乙烯聚合物颗粒具有抗静电修饰，在预先发泡过程中几乎没有结块趋势，而在发泡过程中能良好熔化得到模制品。当烧结预先发泡的颗粒材料以得到具有高耐压强度和高挠曲强度的泡沫模制品时，可实现极短的降压时间。因此，与常规涂料相比，可在较短的脱模时间内得到模制品需要的挠曲强度。由于高效熔化，即使较大模制品也在边缘及外层区域具有均匀耐压强度和挠曲强度，和明显地更光滑的表面。
具体实施方式
实施例：
发明实施例1至4：
涂料组合物制剂：
在干冰辅助下研磨氢化蓖麻油(HCO，熔点＝87℃，(castor Wax NF，CasChem))得到粉末。将磨碎的氢化蓖麻油与硅酸盐(SIPERNAT 
)、甘油单硬脂酸酯(GMS、GMSR，Danisco)和甘油三硬脂酸酯(GTS、Tegin Bl159V，Goldschmitt)混合得到对应于表1中所述混合比例的均匀粉末。
在 
混合机(2.5kg)中将涂料施用于已用抗静电剂743(BASFSE)(150ppm，第一涂层)预先涂覆的可发性聚苯乙烯珠(从BASFAktiengesellschaft获得的 F215)。以经涂覆的可发性聚苯乙烯珠为基准计，涂料组合物(第二涂层)的量同样列于表2。
经涂覆的EPS珠在预先发泡器中预先发泡并在模具中烧结得到密度为17或24g/L的板。
根据EN 826以10％压缩率测定耐压强度，并根据EN12039方法B测定挠曲强度。
比较例C1和C2：
步骤与发明实施例1和2类似，但使用甘油单硬脂酸酯(GMS)代替氢化蓖麻油。
表1：
发明实施例5至8：
涂料制剂：
将氢化蓖麻油(HCO，熔点＝87℃，(HCO Power，Jayant Oil andderivatives Ltd.))与硅酸盐(SIPERNAT 
)、甘油单硬脂酸酯(GMS、GMSR，Danisco)和甘油三硬脂酸酯(GTS、Tegin Bl159V，Goldschmitt)还有硬脂酸锌混合得到对应于表2中所述混合比例的均匀粉末。
在 
混合机(2.5kg)中将所述涂料施用于已用抗静电剂743 (BASF SE)(150ppm)预先涂覆的可发性聚苯乙烯珠(从BASF SE获得的 
X5300)。以经涂覆的可发性聚苯乙烯珠为基准计，涂料组合物的量同样列于表2。
经涂覆的EPS珠在预先发泡器中预先发泡并在模具中烧结得到密度为17g/L的板。
根据EN 826以10％压缩率测定耐压强度，并根据EN12039方法B测定挠曲强度。
比较例C3和C4：
在此情况下，使用不含氢化蓖麻油的常规涂料。
表2：
发明实施例9至11：
涂料制剂：
将氢化蓖麻油(HCO，熔点＝87℃，(HCO Power，Jayant Oil and derivatives Ltd.))与硅酸盐(SIPERNAT 
)、甘油单硬脂酸酯(GMS、GMSR，Danisco)和甘油三硬脂酸酯(GTS、Tegin Bl159V，Goldschmitt)还有硬脂酸锌混合得到对应于表3中所述混合比例的均匀粉末。
在 
混合机(2.5kg)中将所述涂料施用于已用抗静电剂743(BASF SE)(150ppm)预先涂覆的可发性聚苯乙烯珠(从BASF SE获得的 
P426)。以经涂覆的可发性聚苯乙烯珠为基准计，涂料组合物的量同样列于表3。
经涂覆的EPS珠在预先发泡器中预先发泡并在模具中烧结得到密度为24g/L的板。
根据EN 826以10％压缩率测定耐压强度，并根据EN12039方法B测定挠曲强度。
比较例C3和C4：
在此情况下，使用不含氢化蓖麻油的常规涂料。
表3：
Claims (5)
1.一种用于可发性苯乙烯聚合物颗粒的涂料组合物制剂，包含：
(A)10至90重量％的熔点在60至65℃范围内的三硬脂基酯，
(B)10至90重量％的熔点在70至95℃范围内的羟基C16-C18油酸的三酸甘油酯；
其中将三硬脂酸甘油酯用作三硬脂基酯(A)。
2.权利要求1的用于可发性苯乙烯聚合物颗粒的涂料组合物制剂，其基本由以下物质组成：
(A)20至80重量％的熔点在60至65℃范围内的三硬脂基酯，
(B)15至50重量％的熔点在70至95℃范围内的羟基C16-C18油酸的三酸甘油酯，
(C)5至30重量％的亲水或疏水硅酸盐，
(D)0至40重量％的C16-C18脂肪酸的甘油单酯，
(E)0至10重量％的季铵盐、锍盐或亚乙基二硬脂基二酰胺；
其中组分(A)至(E)总计为100重量％；
其中将三硬脂酸甘油酯用作三硬脂基酯(A)。
3.权利要求1或2的用于可发性苯乙烯聚合物颗粒的涂料组合物制剂，其中将氢化蓖麻油用作羟基C16-C18油酸的三酸甘油酯(B)。
4.一种可发性苯乙烯聚合物颗粒，其包含至少一个具有权利要求1至3中任一项的涂料组合物制剂的涂层。
5.权利要求4的可发性苯乙烯聚合物颗粒，其具有
(I)一个第一涂层，其由基于所述可发性苯乙烯聚合物计0.1至2重量％的至少一种选自甘油单硬脂酸酯、甘油二硬脂酸酯、硬脂酸锌、季铵盐、锍盐和亚乙基二酰胺的化合物构成，和
(II)一个第二涂层，其由基于所述可发性苯乙烯聚合物计0.1至2重量％的权利要求1至2中任一项的涂料制剂构成。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07114072 | 2007-08-09 | ||
| EP07114072.7 | 2007-08-09 | ||
| PCT/EP2008/060444 WO2009019310A1 (de) | 2007-08-09 | 2008-08-08 | Beschichtungszusammensetzung für expandierbare styrolpolymerisatpartikel |
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| US (1) | US20110178192A1 (zh) |
| EP (1) | EP2178953B1 (zh) |
| JP (1) | JP2010535882A (zh) |
| KR (1) | KR101494482B1 (zh) |
| CN (1) | CN101778890B (zh) |
| AR (1) | AR067898A1 (zh) |
| BR (1) | BRPI0815086A2 (zh) |
| CA (1) | CA2694782C (zh) |
| CL (1) | CL2008002346A1 (zh) |
| ES (1) | ES2507076T3 (zh) |
| PL (1) | PL2178953T3 (zh) |
| RU (1) | RU2475502C2 (zh) |
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| WO2012130778A1 (de) | 2011-03-29 | 2012-10-04 | Basf Se | Verfahren zur herstellung von expandierbaren styrolpolymerisatpartikeln mit verringerter wärmeleitfähigkeit |
| BR112017019511A2 (pt) * | 2015-03-13 | 2018-05-15 | Basf Se | espumas em partículas eletricamente condutoras baseadas em elastômeros termoplásticos |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1581237A (en) * | 1976-08-27 | 1980-12-10 | Kanegafuchi Chemical Ind | Method of producing expandable thermoplastic polymer particles |
| EP0470455A2 (de) * | 1990-08-06 | 1992-02-12 | BASF Aktiengesellschaft | Perlförmige antistatische expandierbare Styrolpolymerisate |
| EP0485309A1 (fr) * | 1990-11-05 | 1992-05-13 | Pechiney Electrometallurgie | Produit pour désulfuration des fontes ou aciers liquides à base de magnésium enrobé |
| CN1119449A (zh) * | 1993-03-18 | 1996-03-27 | Basf公司 | 珠状可发性苯乙烯聚合物的制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4781983A (en) * | 1987-04-30 | 1988-11-01 | Arco Chemical Company | Method for preparing antistatic expandable polystyrene |
| US5750605A (en) * | 1995-08-31 | 1998-05-12 | National Starch And Chemical Investment Holding Corporation | Hot melt adhesives based on sulfonated polyesters |
| DE19541725C1 (de) | 1995-11-09 | 1997-05-07 | Basf Ag | Expandierbare Styrol-Perlpolymerisate mit verminderter Wasseraufnahmefähigkeit |
| BR0115923A (pt) * | 2000-12-04 | 2004-01-20 | Nova Chem Inc | Partìculas celulares espumadas, sistema para estender a vida em prateleira das partìculas poliméricas expansìveis, artigo de espuma, processo para preparar partìculas celulares espumadas, e, sistema para otimizar o carregamento e embalagem das partìculas poliméricas para uso na produção de artigos de espuma |
| ITMI20012168A1 (it) * | 2001-10-18 | 2003-04-18 | Enichem Spa | Polimeri vinilaromatici espandibili e procedimento per la loro preparazione |
| KR100622807B1 (ko) * | 2004-10-05 | 2006-09-19 | 주식회사 엘지화학 | 고발포가 가능하고 강도가 우수한 발포성 스티렌계 수지,그 제조 방법 및 그 성형품 |
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- 2008-08-08 CN CN2008801024133A patent/CN101778890B/zh not_active Expired - Fee Related
- 2008-08-08 US US12/672,352 patent/US20110178192A1/en not_active Abandoned
- 2008-08-08 SI SI200831276T patent/SI2178953T1/sl unknown
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- 2008-08-08 JP JP2010519472A patent/JP2010535882A/ja not_active Withdrawn
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1581237A (en) * | 1976-08-27 | 1980-12-10 | Kanegafuchi Chemical Ind | Method of producing expandable thermoplastic polymer particles |
| EP0470455A2 (de) * | 1990-08-06 | 1992-02-12 | BASF Aktiengesellschaft | Perlförmige antistatische expandierbare Styrolpolymerisate |
| EP0485309A1 (fr) * | 1990-11-05 | 1992-05-13 | Pechiney Electrometallurgie | Produit pour désulfuration des fontes ou aciers liquides à base de magnésium enrobé |
| CN1119449A (zh) * | 1993-03-18 | 1996-03-27 | Basf公司 | 珠状可发性苯乙烯聚合物的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| SI2178953T1 (sl) | 2014-12-31 |
| RU2475502C2 (ru) | 2013-02-20 |
| WO2009019310A1 (de) | 2009-02-12 |
| EP2178953B1 (de) | 2014-07-23 |
| KR101494482B1 (ko) | 2015-02-17 |
| EP2178953A1 (de) | 2010-04-28 |
| ES2507076T3 (es) | 2014-10-14 |
| PL2178953T3 (pl) | 2014-12-31 |
| JP2010535882A (ja) | 2010-11-25 |
| BRPI0815086A2 (pt) | 2015-02-03 |
| CA2694782A1 (en) | 2009-02-12 |
| CN101778890A (zh) | 2010-07-14 |
| AR067898A1 (es) | 2009-10-28 |
| CL2008002346A1 (es) | 2009-10-23 |
| RU2010107870A (ru) | 2011-09-20 |
| CA2694782C (en) | 2015-07-07 |
| US20110178192A1 (en) | 2011-07-21 |
| KR20100066490A (ko) | 2010-06-17 |
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