CN100528957C - 阻燃热塑性树脂组合物 - Google Patents
阻燃热塑性树脂组合物 Download PDFInfo
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Abstract
根据本发明的阻燃(防火)树脂组合物包括：(A)100重量份的橡胶改性聚苯乙烯树脂，其含有(a1)按重量计20～100%的接枝共聚物，该接枝共聚物通过接枝聚合按重量计5～65%的橡胶聚合物、30～95%的芳族乙烯基单体、0～20%的可与所述芳族乙烯基单体共聚的单体以及0～15%的用于提供良好加工性和耐热性的单体加以制备，和(a2)按重量计0～80%的共聚物，该共聚物通过聚合按重量计60～90%的芳族乙烯基单体、10～40%的可与所述芳族乙烯基单体共聚的单体以及0～30%的用于提供良好加工性和耐热性的单体加以制备；以及(B)15～40重量份的氧杂正膦化合物。
Description
技术领域
本发明涉及具有良好阻燃性和环境友好效果的苯乙烯树脂组合物。更具体地说，本发明涉及通过将氧杂正膦(oxaphosphorane)化合物用作橡胶改性苯乙烯树脂的阻燃剂而具有良好阻燃性和环境友好效果的苯乙烯热塑性树脂组合物。
背景技术
橡胶改性苯乙烯树脂具有良好的加工性、高的机械性能、尤其是冲击强度、以及良好的外观。因此，该树脂已经广泛被用于电气或电子产品和办公用品。然而，由于苯乙烯树脂非常易于着火，所以当将橡胶改性苯乙烯树脂用于放热(发热)产品如计算机、传真机等时就会观察到其缺点。因此，已经开发了用于改善橡胶改性苯乙烯树脂的阻燃性能的方法。
一种广为人知的用于阻燃性的方法是将含卤素的化合物添加到橡胶改性苯乙烯树脂中以获得良好的阻燃性能。用于上述方法中的含卤素化合物的实例为例如聚溴二苯基醚、四溴双酚-A、被溴取代的环氧化合物等。可以将含锑的化合物一起加入以进一步提高阻燃性。
然而，这种通过使用含卤素和含锑化合物来改善阻燃性的方法的缺点在于：由于在模塑工艺过程中释放出卤化氢气体，而含卤素的化合物会引起模具本身的腐蚀，并且由于一旦着火会释放出毒性气体，故能造成致命伤害。尤其是，因为主要用于含卤素阻燃剂的聚溴二苯醚在燃烧过程中会产生毒性气体如戴奥辛(二氧芑，dioxin)或呋喃。因此，该领域的主要关注点就是开发不用含卤素的化合物制备的阻燃树脂。
通常已知的方法是将芳族磷酸酯化合物作为无卤素阻燃剂用于苯乙烯树脂中。然而，仅芳族磷酸酯化合物的使用并不赋予UL 94V1充分的阻燃性。为了解决上述问题，已经提出了将芳族磷酸酯用于苯乙烯树脂和聚苯醚树脂的混合物或苯乙烯树脂和聚碳酸酯树脂的混合物的方法。
美国专利第3,639,506号披露了树脂组合物，其中将单芳族磷酸酯(如磷酸三苯酯)用于高抗冲聚苯乙烯树脂和聚苯醚树脂的混合物。
美国专利第5,061,745号披露了一种热塑性树脂组合物，其中将单磷酸酯用于ABS接技共聚物和聚碳酸酯树脂的混合物。另外，美国专利第5,204,394号披露了一种树脂组合物，其中将低聚磷酸酯作为阻燃剂用于ABS树脂和聚碳酸酯树脂的混合物。
因此，本发明发明人在没有使用聚苯醚树脂或聚碳酸酯树脂的情况下开发了一种阻燃(防火，flameproof)热塑性树脂组合物，。
发明内容
本发明的一个目的是提供一种对燃烧(火)稳定的热塑性树脂组合物。
本发明的另一个目的是提供一种环境友好的热塑性树脂组合物，其不包含在该树脂的制备或燃烧过程中引起环境污染的含卤素的化合物。
本发明的进一步目的是在不使用聚亚苯基树脂或聚碳酸酯树脂的情况下提供一种具有良好阻燃性的热塑性树脂组合物。
根据随后的披露内容和所附权利要求书将使本发明的其它目的和优点更加明显。
根据本发明的阻燃树脂组合物包括：(A)100重量份的橡胶改性聚苯乙烯树脂，其包含(a1)按重量计20～100％的接枝共聚物，该接枝共聚物通过接枝聚合按重量计5～65％的橡胶聚合物、30～95％的芳族乙烯基单体、0～20％的可与所述芳族乙烯基单体共聚的单体以及0～15％的用于提供良好加工性和耐热性的单体加以制备；和(a2)按重量计0～80％的共聚物，该共聚物通过聚合按重量计60～90％的芳族乙烯基单体、10～40％的可与所述芳族乙烯基单体共聚的单体以及0～30％的用于提供良好加工性和耐热性的单体加以制备；以及(B)15～40重量份的氧杂正膦化合物。
具体实施方式
(A)橡胶改性聚苯乙烯树脂
根据本发明的橡胶改性聚苯乙烯树脂是一种聚合物，其中将橡胶相聚合物以颗粒形式分散于通过聚合芳族乙烯基单体和含乙烯基的单体而获得的基质中。橡胶改性聚苯乙烯树脂可以通过聚合芳族乙烯基单体和可选的可与所述芳族乙烯基单体共聚的单体与橡胶相聚合物加以制备。
这样的橡胶改性聚乙烯树脂是通过已知的方法如乳液聚合、悬浮聚合或本体聚合来制备的，并且传统上利用含苯乙烯的接枝共聚物树脂和含苯乙烯的共聚物树脂通过挤出而制备。在本体聚合中，含苯乙烯的接枝共聚物树脂和含苯乙烯的共聚物树脂是在一个工艺中一起制备的。在其它聚合中，含苯乙烯的接枝共聚物树脂和含苯乙烯的共聚物树脂可以分开制备。无论是哪种情形，在最终的橡胶改性聚苯乙烯树脂中，橡胶的含量相对于基础树脂的总重量按重量计优选为5～30％。
在本发明的橡胶改性聚苯乙烯树脂中，可以单独使用接枝共聚物树脂或在考虑其相容性的情况下与共聚物树脂结合使用。
(a1)接枝共聚物
用于制备接枝共聚物的橡胶聚合物的实例是二烯橡胶，如聚丁二烯、聚(苯乙烯-丁二烯)、聚(丙烯腈-丁二烯)等；饱和橡胶，其中氢被加成到所述含二烯的橡胶；异戊二烯橡胶；丙烯酸类橡胶如聚丁基丙烯酸；以及乙烯-丙烯-二烯三元共聚物(EPDM)。优选使用含二烯的橡胶，更优选使用含丁二烯的橡胶。在接枝共聚物中，基于接枝共聚物的总重量，橡胶的含量按重量计优选为在5～65％的范围内。
用于制备接枝共聚物的芳族乙烯基单体的实例是苯乙烯、α-甲基苯乙烯、对甲基苯乙烯等。在以上实例中，苯乙烯是最优选的。
在本发明的接枝共聚物中，可以引入至少一种可与所述芳族乙烯基单体共聚的单体。优选地，可共聚的单体是含氰化乙烯基的化合物(cyanide vinyl-containing compound)如丙烯腈，或不饱和的含腈化合物如甲基丙烯腈。
本发明的接枝共聚物通过接枝共聚按重量计5～65％的橡胶、30～95％的芳香族乙烯基单体以及0～20％的可共聚的单体来制备。
另外，为了获得良好的加工性和耐热性特性，可在接枝聚合中加入单体如丙烯酸、甲基丙烯酸、马来酸酐和N-取代的马来酰亚胺。基于接枝共聚物的总量，这些单体的用量按重量计为在0～15％的范围内。
当制备所述含苯乙烯的接枝共聚物时，为了获得良好的冲击强度和外观，橡胶颗粒的平均尺寸优选为在0.1～4μm的范围内。
(a2)共聚物
本发明的共聚物通过共聚芳族乙烯基单体和可共聚的单体来制备，这取决于在该接枝共聚物中除了橡胶外的单体之间的比率和相容性。
芳族乙烯基单体的实例有苯乙烯、α-甲基苯乙烯、对甲基苯乙烯等。苯乙烯是最优选的。在全部共聚物中，芳族乙烯基单体的含量按重量计为60～90％。
在本发明的共聚物中，可以引入至少一种可与所述芳族乙烯基单体共聚的单体。该可共聚的单体的实例是含氰化乙烯基的化合物如丙烯腈，以及不饱和的含腈化合物如甲基丙烯腈。相对于全部共聚物，优选使用按重量计为10～40％的可共聚的单体。
另外，可以加入按重量计0～30wt％的其他单体如丙烯酸、甲基丙烯酸、马来酸酐和N-取代的马来酰亚胺并共聚，以便获得良好的加工性和耐热性特性。
橡胶改性聚苯乙烯树脂的实例是丙烯腈-丁二烯-苯乙烯(ABS)共聚物树脂、丙烯腈-乙丙橡胶-苯乙烯(AES)共聚物树脂、丙烯腈-丙烯酸类橡胶-苯乙烯(AAS)共聚物树脂、高抗冲聚苯乙烯树脂(HIPS)等。
在本发明中，橡胶改性聚苯乙烯树脂(A)包含按重量计20～100％的接枝共聚物(a1)和按重量计0～80％的共聚物(a2)。
(B)氧杂正膦化合物
本发明的氧杂正膦化合物由下面的化学式(I)表示：
其中R1为H、C1-4烷基或C6-10芳基；R2和R3相互独立地为H或C1-4烷基；以及n为1～3。
氧杂正膦化合物的优选实例是2-甲基-2，5-二氧代-1-氧杂-2-正膦和2-苯基-2，5-二氧代-1-氧杂-2-正膦。氧杂正膦化合物可以单独或组合使用。
在本发明中，每100重量份橡胶改性聚苯乙烯树脂，氧杂正膦化合物的用量为15～40重量份，优选为20～35重量份。如果氧杂正膦化合物的用量小于15重量份，则该树脂组合物不能获得足够的阻燃性，而如果氧杂正膦化合物的用量大于40重量份，则基础树脂和氧杂正膦化合物之间的相容性变差。
在本发明的热塑性树脂组合物中可以使用其他的添加剂。添加剂包括防流挂剂、热稳定剂、抗氧化剂、增容剂、光稳定剂、有机或无机颜料和/或染料、无机填料等。对于每100重量份的基础树脂，添加剂的用量为0～30重量份。
参照下面的实施例可以更好地理解本发明，这些实施例只用于描述说明本发明的目的，而不能以任何方式解释为限制由所附权利要求书限定的本发明的范围。
实施例
用于制备实施例1～3和比较实施例1～3中的热塑性树脂组合物的成分如下：
(A)橡胶改性聚苯乙烯树脂
(a1)接枝共聚物树脂
(a11)含苯乙烯-丙烯腈的接枝共聚物树脂
将50份的丁二烯橡胶胶乳粉末、36份的苯乙烯、14份的丙烯腈、以及150份的去离子水加以混合。向该混合物中加入1.0份的油酸钾、0.4份的异丙苯过氧化氢(cumenhydroperoxide)、0.2份的含硫醇的链转移剂、0.4份的葡萄糖、0.01份的硫酸亚铁水合物、以及0.3份的焦磷酸钠。将混合物在75℃保持5小时以获得g-ABS胶乳。向该g-ABS胶乳中加入0.4份的硫酸，然后凝结并干燥以获得粉末形式的橡胶改性聚苯乙烯树脂(g-ABS)。
(a12)高抗冲聚苯乙烯(HIPS)
使用的高抗冲聚苯乙烯(产品名：HR-1380)具有按重量计7％的丁二烯树脂含量、1.5μm的平均橡胶颗粒尺寸，其由韩国CheilIndustries Inc.生产。
(a2)共聚物树脂
将75份的苯乙烯、25份的丙烯腈、以及120份的去离子水加以混合。向该混合物中加入0.2份的偶氮二异丁腈(AIBN)、0.4份的磷酸三钙以及0.2份的含硫醇的链转移剂。将所得的溶液在90分钟内加热到80℃并保持180分钟。将所得产物进行洗涤、脱水并干燥，以获得粉末形式的苯乙烯-丙烯腈共聚物树脂(SAN)。
(B)氧杂正膦化合物
使用熔点为102～104℃的2-甲基-2，5-二氧代-1-氧杂-2-正膦。
(B′)芳族磷酸酯化合物
使用熔点为48℃的磷酸三苯酯(TPP)。
(C)氟化聚烯烃树脂
将由Dupont公司生产的Teflon(注册商标)7AJ用作防流挂剂。
实施例1～3
将如表1所示的各成分加以混合，并将该混合物用传统的双螺杆挤出机在180～250℃下挤出造粒。将该树脂颗粒在80℃下干燥3小时，然后利用在180～280℃的6盎司注射成型机并且模制温度为40～80℃下模制成试样。依照UL94VB，分别用1/8”和1/12”的厚度检测试样的阻燃性。
比较实施例1～3
除了没有使用氧杂正膦化合物外，用与实施例1相同的方式实施比较实施例1。除了使用芳族磷酸酯化合物代替氧杂正膦化合物作为阻燃剂外，分别用与实施例2～3相同的方式实施比较实施例2～3。测试结果示于表1中。
表1
如以上所示出的，使用了氧杂正膦化合物作为阻燃剂的树脂组合物表现出良好的UL94-阻燃性。然而，没有使用任何阻燃剂的比较实施例1和使用了芳族磷酸酯化合物代替氧杂正膦化合物的比较实施例2～3的树脂组合物表现出较差的阻燃性。
本领域的普通技术人员可以很容易实施本发明。可以将许多更改和变化视为在由所附权利要求书限定的本发明的范围内。
Claims (7)
1.一种阻燃热塑性树脂组合物，包括：
(A)100重量份的橡胶改性聚苯乙烯树脂，其含有：(a1)按重量计20～100％的接枝共聚物，所述接枝共聚物通过接枝共聚按重量计5～65％的橡胶聚合物、30～95％芳族乙烯基单体、0～20％的可与所述芳族乙烯基单体共聚的单体以及0～15％的用于提供良好的加工性和耐热性的单体来制备；以及(a2)按重量计0～80％的共聚物，所述共聚物通过聚合按重量计60～90％的芳族乙烯基单体、10～40％的可与所述芳族乙烯基单体共聚的单体以及0～30％的用于提供良好加工性和耐热性的单体来制备；以及
(B)15～40重量份的氧杂正膦化合物，
其中，所述热塑性树脂组合物不包含聚苯醚树脂，
并且其中，可与所述芳族乙烯基单体共聚的所述单体选自不饱和的含腈化合物；
用于提供良好加工性和耐热性的所述单体选自由丙烯酸、甲基丙烯酸、马来酸酐和N-取代的马来酰亚胺组成的组；
所述氧杂正膦化合物(B)由下面的化学式(I)表示：
其中R1为H、C1-4烷基或C6-10芳基；R2和R3相互独立地为H或C1-4烷基；以及n为1～3。
2.根据权利要求1所述的阻燃热塑性树脂组合物，其中，所述橡胶聚合物选自由二烯橡胶、其中氢被加成到所述含二烯的橡胶的饱和橡胶、以及丙烯酸类橡胶组成的组。
3.根据权利要求1所述的阻燃热塑性树脂组合物，其中，所述芳族乙烯基单体选自由苯乙烯、α-甲基苯乙烯、以及对甲基苯乙烯组成的组。
4.根据权利要求1所述的阻燃热塑性树脂组合物，其中，所述橡胶改性聚苯乙烯树脂(A)选自由丙烯腈-丁二烯-苯乙烯共聚物树脂、丙烯腈-丙烯酸类橡胶-苯乙烯共聚物树脂、丙烯腈-乙丙橡胶-苯乙烯、以及高抗冲聚苯乙烯树脂组成的组。
5.根据权利要求1所述的阻燃热塑性树脂组合物，进一步包括0～30重量份的添加剂，所述添加剂选自防流挂剂、热稳定剂、抗氧化剂、增容剂、光稳定剂、颜料和/或染料。
6.根据权利要求2所述的阻燃热塑性树脂组合物，其中，所述二烯橡胶为异戊二烯橡胶、或乙烯-丙烯-二烯的三元共聚物。
7.根据权利要求1所述的阻燃热塑性树脂组合物，其中，所述不饱和的含腈化合物为含氰化乙烯基的化合物。
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| US6797754B2 (en) * | 2002-05-06 | 2004-09-28 | Cheil Industries Inc. | Flame retardant styrenic compositions containing oxaphospholane compound as flame retardant |
| DE19903709A1 (de) * | 1999-01-30 | 2000-08-10 | Clariant Gmbh | Flammschutzmittel-Kombination für thermoplastische Polymere II |
| JP2000290462A (ja) * | 1999-04-05 | 2000-10-17 | Techno Polymer Kk | 難燃性樹脂組成物 |
| JP2001151974A (ja) * | 1999-11-29 | 2001-06-05 | Denki Kagaku Kogyo Kk | 難燃性樹脂組成物 |
| JP2001214023A (ja) * | 2000-02-04 | 2001-08-07 | Techno Polymer Co Ltd | 熱可塑性樹脂組成物 |
| KR100520790B1 (ko) * | 2000-02-17 | 2005-10-12 | 제일모직주식회사 | 열가소성 난연성 수지조성물 |
| US6610442B2 (en) * | 2000-06-05 | 2003-08-26 | Mitsubishi Engineering-Plastics Corporation | Resin composition and resin moldings using the same |
| KR100406593B1 (ko) * | 2001-06-08 | 2003-11-20 | 제일모직주식회사 | 난연성 열가소성 수지조성물 |
| KR100401326B1 (ko) * | 2001-06-08 | 2003-10-10 | 제일모직주식회사 | 난연성 열가소성 수지조성물 |
| KR100458071B1 (ko) * | 2002-04-16 | 2004-11-20 | 제일모직주식회사 | 난연성 스티렌계 수지 조성물 |
| KR100568080B1 (ko) * | 2002-12-27 | 2006-04-05 | 제일모직주식회사 | 난연성 열가소성 수지 조성물 |
| KR100552999B1 (ko) * | 2003-08-04 | 2006-02-15 | 제일모직주식회사 | 난연성 열가소성 수지 조성물 |
-
2004
- 2004-06-17 EP EP04773952A patent/EP1756216A4/en not_active Withdrawn
- 2004-06-17 WO PCT/KR2004/001454 patent/WO2005123832A1/en active Application Filing
- 2004-06-17 JP JP2007516369A patent/JP2008502767A/ja active Pending
- 2004-06-17 US US11/570,729 patent/US20070244229A1/en not_active Abandoned
- 2004-06-17 CN CNB2004800433341A patent/CN100528957C/zh not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US20070244229A1 (en) | 2007-10-18 |
| EP1756216A4 (en) | 2010-09-22 |
| CN1969010A (zh) | 2007-05-23 |
| WO2005123832A1 (en) | 2005-12-29 |
| JP2008502767A (ja) | 2008-01-31 |
| EP1756216A1 (en) | 2007-02-28 |
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Effective date of registration: 20170303 Address after: Jeonnam, South Korea Patentee after: LOTTE ADVANCED MATERIALS Co.,Ltd. Address before: Gyeonggi Do, South Korea Patentee before: Samsung SDI Co.,Ltd. Effective date of registration: 20170303 Address after: Gyeonggi Do, South Korea Patentee after: Samsung SDI Co.,Ltd. Address before: Gyeongbuk, South Korea Patentee before: Cheil Industries Inc. |
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