CN1213676A - 具有阻燃特性的泡沫聚酯树脂 - Google Patents
具有阻燃特性的泡沫聚酯树脂 Download PDFInfo
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- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
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Abstract
阻燃剂组合物,含有一种熔体强度大于8厘牛顿而特性粘度大于0.8dl/g,适于制备发泡蜂窝材料的芳族聚酯树脂和一种阻燃剂化合物,这种阻燃剂化合物能够使树脂在10%重量的阻燃剂化合物存在下,在氮气氛中在280℃加热试验10分钟,扭矩吸收的降低不小于3Nm。
Description
本发明涉及含有适于制备可以形成泡沫蜂窝状材料的流变特性的芳族聚酯树脂的阻燃剂组合物和由它们制成的泡沫材料。
由芳族聚酯树脂，其代表为聚对苯二甲酸乙二醇酯(PET)，制成的泡沫蜂窝状材料(泡沫)，发现由于绝热特性和作为结构材料，在汽车和家居领域的应用不断增大。
对于这些应用，泡沫材料具备良好的阻燃性能是必要的。
将阻燃剂化合物加入到形成具备宝贵性能的泡沫状材料的具有流变特性的芳族聚酯中，具有降低－并且是很大程度地降低树脂流变特性的效果，从而使之不适于泡沫的制备。一些化合物引起如此显著的树脂降解以至于妨碍它们作为塑料材料使用。
流变特性的变劣是因为泡沫制备过程中使用了高温。
令人奇怪的是，变劣只表现于熔体强度和熔融粘度性能高的树脂而不表现于熔体强度性能较低的树脂，不适于制备令人满意性能的泡沫。已经发现可用于本发明的组合物的阻燃剂化合物是指不引起树脂流变特性降低的那些化合物，在加入10％(重量)阻燃剂化合物的树脂的热测试中，在氮气氛的流变混合器中，在280℃操作10分钟，相应的扭矩吸收的降低小于3 Nm。
满足上述测试的阻燃剂化合物包括含有大于50％(重量)溴和在200℃加热重量损失小于5％(重量)(以加热速度10℃/分钟的热重量分析法测定)的芳族溴化合物。
代表的化合物是N,N’-乙烯-双(四溴邻苯二甲酰亚胺)、四溴邻苯二甲酸酐、十溴二苯醚、八溴二苯醚、双(三溴苯氧基)乙烷、双(溴苯氧基)乙烷。
当然，由于其熔点高、稳定性好和对聚酯树脂降解作用小，N,N’-乙烯-双(四溴邻苯二甲酰亚胺)是优选的化合物。这种化合物以注册商标Albermarle的Saytex BT93在市场上供应。
另一种特别适用的溴化合物以注册商标Albermarle的Saytex 8010在市场上供应。
阻燃剂化合物的用量可以是1～15％(重量)。
对于四溴磷苯二甲酰亚胺，使用10％(重量)的化合物得到根据DIN 4102可燃性试验分类为B1的泡沫和根据UNE 23727-90试验分类为M2的泡沫。使用5％(重量)的Saytex 8010，得到根据UNE23727-90试验分类为M1的泡沫。
另一种可使用的不属于溴化合物类的化合物是Alcoa出售的以BAO命名的碱式草酸铝。
含有阻燃剂的本发明的泡沫具有与不含这类添加剂的泡沫类似的性质。
这种溴化合物可以与0.5～5％(重量)的例如锑酸钠、三氧化锑、五氧化锑之类的锑化合物混合使用。对于锑酸钠，用量为0.5～10％(重量)；对于锑氧化物，用量是1～10％(重量)。
在锑酸钠的情形中，也可以使用占树脂重量0.05～2％的二氧化硅。
阻燃剂化合物可以在挤出发泡步骤之前或在这个步骤期间加入。
它们可以直接加入或采用以聚碳酸酯、聚对苯二甲酸丁二酯或聚乙烯为基的母料的形式加入。
如已指明的那样，将上述溴化合物加入到不具备必要的流变特性的聚酯树脂中，例如用12,4-苯三酸酐得到的、(I.V.=0.95 dl/g)熔体强度不足够大的接枝型PET或不使用1,2,4,5-苯四酸二酐经固态缩聚得到的熔体强度小于8厘牛顿的高I.V.(1.1 dl/g)线型PET，没有明显地降低聚合物的流变特性。
加入10％(重量)阻燃剂化合物例如Saytex BT 93的PET的扭矩吸收保持不变(在氮气氛的流变混合器中，在280℃测试10分钟)。
本发明的组合物的泡沫蜂窝材料的制备是按照现有的方法在发泡剂存在下通过挤出-发泡进行的。
可用于制备本发明的泡沫的聚酯树脂的特性为熔体强度值大于8厘牛顿而特性粘度大于0.8 dl/g。
上述值指的是挤出-发泡加工之前的树脂，以及在挤出的条件下，在挤出步骤期间达到这些值的树脂。
获得具有适合本发明的泡沫形成的流变特性的聚酯树脂的一种方法包括，挤出I.V.0.5～0.7 dl/g、添加了一种四羧酸二酐，优选芳族酸，(最好是1,2,4,5-苯四酸二酐，加入量为0.1～1％(重量)的聚酯树脂，并且将该树脂在固态加聚直到其最终粘度值达到0.85～1.95 dl/g。
这种四羧酸二酐可以以聚碳酸酯、聚对苯二甲酸丁二酯或聚乙烯为母料的形式加入，(加入量为1～50％(重量))。
另一种方法包括，将特性粘度为0.85～1.95 dl/g、添加了含量为1～50％(重量)二酐以聚碳酸酯、聚对苯二甲酸丁二酯或聚乙烯的二酐为母料的聚酯树脂挤出。
母料的加入量相应于聚酯树脂中二酐的浓度为0.1～1％(重量)。在母料中优选的二酐是1,2,4,5-苯四酸二酐。
可用于本发明的组合物中的芳族聚酯树脂通过芳族二羧酸(优选对苯二甲酸或其低级烷基酯)与2～10个碳原子的脂族二醇(有代表性的是乙二醇、1,4-丁二醇、1,4-环己二甲醇)的缩聚反应获得。
优选的树脂是聚对苯二甲酸乙二醇酯或共聚对苯二甲酸乙二酯，其中对苯二甲酸的高达20％单元用间苯二酸或萘二羧酸衍生单元取代。
特性粘度是在0.5g聚酯于100ml的60/40(重量)的苯酚-四氯乙烷混合物的溶液里在25℃按照ASTMD 4603-86测量。
熔体强度的测量，是在Goettfert流变计毛细管中挤出聚合物丝，该流变计有一个几何尺寸为长30mm直径1mm、进口角90°的毛细管。
活塞速度是0.2mm/s。挤出丝被卷入钢制嵌齿之间，对嵌齿施加一圆周速度的线性加速度。这个加速度是60mm/s2，记录下的张力是挤出丝在最大速度(1000m/s)处施加给齿轮的力。
测量按照ASTMD 4440在270℃进行。
压缩变定和抗压模量的测量按照ASTM D 1621和D 1623进行。
提供的以下实施例具体说明而不是限制本发明。
实施例1
将2.25g的Saytex 8010和42.75g高等级PET－acronym PET-F(I.V.=1.2dl/g，熔体强度20～25厘牛顿，通过在207℃与I.V.=0.63 dl/g、加有0.4％(重量)PMDA的PET在固态加聚13小时得到；PET-F先在120℃在真空下干燥16小时)的混合物装入Rheomix-Haake的小室里。
小室加热至280℃并置于氮气氛下。流变计的转速是20 rpm。
5分钟后熔融混合物的扭矩吸收大约是6 Nm；10分钟后是大约4 Nm而20分钟后大约是2Nm。
由这种添加的PET-F(在240-280℃挤出-发泡，使用1～5％(重量)的CO2、N2或一种氯氟烷作为发泡剂)得到的一种发泡材料根据UNE 23727-90标准试验分类为M1。
这种发泡材料的抗压模量是6.87MPa；压缩变定是0.438MPa。
对比实施例1
重复实施例1，唯一不同之处是仅使PET-F。
加热10分钟后扭矩吸收大约是8 Nm；10分钟后是大约4 Nm，而20分钟后大约是2Nm。
实施例2
将40.5g在实施例1中使用的PET-F和4.5g的Saytex BT 93装入Rheomix-Haake里并在实施例1的条件下进行试验。
5分钟后扭矩吸收大约是7Nm；10分钟后是大约4 Nm而20分钟后大约是3 Nm。
在实施例1的条件下得到的发泡材料根据DIN 4102可燃性试验分类为B1。
实施例3
将实施43.2g例1的PET-F和1.3g的Saytex BT93(3％重量)的混合物、0.225g的锑酸钠(0.3％重量)和0.225g含10％(重量)PMDA(相当于在混合物中0.3％的PMDA)的聚碳酸酯母料在120℃在真空下干燥16小时。
混合物装入Rheomix-Haake的小室里并在实施例1的条件下加热。
5分钟后扭矩吸收大约是9 Nm；10分钟后是大约5 Nm,20分钟后大约是2Nm。
挤出这种添加的聚酯以生成泡沫；这种泡沫具有可与实施例1相比较的机械特性。
这种材料根据DIN4102分类为B1。
对比实施例2
将含有20％(重量)多磷酸铵的PET-F(由Bundenheim Iberical以FR CROSS484提供)和8％三聚氰胺(由Bundenheim Iberica以PLASTISANB提供)和0.3％的Aerosil OX 50(由Degussa提供)的混合物装入Rheomix-Haake的小室里并在实施例1的条件下加热。
2分钟后扭矩吸收大约是2Nm；5分钟后吸收实际上减至0。
只使用FR CROSS 484加入或不加入二氧化硅作为阻燃剂也得到这样的结果。这种添加的PET不能用于形成泡沫材料。
对比实施例3
将在实施例1中的PET-F和3.5％(重量)的AmgordP 45(一种有机磷化合物，由Albright & Wilson提供)的混合物在实施例1描述的热式验中使用。
5分钟后扭矩吸收大约是3Nm；10分钟后大约是1Nm。
这种材料不能形成泡沫。
对比实施例4
由I.V.=0.63 dl/g的PET(这种PET不加入PMDA)通过固态缩聚反应得到I.V.=1.19dl/g(先在120℃在真空下干燥16小时)的PET与5％(重量)Saytex 8010相混合。混合物在实施例1的条件下进行加热。
5分钟后扭矩吸收大约是3 Nm，而10分钟后大约是2 Nm。
这种材料不能形成泡沫。
Claims (11)
1、能够用于发泡蜂窝材料的组合物，包括一种熔体强度大于8厘牛顿而特性粘度大于0.8 dl/g的芳族聚酯树脂和一种加入量为组合物重量的1～15％的阻燃剂化合物，当加入10％重量的化合物时，这种阻燃剂化合物能够使树脂在氮气氛的流变混合仪中在280℃加热10分钟，树脂的扭矩吸收的降低不小于3Nm。
2、根据权利要求1的组合物，其中阻燃剂化合物选自于含有大于50％(重量)溴和在200℃加热时(加热速度10℃/分钟)重量损失小于5％(重量)的芳族溴化合物。
3、根据权利要求2的组合物，其中溴化合物选自于N,N’-乙烯-双(四溴邻苯二甲酰亚胺)、十溴二苯醚、双(三溴苯氧基)乙烷和双(五溴苯氧基)乙烷。
4、根据权利要求3的组合物，其中的溴化合物是N,N’-乙烯-双(四溴邻苯二甲酰亚胺)。
5、根据权利要求1～4的组合物，其中聚酯树脂是通过一种特性粘度为0.5～0.7 dl/g、添加了0.1～1％重量的一种芳族四羧酸二酐的树脂在固态加聚得到的。
6、根据权利要求5的组合物，其中的二酐是1,2,4,5-苯四酸二酐。
7、根据权利要求1～4的组合物，其中聚酯树脂是通过将一种特性粘度0.8～1.95 dl/g的树脂在选自于含1～50％重量的芳族四羧酸二酐的聚碳酸酯、聚乙烯和聚对苯二甲酸乙二酯的母料存在下挤出而得到的，该母料的加入量是使加入的二酐重量为0.1～1％。
8、根据权利要求7的组合物，其中的母料含有1,2,4,5-苯四酸二酐。
9、根据权利要求1～8的组合物，其中的阻燃剂化合物是在树脂加工转化为蜂窝泡沫材料之前或之中加入树脂中的。
10、根据权利要求1～9的组合物，其中的聚酯树脂选自于聚对苯二甲酸乙二酯、共聚对苯二甲酸乙二酯，其中由对苯二甲酸衍生的高达20％单元用间苯二酸或萘二羧酸衍生单元取代。
11、由上述权利要求1～10的组合物得到的发泡的阻燃蜂窝材料阻燃剂。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT97MI002264A IT1298704B1 (it) | 1997-10-06 | 1997-10-06 | Resine poliestere espanse con proprieta' antifiamma |
| ITMI97A002264 | 1997-10-06 |
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| CN1213676A true CN1213676A (zh) | 1999-04-14 |
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| CN98120625A Pending CN1213676A (zh) | 1997-10-06 | 1998-10-05 | 具有阻燃特性的泡沫聚酯树脂 |
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| US (1) | US6444717B1 (zh) |
| EP (1) | EP0908488A1 (zh) |
| JP (1) | JPH11302428A (zh) |
| KR (1) | KR19990036795A (zh) |
| CN (1) | CN1213676A (zh) |
| CA (1) | CA2247787A1 (zh) |
| IT (1) | IT1298704B1 (zh) |
| MX (1) | MXPA98008250A (zh) |
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| US20070059511A1 (en) * | 2004-03-31 | 2007-03-15 | Edwards Walter L | Low density foamed polymers |
| DK2258754T3 (da) * | 2009-06-02 | 2012-07-09 | Armacell Enterprise Gmbh | Polyesterskummateriale med flammebestandig adfærd |
| CN101805444B (zh) * | 2010-03-16 | 2012-04-25 | 四川大学 | 耐熔滴阻燃聚酯及其纳米复合材料和它们的制备方法 |
| EP4265684A1 (en) | 2022-04-21 | 2023-10-25 | Nexam Chemical AB | An improved flame retardant polyester |
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| US4374220A (en) * | 1968-09-18 | 1983-02-15 | Raychem Corporation | Imide flame retardants and compositions containing them |
| US3957598A (en) * | 1972-05-22 | 1976-05-18 | Merkl George | Metal hydrates and salts of carboxylic acids |
| US4010219A (en) * | 1972-12-28 | 1977-03-01 | Toray Industries, Inc. | Flame retardant polyester composition |
| DE2608925A1 (de) * | 1976-03-04 | 1977-09-08 | Dynamit Nobel Ag | Treibmittelkonzentrat |
| US4280005A (en) * | 1978-05-05 | 1981-07-21 | General Electric Company | Foamable polyester composition |
| US4399244A (en) * | 1979-11-19 | 1983-08-16 | Bayer Aktiengesellschaft | Glass fiber reinforced polyethylene terephthalate compositions having improved heat distortion temperatures |
| KR910007599B1 (ko) * | 1983-01-27 | 1991-09-28 | 세끼스이 가세이힌 고오교오 가부시끼가이샤 | 과립상 유기할로겐화물 난연제 첨가제 |
| US4546126A (en) * | 1983-07-13 | 1985-10-08 | Ciba Geigy Corporation | Flame-retarding, reinforced moulding material based on thermoplastic polyesters and the use thereof |
| JPH0794570B2 (ja) | 1990-10-03 | 1995-10-11 | 積水化成品工業株式会社 | 難燃性の熱可塑性ポリエステル系樹脂発泡体用組成物 |
| IT1252223B (it) | 1991-12-16 | 1995-06-05 | M & G Ricerche Spa | Resine poliestere cellulari e loro procedimento di preparazione |
| US5536793A (en) | 1993-01-29 | 1996-07-16 | Amoco Corporation | Concentrate for use in the melt fabrication of polyester |
| IL110514A0 (en) * | 1993-10-04 | 1994-10-21 | Eastman Chem Co | Concentrates for improving polyester compositions and a method for preparing such compositions |
| JPH07179736A (ja) * | 1993-12-24 | 1995-07-18 | Kanegafuchi Chem Ind Co Ltd | 高溶融粘弾性発現性樹脂組成物およびそれを用いた芳香族ポリエステル系樹脂発泡体の製造法 |
| US5391582A (en) * | 1994-04-19 | 1995-02-21 | E. I. Du Pont De Nemours And Company | Poly(ethylene terephthalate) foams comprising recycled plastic and methods relating thereto |
| US5482977A (en) * | 1995-05-08 | 1996-01-09 | Eastman Chemical Company | Foamable branched polyesters |
| EP0764683B1 (de) * | 1995-09-21 | 2006-05-31 | Lanxess Deutschland GmbH | Laserbeschriftbare Polymer-Formmassen |
| US5696176A (en) * | 1995-09-22 | 1997-12-09 | Eastman Chemical Company | Foamable polyester compositions having a low level of unreacted branching agent |
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- 1998-09-18 CA CA002247787A patent/CA2247787A1/en not_active Abandoned
- 1998-09-22 US US09/159,373 patent/US6444717B1/en not_active Expired - Fee Related
- 1998-10-02 JP JP10281029A patent/JPH11302428A/ja active Pending
- 1998-10-02 KR KR1019980041519A patent/KR19990036795A/ko not_active Application Discontinuation
- 1998-10-05 CN CN98120625A patent/CN1213676A/zh active Pending
- 1998-10-05 EP EP98121944A patent/EP0908488A1/en not_active Withdrawn
- 1998-10-06 MX MXPA98008250A patent/MXPA98008250A/es not_active IP Right Cessation
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| Publication number | Publication date |
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| EP0908488A1 (en) | 1999-04-14 |
| KR19990036795A (ko) | 1999-05-25 |
| CA2247787A1 (en) | 1999-04-06 |
| JPH11302428A (ja) | 1999-11-02 |
| MXPA98008250A (es) | 2005-06-29 |
| US6444717B1 (en) | 2002-09-03 |
| ITMI972264A1 (it) | 1999-04-06 |
| IT1298704B1 (it) | 2000-01-12 |
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