CN1075728A - 阻燃聚酰胺组合物 - Google Patents
阻燃聚酰胺组合物 Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 78
- 239000003063 flame retardant Substances 0.000 title abstract description 12
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title abstract description 7
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- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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Abstract
本发明涉及红磷阻燃的聚酰胺组合物,特别是涉
及其中包括锌化合物如氧化锌,硼酸锌和/或硫化锌
以降低对金属和合金的腐蚀并减少各成分的迁移的
组合物,可特别用于生产模制品。
Description
本发明涉及包括聚酰胺新组合物,用红磷达到阻燃,其中该组合物特别用于制造电器和电子工业产品,更具体是涉及可制成综合性能好,尤其是耐火性,弹性,抗电弧扩展性和表面外观好以及腐蚀性低的阻燃制品的组合物。
已知在聚酰胺组合物中加红磷可得到高度阻燃性。
US3883475说明了阻燃聚酰胺组合物,其目的首先阻止产生高毒性磷,其中在聚合物中存在的微量水和转化所需高热量作用下红磷彼此反应而形成毒性磷,该方法中将优选由氧化铜组成的金属化合物加入组合物中。
FR2367100提出了用氧化镉而不是CuO达到改进,其中除其防止磷产生的有效性(至少等于CuO)而外,氧化镉可制成抗电弧扩展性特别高(按法国标准NFC26220)的制品,其中在不含填料的组合物情况下等于或大于400V,而在含25wt%以上玻璃填料的组合物情况下为等于或大于375V。
FRNo.2553783和2621594提出了镧系化合物组成的氧化镉替代产品(有些毒性),得到的加该添加剂的阻燃聚酰胺组合物可制成综合性能好,尤其是阻燃性,弹性和抗电弧扩展性均好于用氧化镉的情况的制品。
但用红磷并必要时包括其它可阻止磷产生的成分的这些阻燃组合物对与该聚合物接触的金属物料的零部件有一定腐蚀性或用这些组合物通过模塑而制成模制品时亦如此,尤其是在用于电器或电子工业以支持金属接触件,如铜接触件的模制零部件时可看到这种现象。
本发明目的之一尤其是克服这些缺点,其中提出具有良好机械性及良好抗电弧性并且金属腐蚀性低的阻燃性聚酰胺组合物。
本发明因此提出含红磷的聚酰胺组合物,其特征在于其中包括选自氧化锌,含氧锌盐和硫化锌的锌化合物添加剂,也可用至少两种这些化合物的混合物。
本发明优选方案中以锌重量相对于红磷重量计的锌化合物量为约10-约100%,优选20-80%,更优选40-80%。
聚酰胺组合物可含填料如无机填料。
无机填料例子为矿物纤维如玻璃或石棉纤维,玻璃微珠,二氧化硅,云母,高岭土,膨润土或其混合物。
本发明另一优选特征是锌化合物为硼酸锌或其与氧化锌的混合物。用于填充有玻璃纤维的聚酰胺组合物时,该化合物尤其具有不会严重影响组合物机械性能的优点。因此填充有玻璃纤维的聚酰胺组合物的冲击强度不会因加入硼酸锌而受到严重影响。
本发明优选方案中组合物包括硼酸锌和氧化锌的混合物,其中以Zn相对于磷的浓度为15-60wt%氧化锌和15-40wt%硼酸锌,当然锌化合物总浓度处在上述范围内。
本发明用阻燃聚酰胺尤其包括饱和6-12碳脂肪二酸与6-12碳饱和脂族二伯二胺缩聚反应所得酰胺,含4-12碳烃链的ω-氨基烷酸直接均缩聚反应或上述酸衍生的内酰胺水解开链和聚合所得聚氨基酸,上述聚酰胺初始单体得到的共聚酰胺,而且该共聚酰胺的酸组分也可部分由邻苯二酸和/或间苯二酸组成以及聚酰胺的混合物。
作为例子,可由二酸和二胺缩聚反应得聚酰胺:尼龙6,6(六亚甲基二胺和己二酸的聚合物),尼龙6,9-(六亚甲基二胺和壬二酸的聚合物),尼龙6,10(六亚甲基二胺和癸二酸的聚合物)和尼龙6,12(六亚甲基二胺和十二烷二酸的聚合物)。
作为聚氨基酸例子可举出尼龙4(4-氨基丁酸或γ-丁内酰胺的聚合物),尼龙5(5-氨基戊酸或δ-戊内酰胺的聚合物),尼龙6(ε-己内酰胺的聚合物),尼龙7(7-氨基庚酸的聚合物),尼龙8(辛内酰胺聚合物),尼龙9(9-氨基壬酸的聚合物),尼龙10(10-氨基癸基酸的聚合物),尼龙11(11-氨基十一烷酸的聚合物)和尼龙12(12-氨基十二烷酸或月桂内酰胺的聚合物)。
作为共聚酰胺的例子可举出尼龙6,6/6,10(六亚甲基二胺,己二酸和癸二酸的共聚物)和尼龙6,6/6(六亚甲基二胺,己二酸和己内酰胺的共聚物)。
本发明优选阻燃聚酰胺为尼龙6,6,尼龙6,10,尼龙6,尼龙6,6/6,10和尼龙6,6/6。
本发明中“红磷”指各种色彩的同素异形磷(红,紫或黑色磷),市场上以红磷商名推出。
红磷量以阻燃聚酰胺重量计为1-30wt%,优选2-15wt%,更优选4-10wt%。一般用细粉碎红磷,如平均直径不超过200μm,优选1-100μm的颗粒。
红磷可就这样应用,也可做成涂聚合物表层的颗粒应用,其中聚合物例子可具体举出:环氧树脂(如法国专利FR.2314221),带马来酰,富马酰或烯丙基不饱和键的聚合物(如法国专利FR.2314219),熔点50-90℃且分子量小于10000的饱和聚酯(如法国专利FR.2373575),酚醛清漆类型的热塑性酚-醛缩聚产物(如法国专利No.2344615)和热塑性酚-异丁醛缩聚产物(如欧洲专利申请No.82106329,4,公开号No.0071788),本发明特别优选应用热塑性酚-醛缩聚产物。必要时用于磷粉涂层的聚合物量可在很宽范围内变化,一般为红磷/涂层聚合物混合物总重量的5-50%,但应当注意到可毫无妨害地应用高达红磷/涂层聚合物混合物总重的90%的大量涂层聚合物。
锌化合物可按各种形式如粉状加入本发明组合物中,当然也可呈结晶或无水或无定形状态,但有效的是锌化合物在组合物转化温度和在组合物正常应用温度下必须稳定或基本稳定。这种粉的特征并不关键,因此将锌化合物的形状和尺寸以及引入聚酰胺组合物并加以混合的方法被确定为生产用任何方法,如模制,挤出或注塑而转化的热塑性聚合物组合物的常见标准的函数。所以说优选用细粒粉或物料,一般来说,粉粒径越好,效果越好。
这些组合物的适宜制造方法为常用于生产聚酰胺组合物的方法。
因此,将各成分以宜于得到均匀组合物的任何适宜方式简单混合即可制得本发明组合物。将粉或粒状各成分混合的优选办法是先在常规混合器中冷却预混后将整个物料均化,其中在单螺杆或多螺杆挤出器中热混合,挤出优选在惰性气氛如氮气或氩气中进行。在该处理结束时,将所得条在水中冷却后切成颗粒,然后必要时干燥。还可将部分阻燃聚酰胺,红磷和锌化合物制成颗粒预混合物,然后在使用前与剩下的阻燃聚酰胺颗粒而得本发明组合物。
上面用其基本成分定义了这些组合物。不用说,以一定方式,如按以下方式改进这些组合物亦在本发明范围之内。
例如在用于生产成型制品时,本发明组合物可含各种添加剂:其中可如上述含增强或胶凝填料,如玻璃或石棉纤维,玻璃微珠,高岭土,二氧化硅,云母,膨润土,皂土或其混合物,最常用玻璃纤维,其平均直径1-15μm,长2-8mm。为得到具有优化机械性能的制品,可用例如环氧树脂,聚酯树脂,聚氨酯树脂或乙烯基树脂上装的纤维,其中这些树脂一般与氨基硅烷类偶合剂结合,而填料比例相对于组合物中聚酰胺重量的例如10-60wt%。
也可用其它添加剂,如润滑剂,稳定剂,冲击改进剂,颜料或染料,抗静电剂,结晶剂和红磷稳定剂,这些添加剂及其应用已广泛见于文献。
本发明组合物可用常见如注塑法或挤出法制成成品或半成品。
本发明组合物具有红磷阻燃组合物的优点,即耐火性和“Underwriters Laboratories”UL94垂直试验(试件1.6mm厚)中燃烧性达到V0至V1范围内。与无锌化合物的组合物相比,这一性能甚至也得到了改进。
但存在锌化合物提高了抗电弧扩展性(该性能称为IRC)。在填充有至少25wt%玻璃纤维的组合物情况下,该性能大于600V。
另外,本发明组合物对金属材料如铜的腐蚀性大大低于无锌化合物的组合物。在组合物含黑色着色剂时,这些改进达到更高的高度。组合物的侵蚀性也由以下试验确定:
150g含组合物的粒状复合物加入防漏容器中。
金属试件由铜、黄铜,银和青铜制成,将其悬在容器内的复合物上面。
将容器25℃加热336小时。
测定试件重量变化(一般增加)而确定腐蚀程度。
其它性能按以下方法测定:
抗电弧扩展性(IRC),V:
按DIN标准53480/1972所述“KC技术”测定。
燃烧性(UL94):
按UL94用1.6mm厚的试件测定垂直燃烧,其中:
在50%相对温度下调制48小时后评价
在70℃调制一星期后评价。
迁移性:
尺寸100mm×100mm且3.2mm厚的复合物片放在含硫酸液的室中以达到93%的湿度。这些片经过17次24小时循环,其中70℃下8小时且23℃下16小时。每一片然后用400ml水40℃洗4小时并测定洗涤水导电性。
Charpy冲击强度:
按ISO标准179测定。
本发明阻燃组合物特别宜于生产可用于电器工业(如电器和电子产业,电器设备,无线电和汽车工业)的成型制品。这些组合物特点也使其右经挤出和成膜法制成成品。
下述非限制性实施例详述本发明。
将组合物各成分在WernerPfleiderer类ZSK40挤出机中混合,其中由WernerZSB双进料螺杆送入玻璃纤维。
挤出机螺杆转速250rpm,温度280℃,挤出量70kg/h,脱气压56×102Pa。
所用原料为:
尼龙6,6(六亚甲基二胺和己二酸的聚合物):为粘度指数133ml/g(按ISO标准R307,1977版用可溶成分的90%甲酸液测定)为133ml/g的产品;
R23D×1玻璃纤维,由Owens Corning Fiberglass投放市场,浓度25wt%;
润滑剂:硬脂酸铝0.4wt%;着色剂1.16wt%,由Williams公司以商名Nigrosine Oisol Black N投放市场;
红磷阻燃剂,由Wilbright和Wilson公司以商名CPC400投放市场。
锌化合物,选自硼酸锌,硫化锌和氧化锌,可为无水态或结晶态。
各种组合物及其性能见表1,浓度以复合物相对于最终组合物质量的重量百分比表示,氧化锌为无水氧化锌,硼酸锌为水合物。
另一系列组合物用涂有酚-醛树脂的红磷作阻燃剂制成,其中含60wt%红磷,其平均粒径20-30μm并涂有40wt%熔点80℃和分子量800的酚-醛缩聚产物,所得结果列于表2。
腐蚀试验结果列于表3(试件重量增加mg):
表3这些结果清楚地表明了加锌化合物对聚酰胺组合物带来的金属腐蚀性以及减少迁移现象的效果。
Claims (11)
1、含红磷阻燃剂的聚酰胺组合物,其特征在于其中包括氧化锌和/或选自含氧锌盐和硫化物的锌盐。
2、权利要求1的组合物,其特征在于含氧锌盐为硼酸锌。
3、权利要求1的组合物,其特征在于作为添加剂包括硼酸锌和氧化锌的混合物。
4、上述权利要求之一的组合物,其特征在于其中包括10-100%,优选20-80%锌化合物(以金属质量计),相对于红磷质量计。
5、权利要求4的组合物,其特征在于其中包括40-80wt%锌化合物(以金属质量计),相对于红磷质量计。
6、权利要求3-5之一的组合物,其特征在于硼酸锌浓度15-40%,氧化锌浓度15-60%,均以Zn质量相对于红磷重量计。
7、上述权利要求之一的组合物,其特征在于红磷涂有树脂。
8、上述权利要求之一的组合物,其特征在于其中含无机填料。
9、权利要求8的组合物,其特征在于无机填料为玻璃纤维。
10、上述权利要求之一的组合物,其特征在于其中含至少一种润滑剂。
11、上述权利要求之一的组合物模制成的产品。
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CN102482490A (zh) * | 2009-06-19 | 2012-05-30 | 罗地亚经营管理公司 | 聚酰胺和聚酯树脂的混合组合物 |
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CN103797058A (zh) * | 2011-09-15 | 2014-05-14 | 巴斯夫欧洲公司 | 作为用于含有红磷的阻燃性聚酰胺的稳定剂的银/氧化锌混合物 |
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CN103304997B (zh) * | 2013-07-16 | 2015-02-25 | 广东泰昊新材料科技有限公司 | 无酸腐蚀、高电绝缘的红磷阻燃增强尼龙及其制备方法 |
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SG46178A1 (en) | 1998-02-20 |
HU9300434D0 (en) | 1993-05-28 |
ATE155513T1 (de) | 1997-08-15 |
ES2104105T3 (es) | 1997-10-01 |
JPH06145504A (ja) | 1994-05-24 |
EP0557222B1 (fr) | 1997-07-16 |
ES2104105T5 (es) | 2003-02-01 |
SK279749B6 (sk) | 1999-03-12 |
KR930017978A (ko) | 1993-09-21 |
CN1038253C (zh) | 1998-05-06 |
HU212194B (en) | 1996-03-28 |
DE69312116T2 (de) | 1998-01-15 |
DE69312116D1 (de) | 1997-08-21 |
EP0557222A1 (fr) | 1993-08-25 |
BR9300414A (pt) | 1993-08-24 |
CA2089699A1 (fr) | 1993-08-19 |
MX9300813A (es) | 1993-12-01 |
CZ280937B6 (cs) | 1996-05-15 |
CZ22293A3 (en) | 1994-01-19 |
TW245734B (zh) | 1995-04-21 |
KR960012458B1 (ko) | 1996-09-20 |
EP0557222B2 (fr) | 2002-08-21 |
PL171585B1 (pl) | 1997-05-30 |
DK0557222T3 (da) | 1997-08-25 |
SK8693A3 (en) | 1993-10-06 |
FR2687407A1 (fr) | 1993-08-20 |
CA2089699C (fr) | 1999-06-08 |
PL297771A1 (en) | 1993-09-20 |
HUT66448A (en) | 1994-11-28 |
DE69312116T3 (de) | 2003-12-11 |
JP2563057B2 (ja) | 1996-12-11 |
FR2687407B1 (zh) | 1994-08-19 |
US5466741A (en) | 1995-11-14 |
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