CN1196769C - 阻燃组合物 - Google Patents
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Abstract
本发明涉及包含(A)包括乙烯与至少一种包括乙烯基不饱和聚二烃基硅氧烷的其它共聚单体的共聚物的聚合物和(B)至少一种选自铝、镁、钙和钡的氧化物、氢氧化物和碳酸盐的物质的无机填料的阻燃组合物。本发明也涉及含这种组合物的电缆或电线。
Description
本发明涉及阻燃组合物和涉及具有含这种阻燃组合物的阻燃层的电缆或电线。
采用含卤化物的阻燃组合物是众所周知的。
通过向组合物掺入数量较大的、通常为50-60%(重量)的无机填料以增加聚合物组合物的阻燃性也是众所周知的,这种无机填料在200-600℃间经吸热分解会释放一种惰性气体。在本世纪七十年代,普遍采用的是氢氧化铝Al(OH)3。到九十年代更常采用的是Mg(OH)2,同时CaCO3也已用作同一目的。
也已提出将使用硅油的阻燃添加剂系统用于聚烯烃组合物中。例如,EP 0393959公开了一种包括(A)一种有机聚合物,其中至少40%(重量)是含一种或多种选自丙烯酸C1-C6烷基酯、甲基丙烯酸C1-C6烷基酯、丙烯酸、甲基丙烯酸以及乙酸乙烯基酯共聚单体的乙烯共聚物,(B)一种硅油或硅橡胶纯胶料以及(C)一种无机填料的阻燃聚合物组合物,这种无机填料是元素周期表中第IIA族金属的化合物(见Perry等的“Chemical Engineers′Handbook”第五版,1973),但既不是氢氧化物,也基本上不是水合物。
含卤化物的阻燃组合物的缺点是:当燃烧时它们会释放出危害环境的含卤化物的混合物。
已知的含聚硅氧烷组合物的缺点是:硅橡胶纯胶料通常是块状的,而块状是难于处理的。为了使其具有流动性,必须将其预热和泵送。而且,混合的硅橡胶胶料在挤出时往往会在组合物内发生迁移,这可能会在加工所用设备如模头上引起沉积即所谓模头滴料现象。这种沉积现象也会阻塞用于打印电缆标识的压花轮。此外,硅橡胶纯胶料是一种附加的组分,对其进行处理必会延长加工时间和增加成本。
根据本发明,采用含有包括含硅化合物的单体的共聚物的阻燃剂组合物可减轻或消除上述缺点。因此,将含硅化合物聚合在聚合物中,成为聚合物整体的一部分,而不采用与阻燃剂组合物的聚合物相混合的方法。除了防止模头滴料外,还可使组合物中的组分较已知组合物少,并还具有其它的优点,使组合物的均匀性更好。
根据本发明组合物的其它优点是在于新组合物中所需的聚硅氧烷化合物含量较已知组合物中低。
因此,本发明涉及包括下列组分的阻燃组合物:
(A).包含乙烯和至少一种其它的含按照式(I)的乙烯基不饱和聚二烃基硅氧烷的共聚单体的共聚物的聚合物:
式中n=1-1000,R与R′各自为乙烯基;具有1-10个碳原子的支链或非支链烷基;具有6或10个碳原子的芳基;具有7-10个碳原子的烷芳基;或具有7-10个碳原子的芳烷基(优选的是可商购的乙烯基聚二甲基硅氧烷);以及
(B)一种无机填料包括至少一种选自铝、镁、钙和钡的氧化物、氢氧化物和碳酸盐的物质。
本发明也涉及制造含这类组合物的物品,具体说,本发明涉及具有含这种阻燃组合物的阻燃层的电缆或电线。
从下面的说明和所附权利要求书,本发明的特征是显而易见的。
尽管根据本发明的硅氧烷是经聚合的,并因而是键合的,但达到了具有出乎意料地好的极限氧指数(Limiting Oxygen Index,LOI),该数值明显地高于不合任何聚硅氧烷的组合物并与含量相同的、聚合物和硅橡胶胶料的组合物所具有的LOI值相同。
根据ISO 4589-A-IV,极限氧指数(LOI)是产品耐火性的一种量度。为了测定LOI值,将受试的化合物试样置于氮和氧混合物的气氛中燃烧。使N2/O2混合物中氧的含量逐渐降低至试样停止燃烧为止。此时N2/O2混合物中O2的百分含量即为受试化合物的LOI值。LOI值高,意味着维持燃烧所需的氧百分含量高,即该化合物具有好的耐火性。对于阻燃组合物来说,LOI值应当是至少22,更高的LOI值是理想的。
如上所述,含式(I)乙烯基不饱和聚二烃基硅氧烷单体的聚合物是乙烯与式(I)单体、任选一种或多种其它共聚单体的共聚物。这些其它共聚单体最好选自丙烯酸C1-C6烷基酯、甲基丙烯酸C1-C6烷基酯、丙烯酸、甲基丙烯酸、乙酸乙烯基酯、乙烯基三甲氧基硅烷以及乙烯基三乙氧基硅烷。
有关这方面应该指出的是,本文所用名词“共聚物”包括聚合物主链上接枝有一种或多种共聚单体的接枝共聚物。
包括式(I)单体的上述聚合物的优选含量至少为阻燃组合物的40%(重量),更优选至少60%(重量)。
除了上述乙烯共聚物外,根据本发明的组合物还可包括其它的混合的聚烯烃,如乙烯、丙烯与丁烯的均聚物和共聚物及丁二烯或异戊二烯的聚合物。适用的乙烯均聚物和共聚物包括低密度聚乙烯、线型的低、中或高密度聚乙烯以及密度很低的聚乙烯。其它适用的聚合物包括聚酯、聚醚和聚氨酯。弹性体聚合物如乙烯-丙烯橡胶(EPR)、乙烯-丙烯-二烯单体橡胶(EPDM)、热塑性弹性体橡胶(TPE)以及丙烯腈丁二烯橡胶(NBR)也可采用。硅烷可交联的聚合物,即在水和任选硅烷醇缩合催化剂存在下,由具有能通过水解和缩合形成硅烷醇基团的可水解基团的不饱和硅烷单体制备的聚合物,也可采用。硅烷可交联的聚合物可以是例如乙烯与不饱和的硅烷单体(如乙烯基三烷氧基硅烷)的共聚物,这种共聚物可在聚合反应器中由单体共聚合而制得,或者将硅烷单体接枝在聚乙烯主链上而制得。
本发明组合物中乙烯基聚二烃基硅氧烷的用量约为0.01-30%(重量),优选1-10%(重量),而更优选为3-7%(重量)。
适用于本发明阻燃组合物的无机填料是铝、镁、钙和/或钡的氧化物、氢氧化物以及碳酸盐,适用的无机填料的实例是碳酸钙、氧化镁及碳酸钙镁(huntite)Mg3Ca(CO3)4。
在本发明组合物中无机填料的用量是10-70%(重量),优选15-45%(重量)。
除了聚合物和无机填料外,本发明组合物还可含其它成分,例如,抗氧化剂及少量其它常规的聚合物添加剂。
本发明的阻燃组合物中各种组分的适宜用量上文已加以具体说明。然而,对本领域技术熟练的人员来说,选择的用量比例应能得到所需的均衡性能,具体说,使组合物的阻燃性与物理性能之间要达到均衡,这是显而易见的。
根据本发明的阻燃组合物适用于如电缆(如安装电缆和柔性电缆)、管材、管子、软管、电接触器件等。
通过下面实施例对本发明作进一步的说明,但决不能认为这是对本
发明范围的限制。
实施例
将本发明的阻燃组合物与已知的阻燃组合物进行比较。用于本实施例的化合物在160℃下在Brabender(布拉本德)共捏合机中混合而得到 包括含各种已知组合物的混合物以及含本发明组合物的混合物,最后,一种混合物是不含聚硅氧烷的。对这些混合物进行了如上述的LOI-值的评价,研磨挤出物后将所得粒料模塑成3毫米厚片材。
这些混合物及LOI值列于表1中。
混合物1只以碳酸钙作为阻燃物质,不含聚硅氧烷。混合物2和混合物3都含本发明的阻燃组合物。混合物4-6含已知的不同的阻燃组合物。
在实施例2和3中,本发明阻燃组合物中的聚合物是乙烯、乙烯基不饱和聚二甲基硅氧烷与丙烯酸丁酯的三元共聚物。
已知的阻燃组合物是由硅橡胶纯胶料与乙烯-丙烯酸乙酯共聚物及不同的无机阻燃添加剂的混合物所组成的。
表1
组分 | 混合物1 | 混合物2 | 混合物3 | 混合物4 | 混合物5 | 混合物6 |
CaCO3 1Mg(OH)2 2Mg(OH)2 3E/Si/BA-三元共聚物4硅橡胶纯胶料EEA5IB-215(Irganox,稳定剂)密度LOI | 30%69.8%0.2%20.8 | 30%69.8%0.2%1.17g/cm330.6 | 30%69.8%0.2%1.17g/cm329.6 | 30%5%64.8%0.2%1.18g/cm339.2 | 30%5%64.8%0.2%1.18g/cm335.2 | 30%5%64.8%0.2%1.15g/cm337.0 |
1Omya EX-H1 SP
2Kisuma 5J,购自KyowaChemicls
3FR20 MHRM 105,购自Dead Sea Bromine
4含14%BA和3.6%乙烯基聚二甲基硅氧烷的乙烯三元共聚物;式(I)中n为100
5EEA=含15.3%EA(OE5810级,购自Borealis)的乙烯/丙烯酸乙酯共聚物。
根据本发明的混合物2和3得到的LOI值显著地优于不含聚硅氧烷的混合物1,但稍低于含EEA和硅橡胶纯胶料混合物的混合物的LOI值。必须指出混合物2和3中硅氧烷的总量为2.5%,即只有混合物4-6(含5%硅橡胶纯胶料)中所含的一半。提高本发明组合物中硅氧烷含量可以获得较高的LOI值。
Claims (10)
1.一种阻燃组合物,包含:
(A).包含乙烯和至少一种按照式(I)的乙烯基不饱和聚二烃基硅氧烷的其它共聚单体的共聚物的聚合物:
式中n=1-1000,R与R′各自为乙烯基;具有1-10个碳原子的支链或非支链烷基;具有6或10个碳原子的芳基;具有7-10个碳原子的烷芳基;或具有7-10个碳原子的芳烷基;以及
(B)一种无机填料物质,包括至少一种选自铝、镁、钙和钡的氧化物、氢氧化物和碳酸盐的无机填料。
2.根据权利要求1的阻燃组合物,其中共聚物包括至少一种选自丙烯酸C1-C6烷基酯、甲基丙烯酸C1-C6烷基酯、丙烯酸、甲基丙烯酸、及乙酸乙烯酯的其它共聚单体。
3.根据权利要求2的阻燃组合物,其中包括乙烯基不饱和聚二烃基硅氧烷共聚单体的共聚物构成全部组合物中聚合物部分的至少40%(重量)。
4.根据权利要求1-3中任一项阻燃组合物,其中乙烯基聚二烃基硅氧烷共聚单体的用量约为全部组合物重量的0.01-30%。
5.根据权利要求1-4中任一项阻燃组合物,其中乙烯基聚二烃基硅氧烷共聚单体的用量约为全部组合物重量的1-10%。
6.根据权利要求1-5中任一项阻燃组合物,其中乙烯基聚二烃基硅氧烷共聚单体的用量为全部组合物重量的3-7%。
7.根据权利要求1-6中任一项阻燃组合物,其中无机填料的用量约为全部组合物重量的10-70%。
8.根据权利要求1-7任何一项阻燃组合物,其中无机填料的用量约为全部组合物重量的15-45%。
9.根据权利要求1-8中任何一项阻燃组合物,其中聚合物包括乙烯,根据式(I)的乙烯基不饱和聚二甲基硅氧烷及丙烯酸丁酯的共聚物。
10.具有包含根据权利要求1-9任何一项阻燃组合物的阻燃层的电缆或电线。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE96033717 | 1996-09-17 | ||
SE9603371A SE507330C2 (sv) | 1996-09-17 | 1996-09-17 | Flamskyddskomposition och kabel innefattande flammskyddskompostionen |
SE9603371-7 | 1996-09-17 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1176989A CN1176989A (zh) | 1998-03-25 |
CN1196769C true CN1196769C (zh) | 2005-04-13 |
Family
ID=20403902
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB97118481XA Expired - Fee Related CN1196769C (zh) | 1996-09-17 | 1997-09-17 | 阻燃组合物 |
Country Status (13)
Country | Link |
---|---|
US (1) | US6166120A (zh) |
EP (1) | EP0927224B1 (zh) |
JP (1) | JP2001500559A (zh) |
KR (1) | KR100509213B1 (zh) |
CN (1) | CN1196769C (zh) |
AT (1) | ATE227755T1 (zh) |
AU (1) | AU715219B2 (zh) |
BR (1) | BR9712049A (zh) |
CA (1) | CA2265762A1 (zh) |
DE (1) | DE69717130T2 (zh) |
ES (1) | ES2187817T3 (zh) |
SE (1) | SE507330C2 (zh) |
WO (1) | WO1998012253A1 (zh) |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SE507330C2 (sv) * | 1996-09-17 | 1998-05-11 | Borealis As | Flamskyddskomposition och kabel innefattande flammskyddskompostionen |
AU2002952136A0 (en) * | 2002-10-17 | 2002-10-31 | Polymers Australia Pty Limited | "Modified Polymeric Compositions" |
EP1396865A1 (en) * | 2002-09-03 | 2004-03-10 | Borealis Technology Oy | Flame retardant polymer composition |
GB0221349D0 (en) * | 2002-09-14 | 2002-10-23 | Kourgli Mokhtar | Improvements relating to cable guards,cable troughs and fire retardant materials |
DE60323974D1 (de) * | 2003-08-27 | 2008-11-20 | Borealis Tech Oy | Flammengeschützte Polymermischung mit feinen Partikeln |
CN100441653C (zh) * | 2004-02-02 | 2008-12-10 | 支亮 | 一种无卤素低密度防火密封堵料 |
DE602005015078D1 (de) | 2005-02-23 | 2009-08-06 | Borealis Tech Oy | Strom- oder Kommunikationskabel mit einer flammenresistenten Polymerschicht |
EP1695996B1 (en) * | 2005-02-28 | 2008-07-23 | Borealis Technology Oy | Scorch-retarding polymer composition |
ES2328950T3 (es) | 2006-05-31 | 2009-11-19 | Borealis Technology Oy | Composicion polimerica retardante de la llama, que comprende una poliolefina con distribucion de peso molecular amplia. |
DK1862496T3 (da) | 2006-05-31 | 2013-02-11 | Borealis Tech Oy | Flammehæmmende polyethylensammensætning, omfattende polypropylen |
JP4520437B2 (ja) * | 2006-07-26 | 2010-08-04 | 信越化学工業株式会社 | Led用蛍光物質入り硬化性シリコーン組成物およびその組成物を使用するled発光装置。 |
EP2130864B1 (en) | 2008-06-05 | 2012-03-28 | Borealis AG | Flame retardant polyolefin composition comprising a high amount of inorganic filler |
ES2537084T3 (es) | 2008-12-22 | 2015-06-02 | Borealis Ag | Composición retardante de la llama con propiedades mecánicas mejoradas |
JP2012525460A (ja) * | 2009-04-30 | 2012-10-22 | ダウ コーニング コーポレーション | シランにより変性したエラストマー組成物 |
JP2021528527A (ja) | 2018-06-15 | 2021-10-21 | ボレアリス エージー | 難燃性ポリオレフィン組成物 |
EP3956392B1 (en) | 2019-04-16 | 2024-12-11 | BYK-Chemie GmbH | Silyl functional compound for improving flame retardant properties |
WO2020212377A1 (en) | 2019-04-16 | 2020-10-22 | Byk-Chemie Gmbh | Silyl functional compound for improving flame retardant properties |
CN113150486A (zh) * | 2021-03-31 | 2021-07-23 | 大连理工大学 | 一种硅氧烷基陶瓷化聚烯烃及其制备方法与应用 |
CN113185642A (zh) * | 2021-03-31 | 2021-07-30 | 大连理工大学 | 一种含硅氧烷的聚烯烃树脂及其制备方法与应用 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5002996A (en) * | 1988-03-24 | 1991-03-26 | Sumitomo Bakelite Company Limited | Flame retardant olefinic resin composition |
US5091453A (en) * | 1989-04-21 | 1992-02-25 | Bp Chemicals Limited | Flame retardant polymer composition |
US5234360A (en) * | 1992-06-25 | 1993-08-10 | Robert V. Smith | Multiple outlet extension cord |
SE507330C2 (sv) * | 1996-09-17 | 1998-05-11 | Borealis As | Flamskyddskomposition och kabel innefattande flammskyddskompostionen |
-
1996
- 1996-09-17 SE SE9603371A patent/SE507330C2/sv not_active IP Right Cessation
-
1997
- 1997-09-16 WO PCT/SE1997/001561 patent/WO1998012253A1/en active IP Right Grant
- 1997-09-16 JP JP10514584A patent/JP2001500559A/ja active Pending
- 1997-09-16 BR BR9712049A patent/BR9712049A/pt active Search and Examination
- 1997-09-16 ES ES97942349T patent/ES2187817T3/es not_active Expired - Lifetime
- 1997-09-16 CA CA002265762A patent/CA2265762A1/en not_active Abandoned
- 1997-09-16 AT AT97942349T patent/ATE227755T1/de not_active IP Right Cessation
- 1997-09-16 AU AU44067/97A patent/AU715219B2/en not_active Ceased
- 1997-09-16 DE DE69717130T patent/DE69717130T2/de not_active Expired - Fee Related
- 1997-09-16 KR KR10-1999-7002210A patent/KR100509213B1/ko not_active IP Right Cessation
- 1997-09-16 EP EP97942349A patent/EP0927224B1/en not_active Expired - Lifetime
- 1997-09-17 CN CNB97118481XA patent/CN1196769C/zh not_active Expired - Fee Related
-
1999
- 1999-03-04 US US09/262,372 patent/US6166120A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN1176989A (zh) | 1998-03-25 |
SE9603371L (sv) | 1998-03-18 |
EP0927224A1 (en) | 1999-07-07 |
KR20030029656A (ko) | 2003-04-16 |
SE9603371D0 (sv) | 1996-09-17 |
DE69717130D1 (de) | 2002-12-19 |
DE69717130T2 (de) | 2003-10-09 |
EP0927224B1 (en) | 2002-11-13 |
BR9712049A (pt) | 1999-08-24 |
AU4406797A (en) | 1998-05-11 |
ATE227755T1 (de) | 2002-11-15 |
AU715219B2 (en) | 2000-01-20 |
WO1998012253A1 (en) | 1998-03-26 |
JP2001500559A (ja) | 2001-01-16 |
ES2187817T3 (es) | 2003-06-16 |
CA2265762A1 (en) | 1998-03-26 |
KR100509213B1 (ko) | 2005-08-24 |
US6166120A (en) | 2000-12-26 |
SE507330C2 (sv) | 1998-05-11 |
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