CN1066765C - 用于导线绝缘的聚酯组合物 - Google Patents
用于导线绝缘的聚酯组合物 Download PDFInfo
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- CN1066765C CN1066765C CN94190946A CN94190946A CN1066765C CN 1066765 C CN1066765 C CN 1066765C CN 94190946 A CN94190946 A CN 94190946A CN 94190946 A CN94190946 A CN 94190946A CN 1066765 C CN1066765 C CN 1066765C
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
- H01B3/421—Polyesters
- H01B3/422—Linear saturated polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08K3/20—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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
- Insulated Conductors (AREA)
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Abstract
具有改进的热老化性能的主要用作导线绝缘层的聚酯组合物,该新型组合物包括聚合物组分,而聚合物组分又包括:
(A)60~95%的至少一种芳族聚酯;
(B)3~20%的至少一种脂族聚酯;和
(C)3~20%的至少一种热塑性弹性体;
其中百分数是以聚合物组分的重量为基准的重量百分数。
Description
本发明涉及适用作导线绝缘层的聚酯组合物。
已知有许多聚酯组合物,包括可以在导体周围熔融成型(如熔融挤塑)而提供绝缘层的组合物。这类聚酯组合物的物理及电性质是非常重要的,如可燃性,燃烧时的生烟情况等。已经提出大量聚酯组合物可作导线的绝缘层。例如可参考:USP2,167,278、3,671,487、3,835,089、4,048,128、4,332,855和PCT91/19760(MP1360)以及EP0057415。
我们发现了一些新型聚酯组合物,它们具有很好的热老化性能。这些新型组合物包括一种聚合物组分,该聚合物组分包括:
(A)60~95%的至少一种芳族聚酯;
(B)3~20%的至少一种脂族聚酯,和
(C)3~20%的至少一种热塑性弹性体;上述百分数是以聚合物组分重量为基准的重量百分数。在一种实施方案中,聚合物组分含有(A)75-85%芳族聚酯;(B)6-10%的脂族聚酯和(C)6-10%的热塑性弹性体。
在此,主要针对能够在导体周围熔融成型,优选熔融挤塑而在其上提供绝缘层的电绝缘组合物来描述本发明,导体的实例有实心导线或绞合导线。新型组合物的绝缘层可以是导线外面唯一的绝缘层,也可以是导线外面数层绝缘层中的一层。如果有数层绝缘层,该聚酯组合物可以是最内层,也可以是最外层或中间层。然而,本发明也适用于其它熔融成型的构型,如软管、模塑制件等,也适用于可以其它的方式成型的组合物和主要作用不是电绝缘的组合物。
芳族聚酯优选为聚(对苯二甲酸-1,4-丁二醇酯);其它可使用的芳族聚酯包括聚(对苯二甲酸乙二醇酯)以及上述参考文献中所公开的那些。脂族聚酯优选聚己内酯。热塑性弹性体优选聚酯热塑性弹性体,如以商品名Arnitel和Hytrel出售的聚合物。热塑性弹性体例如可以含有例如通过尿烷键相互连结的芳族聚酯嵌段[如聚(对苯二甲酸-1,4-丁二醇酯)嵌段]和脂族聚酯嵌段[如聚(丁二酸-1,4-T二醇酯)嵌段]。Arnitel正是这样一种热塑性弹性体。聚合物(A)、(B)和(C)优选占聚合物组分重量的80~100%,特别优选90~100%。可以存在于聚合物组分中的其它聚合物包括聚烯烃以及上述参考文献中公开的那些聚合物,尤其是USP4,332,855中所公开的聚合物。优选组合物中的所有聚合物都与芳族聚酯相容,而且与芳族聚酯的溶度参数的差别至多为1.5。优选组合物中的所有聚合物均不含卤素。
本发明的新型组合物表现出特别好的热老化性能,尤其在高温下例如在150℃下老化168小时时,仍保持其伸长率和抗张强度。优选的组合物以导线涂盖层形式在150℃老化168小时,优选在180℃老化168小时后,仍保持至少50%的伸长率和至少80%的抗张强度(在室温下)。这种改善的保持其物理性质的能力显然源自组分(B)和组分(C)的存在,同时也使得可在组合物中包括较多改善阻燃性和/或消烟性的添加剂,而不产生无法接受的伸长率和/抗张强度的下降。这一点在用于汽车、火车、电车和其它的运输车辆以及其它电线处于高环境温度的用途时尤为重要。
我们发现当新型组合物含有SnO或ZnO,尤其是含有SnO时,新型组合物在阻燃性和/或消烟性等方面表现出极大的改善。SnO或ZnO的量经适当选择,达到所需的改善的阻燃性和/或消烟性的水平,而对其它物理和/或电性能不产生不能接受的损害,其量通常为组合物重量的3~60%,如10~50%,优选15~45%。金属氧化物可以是向组合物提供阻燃和/或消烟性的唯一成分,也可以同时使用其它这类成分。其它成分包括其它的金属氧化物和已知的各种添加剂,如上述参考文献中所公开的添加剂。但该组合物优选无含卤素的成分。SnO的存在使得可减少这类已知的添加剂的用量。优选SnO与其它添加剂的总重量百分数比在组成相同而仅仅不含SnO的组合物中产生同样水平的阻燃和/或消烟性能所需的那些添加剂的重量百分数低(优选低至少3%,特别优选低至少10%),上述性质的检测用下述标准之一,如极限氧指数(ASTM D2863-74),可燃性(SAE J1128 MIL-W-81044,或ASTM D3032-84)或烟雾产生性(ASTM E662)。还可存在的其他成分包括含磷的阻燃剂和/或Mg(OH)2,其中Mg(OH)2的用量减少到避免特别是聚酯的降解和发泡等问题的水平,这类问题在以其他方式同时使用这些成分时常出现。
本发明的新型组合物优选无增强填充剂,例如玻璃纤维。当组合物优选用作导线的涂盖层时,涂盖层可以有任意适当的厚度,如0.025英寸(0.063 5cm),优选0.008~0.018英寸(0.02-0.046cm)。也可以使用薄至0.005英寸(0.0125cm)厚的涂盖层,尤其是在与其它涂盖层一起使用时。
在使用SnO的结构中,涂盖层是灰色的。为了外观的要求可能加上一层由不同聚合物构成的最外层。然而,如上所述这里所描述的新型组合物构成的层可以是最内层、最外层或中间层。
实施例1-10
将表中所示的成分并按其数量在Brabender中混合在一起,然后熔融挤出在涂锡的20AWG 19/32绞合铜导线上,涂盖层厚度0.010英寸(0.025cm)。对该产品进行测试,结果列于表中。
在实施例1-10中所用的聚(对苯二甲酸-1,4-丁二醇酯)(PBT)是从Hoechst-Celanese得到的Celanex 1600A。ToneP700,Tone P767和Tone P787是从Union Carbide得到的不同分子量的聚己内酯。所用的Arnitel是具有聚酯嵌段的热塑性弹性体,由AKZO制造。实施例1-4和6-10中所用的稳定剂配方是1.75%的聚碳化二亚胺(PCD),1.75%的受阻碍酚性抗氧剂(Irganox 1010)和0.88%的脂族亚磷酸酯(Western619)。实施例5中所用的稳定剂的配方为2.2%的聚碳化二亚胺(PCD),2.2%的受阻碍酚性抗氧剂(Irganox 1010)和1.2%的脂族亚磷酸酯(Western 619)。
伸长率和抗张强度测试用3英寸(7.5cm)的从导线上剥下的试样进行。VW-1测试根据VLVW-1试验进行,结果用x/y表示,其中y为受试样品的数量,x为通过测试的样品的数量。
表·实施例1和2是不按本发明的比较例。
Claims (8)
1.一种绝缘导线,包括:
(1)实心或绞合导线,和
(2)在导线上的绝缘层,所述绝缘层由一种聚合物组合物构成,所述聚合物组合物的聚合物组分包括:
(A)60~95%的至少一种芳族聚酯;
(B)3~20%的至少一种脂族聚酯;和
(C)3~20%的至少一种热塑性弹性体;
其中百分数是以聚合物组分的重量为基准的重量百分数;并且占聚合物组分重量的80-100%。
2.根据权利要求1的绝缘导线,其中聚合物组分包括:
(A)75~85%的芳族聚酯;
(B)6~10%的脂族聚酯;和
(C)6~10%的热塑性弹性体;
其中百分数是以聚合物组分的重量为基准的重量百分数;并且占聚合物组分重量的80-100%。
3.根据权利要求2的绝缘导线,其中芳族聚酯是聚(对苯二甲酸-1,4-丁二醇酯),脂族聚酯是聚己内酯,热塑性弹性体是含有聚酯嵌段的热塑性弹性体。
4.根据权利要求1、2或3的绝缘导线,其中含有占组合物重量的3~60%的SnO和/或ZnO。
5.根据权利要求1、2或3的绝缘导线,其中含有占组合物重量的10~50%的SnO。
6.根据权利要求1、2或3的绝缘导线,其中含(a)SnO,和(b)下列一种或两种物质:Mg(OH)2和含磷阻燃剂。
7.根据权利要求1、2或3的绝缘导线,其中无含卤素的组分。
8.根据权利要求1、2或3的绝缘导线,其中在所述组合物构成的层外边还含有第二绝缘层。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US474993A | 1993-01-14 | 1993-01-14 | |
US08/004,749 | 1993-01-14 |
Publications (2)
Publication Number | Publication Date |
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CN1116431A CN1116431A (zh) | 1996-02-07 |
CN1066765C true CN1066765C (zh) | 2001-06-06 |
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Application Number | Title | Priority Date | Filing Date |
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CN94190946A Expired - Fee Related CN1066765C (zh) | 1993-01-14 | 1994-01-13 | 用于导线绝缘的聚酯组合物 |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0679171B1 (zh) |
JP (1) | JPH08506129A (zh) |
CN (1) | CN1066765C (zh) |
AT (1) | ATE220415T1 (zh) |
AU (1) | AU690537B2 (zh) |
DE (1) | DE69430947T2 (zh) |
WO (1) | WO1994016014A1 (zh) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US6087591A (en) * | 1995-04-26 | 2000-07-11 | Nguyen; Phu D. | Insulated electrical conductors |
JPH11504365A (ja) * | 1995-04-26 | 1999-04-20 | レイケム・コーポレイション | ポリエステル組成物 |
JP5205979B2 (ja) * | 2007-01-23 | 2013-06-05 | 日立電線株式会社 | 絶縁電線 |
JP5200563B2 (ja) * | 2008-02-01 | 2013-06-05 | 日立電線株式会社 | 絶縁電線 |
CN108231255A (zh) * | 2017-12-27 | 2018-06-29 | 深圳市凯中和东新材料有限公司 | 一种无卤环保f级直焊三层绝缘线 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3835089A (en) * | 1972-06-23 | 1974-09-10 | Gen Electric | Polylactone-modified linear polyesters and molding compositions containing the same |
US5081176A (en) * | 1990-09-24 | 1992-01-14 | General Electric Company | Polyalkylene Terephthalate compositions having improved burning characteristics |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3985926A (en) * | 1975-08-27 | 1976-10-12 | Allied Chemical Corporation | Flame-retardant carpet |
US4332855A (en) * | 1978-04-14 | 1982-06-01 | Raychem Corporation | Polymeric compositions |
DE3276178D1 (en) * | 1981-01-30 | 1987-06-04 | Teijin Ltd | Polyester resin composition |
EP0186050B1 (en) * | 1984-12-19 | 1990-01-31 | General Electric Company | Copolyester-carbonate composition |
US5248713A (en) * | 1990-06-13 | 1993-09-28 | Raychem Corporation | Stabilized polymeric compositions |
BR9106186A (pt) * | 1990-10-15 | 1993-03-16 | Gen Electric | Composicoes de moldagem termoplasticas altamente densas tendo resistencia ao impacto aperfeicoada |
-
1994
- 1994-01-13 EP EP94907242A patent/EP0679171B1/en not_active Expired - Lifetime
- 1994-01-13 WO PCT/US1994/000624 patent/WO1994016014A1/en active IP Right Grant
- 1994-01-13 AT AT94907242T patent/ATE220415T1/de not_active IP Right Cessation
- 1994-01-13 DE DE69430947T patent/DE69430947T2/de not_active Expired - Fee Related
- 1994-01-13 AU AU60900/94A patent/AU690537B2/en not_active Ceased
- 1994-01-13 CN CN94190946A patent/CN1066765C/zh not_active Expired - Fee Related
- 1994-01-13 JP JP6516359A patent/JPH08506129A/ja active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3835089A (en) * | 1972-06-23 | 1974-09-10 | Gen Electric | Polylactone-modified linear polyesters and molding compositions containing the same |
US5081176A (en) * | 1990-09-24 | 1992-01-14 | General Electric Company | Polyalkylene Terephthalate compositions having improved burning characteristics |
Also Published As
Publication number | Publication date |
---|---|
AU690537B2 (en) | 1998-04-30 |
AU6090094A (en) | 1994-08-15 |
EP0679171B1 (en) | 2002-07-10 |
JPH08506129A (ja) | 1996-07-02 |
CN1116431A (zh) | 1996-02-07 |
DE69430947T2 (de) | 2003-03-13 |
EP0679171A1 (en) | 1995-11-02 |
DE69430947D1 (de) | 2002-08-14 |
ATE220415T1 (de) | 2002-07-15 |
WO1994016014A1 (en) | 1994-07-21 |
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