CN1751069A - 湿交联的聚合物组合物 - Google Patents
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- C08L2312/00—Crosslinking
- C08L2312/08—Crosslinking by silane
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Abstract
本发明是包含硅氧烷官能聚烯烃聚合物和热处理的炭黑的湿交联的聚合物组合物。本发明还包括由该湿交联的聚合物组合物制备的涂料以及通过在电线或电缆上施加该涂料制备的电线和电缆构造物。
Description
本发明涉及湿交联(moisture-crosslinkable)的聚合物组合物，该组合物用于电线和电缆应用，特别是低压室外应用和中等和高压半导屏蔽应用。
湿交联相对于过氧化物或辐射诱导的交联具有许多益处。然而，使用目前可获得的湿交联的聚合物组合物的一个缺点是挤出工艺中的过早交联(或焦烧)。此过早交联阻碍均匀的产物平滑度和质量。因此，需要能够避免过早交联的湿交联的聚合物组合物。
湿交联的组合物可以通过(a)将乙烯基烷氧基硅烷接枝到乙烯均聚物或(b)聚合乙烯基烷氧基硅烷与乙烯而制备。相信当应用到此湿交联的组合物时，硅烷交联化学依赖于水的参与以水解侧烷氧基硅烷、然后缩合到稳定、交联的硅氧烷结构。目前可获得的湿交联的聚合物组合物不能充分地防止过早交联。
如果能获得合适的湿交联的聚合物组合物，其允许使用常规的热塑性塑料加工设备，导致低资本投资，要求较少的制造空间，和允许应用类型中的更大灵活性。显著地，如果避免过早交联，其阻止聚合物凝胶粘附到常规挤出设备的表面，促进设备的连续操作。
本发明是包含硅氧烷官能聚烯烃聚合物和热处理的炭黑的湿交联的聚合物组合物。本发明还包括从湿交联的聚合物组合物制备的涂料以及通过在电线或电缆上施加该涂料制备的电线和电缆构造物。
使用在此公开的信息，本领域技术人员可容易地确定合适的电线和电缆构造物，其可以由本发明的湿交联的聚合物组合物制备。
本发明的湿交联的聚合物组合物包含硅氧烷官能聚烯烃聚合物和热处理的炭黑。
合适的硅氧烷官能聚烯烃聚合物包括(a)含有接枝到其上的硅烷化合物的乙烯均聚物和(b)硅烷化合物和乙烯的聚合产物。乙烯基烷氧基硅烷是接枝到乙烯均聚物上的合适的硅烷化合物。聚合产物包括共聚物和三元共聚物。共聚物的一个例子是乙烯和乙烯基烷氧基硅烷的共聚物。三元共聚物的一个例子是乙烯、不饱和酯和乙烯基烷氧基硅烷的三元共聚物。优选的不饱和酯具有4-20个碳原子。
优选，热处理的炭黑是在至少400摄氏度的温度下反应器后(postreactor)热处理的炭黑。炭黑可以是炉黑、热裂炭黑、凯金(Ketjen)炭黑、乙炔黑、或在ASTM N110、N351、N472或N550中描述的任何等级炭黑。此外优选，热处理的炭黑在900摄氏度下在氮气气氛中的挥发物损失小于1.0wt％。更优选，热处理的炭黑在900摄氏度下在氮气气氛中的挥发物损失小于0.1wt％。
此外，组合物可包含其它添加剂如抗氧剂、润滑剂、防粘连剂、催化剂、填料、和加工助剂。
在另一个实施方案中，本发明是由硅氧烷官能聚烯烃聚合物和热处理的炭黑的湿交联的聚合物组合物制备的涂料。在另一个实施方案中，本发明是通过在电线或电缆上施加该涂料制备的电线或电缆构造物。
实施例
如下非限制性实施例说明本发明。
实施例1-12：炭黑母料对比物
炭黑母料使用六种市售炭黑材料制备。
市售炭黑材料包括：(1)CC1150U；(2)CSX362；(3)M8；(4)M5；(5)M2；和(6)BP3700。CC1150U购自Columbian Chemicals Company，其它炭黑材料购自Cabot Corporation。对于每种炭黑，供应商提供指示如下参数的规格：根据ASTM D1510测量的材料碘吸附(mg/g)和根据ASTM D2414测量的DBP吸附(cc/100g)。每种炭黑的水分含量由卡尔费歇尔(Karl Fischer)滴定测量。
表I
| 炭黑 | ||||||
| 性能 | Ex.1C1150U | Ex.2CSX362 | Ex.3M8 | Ex.4M5 | Ex.5M2 | Ex.6BP3700 |
| 碘吸附，mg/g | 172 | 125 | 136 | 84 | 44 | 44 |
| DBP吸附，cc/100g | 115 | 106 | 118 | 71 | 94 | 118 |
| 湿气，ppm | 5000 | 5000 | 3000 | 3700 | 3000 | 1000 |
期望热处理的炭黑的湿气含量小于200份每百万份(ppm)。
每种炭黑母料使用(1)丙烯酸乙酯存在量为18wt％和熔融指数为20g/10min的乙烯丙烯酸乙酯共聚物(″EEA″)、(2)炭黑、(3)环境固化(快固化速度)缩合催化剂、和(4)抗氧剂混合物制备。母料使用如下重量百分比制备：(1)47％EAA；(2)45％炭黑；(3)4％缩合催化剂；和(4)4％抗氧剂混合物。
表II
| 炭黑母料 | ||||||
| 实施例 | 7 | 8 | 9 | 10 | 11 | 12 |
| 炭黑 | CC1150U | CSX362 | M8 | M5 | M2 | BP3700 |
| 湿气，ppm | 1024 | 1260 | 993 | 1040 | 1221 | 677 |
期望从热处理的炭黑制备的或含有热处理的炭黑的炭黑母料的湿气含量小于200份每百万份(ppm)。
实施例13-19：挤出的电缆
将每种炭黑母料与市售硅烷-反应器共聚物在5.8母料对94.2硅烷-乙烯共聚物的比例下干燥共混。将共混的组合物使用Brabender挤出机在14AWG铜线上挤出以获得30密耳的壁厚度。每个挤出电缆的表面(实施例13-18)是粗糙的，表明由于过早交联造成的焦烧。
使用非环境固化(更缓慢固化速度)，三组分，硅烷交联体系(实施例19)挤出对照电缆，该体系以，SI-LINKTM PE湿气固化购自DowChemical Company。对照电缆在挤出之后显示平滑的表面，证实挤出条件可在预固化不存在下产生平滑表面。
期望从环境固化(快固化速度)湿交联的聚合物组合物挤出的电缆在挤出之后显示平滑表面，该组合物由热处理的炭黑制备或含有热处理的炭黑。
Claims (13)
1.一种湿交联的聚合物组合物，其包含：
a.硅氧烷官能聚烯烃聚合物，和
b.热处理的炭黑。
2.根据权利要求1所述的湿交联的聚合物组合物，其中硅氧烷官能聚烯烃聚合物是含有接枝到其上的硅烷化合物的乙烯均聚物。
3.根据权利要求2所述的湿交联的聚合物组合物，其中硅烷化合物是乙烯基烷氧基硅烷。
4.根据权利要求1所述的湿交联的聚合物组合物，其中硅氧烷官能聚烯烃聚合物是硅烷化合物和乙烯的聚合产物。
5.根据权利要求4所述的湿交联的聚合物组合物，其中硅氧烷官能聚烯烃聚合物是乙烯和乙烯基烷氧基硅烷的共聚物。
6.根据权利要求4所述的湿交联的聚合物组合物，其中硅氧烷官能聚烯烃聚合物是乙烯、不饱和酯和乙烯基烷氧基硅烷的三元共聚物。
7.根据权利要求4所述的湿交联的聚合物组合物，其中硅烷化合物是乙烯基烷氧基硅烷。
8.根据权利要求1所述的湿交联的聚合物组合物，其中热处理的炭黑是在至少400摄氏度的温度下反应器后热处理的炭黑。
9.根据权利要求8所述的湿交联的聚合物组合物，其中炭黑选自炉黑、热裂炭黑、凯金炭黑、或乙炔黑。
10.根据权利要求1所述的湿交联的聚合物组合物，其中热处理的炭黑在900摄氏度下在氮气气氛中的挥发物损失小于1.0wt％。
11.根据权利要求1所述的湿交联的聚合物组合物，其中热处理的炭黑在900摄氏度下在氮气气氛中的挥发物损失小于0.1wt％。
12.由根据权利要求1所述的湿交联的聚合物组合物制备的涂料。
13.通过在电线或电缆上施加根据权利要求12所述的涂料制备的电线或电缆构造物。
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| DK89087A (da) * | 1987-02-20 | 1988-08-21 | Nordiske Kabel Traad | Fremgangsmaade til fremstilling af en elektrisk halvledende, stripbar plastblending |
| JPH10265583A (ja) * | 1997-03-25 | 1998-10-06 | Hitachi Cable Ltd | 架橋成形物及び電線・ケーブル |
| JPH11209637A (ja) * | 1998-01-30 | 1999-08-03 | Kanegafuchi Chem Ind Co Ltd | 作業性の改善された硬化性組成物および作業性改善方法 |
| JP2000290437A (ja) * | 1999-04-02 | 2000-10-17 | Yazaki Corp | シラン架橋半導電層用樹脂組成物 |
| JP4399076B2 (ja) * | 1999-04-28 | 2010-01-13 | 日本ユニカー株式会社 | 水架橋ポリエチレン絶縁電力ケーブル外部半導電層用剥離性半導電性樹脂組成物 |
| JP4399077B2 (ja) * | 1999-06-09 | 2010-01-13 | 日本ユニカー株式会社 | 水架橋ポリエチレン絶縁電力ケーブル内部半導電層用密着性半導電性樹脂組成物 |
| US6086792A (en) * | 1999-06-30 | 2000-07-11 | Union Carbide Chemicals & Plastics Technology Corporation | Cable semiconducting shields |
| US20050063892A1 (en) * | 2003-09-18 | 2005-03-24 | Deepak Tandon | Thermally modified carbon blacks for various type applications and a process for producing same |
-
2004
- 2004-02-18 EP EP04712291A patent/EP1597288B1/en not_active Expired - Lifetime
- 2004-02-18 JP JP2006503606A patent/JP2006518797A/ja not_active Withdrawn
- 2004-02-18 WO PCT/US2004/004463 patent/WO2004076548A2/en active IP Right Grant
- 2004-02-18 CA CA2516415A patent/CA2516415C/en not_active Expired - Lifetime
- 2004-02-18 AT AT04712291T patent/ATE327263T1/de not_active IP Right Cessation
- 2004-02-18 CN CNB2004800047233A patent/CN100393755C/zh not_active Expired - Lifetime
- 2004-02-18 MX MXPA05008795A patent/MXPA05008795A/es active IP Right Grant
- 2004-02-18 US US10/546,177 patent/US20060269772A1/en not_active Abandoned
- 2004-02-18 DE DE602004000981T patent/DE602004000981T2/de not_active Expired - Lifetime
- 2004-02-20 TW TW093104278A patent/TWI349019B/zh not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| CA2516415A1 (en) | 2004-09-10 |
| ATE327263T1 (de) | 2006-06-15 |
| TWI349019B (en) | 2011-09-21 |
| CN100393755C (zh) | 2008-06-11 |
| TW200420652A (en) | 2004-10-16 |
| EP1597288B1 (en) | 2006-05-24 |
| DE602004000981D1 (de) | 2006-06-29 |
| DE602004000981T2 (de) | 2006-12-07 |
| MXPA05008795A (es) | 2005-10-18 |
| WO2004076548A3 (en) | 2004-10-21 |
| CA2516415C (en) | 2012-03-27 |
| WO2004076548A2 (en) | 2004-09-10 |
| JP2006518797A (ja) | 2006-08-17 |
| US20060269772A1 (en) | 2006-11-30 |
| EP1597288A2 (en) | 2005-11-23 |
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