阅读说明：本技术 非极性有机聚合物、极性有机聚合物和超低可湿性碳黑的复合物 (Composite of non-polar organic polymer, polar organic polymer and ultra-low wettability carbon black ) 是由 蓝天 余心迪 M·Q·特兰 P·J·布里格兰迪 J·M·柯吉恩 T·J·珀森 张亦弛 于 2019-03-22 设计创作，主要内容包括：一种半导体复合材料,其包含非极性有机聚合物、极性有机共聚物和导电有效量的超低可湿性碳黑。此外,一种制造所述复合材料的方法；交联聚乙烯产品,其通过固化所述复合材料制成；制品,其包含成型形式的本发明的复合材料或产品；和使用本发明的复合材料、产品或制品的方法。(A semiconducting composite comprising a non-polar organic polymer, a polar organic copolymer, and an electrically conductive effective amount of ultra-low wettability carbon black. Further, a method of manufacturing the composite material; a cross-linked polyethylene product made by curing the composite material; an article comprising the composite or product of the invention in shaped form; and methods of using the composites, products or articles of the invention.)

1. A semiconductive composite comprising (a) a non-polar polyolefin polymer in a first phase; (AA) a polar vinyl copolymer in a second phase that is at least partially immiscible in the first phase; and an electrically conductive effective amount of (B) an ultra-low wettability carbon black (ULW-CB) having a BET nitrogen surface area of from 35 to 190 square meters per gram (m) as measured by the Brunauer-Emmett-Teller, BET) nitrogen surface area test method ²(iv)/g); and an Oil Absorption Number (OAN) of 115 to 180 milliliters of oil per 100 grams (mL/100g) as measured by the oil absorption number test method.

2. The semiconductor composite of claim 1, wherein the (B) ULW-CB is characterized by any one of the limits (i) to (iii): (i) the BET nitrogen surface area of the (B) ULW-CB is 40 to 63m as measured by the BET nitrogen surface area test method²(ii)/g; and an OAN of 120 to 150mL/100g as measured by the oil absorption number test method; (ii) the BET nitrogen surface area of the (B) ULW-CB is 120 to 180m as measured by the BET nitrogen surface area test method²(ii)/g; and an OAN of 150 to 175mL/100g as measured by the oil absorption number test method; and (iii) said (B) ULW-CB is a ULW-CB blend having (i) and (ii).

3. A semiconductive composite comprising (a) a non-polar polyolefin polymer in a first phase; (AA) a polar vinyl copolymer in a second phase that is at least partially immiscible in the first phase; and a conductively effective amount of (B) an ultra-low wettability carbon black (ULW-CB) having a surface wettability profile characterized by: the wettability at 0.02 surface coverage is 0.0101 or less, and the wettability at 0.04 surface coverage is 0.0101 or less, and the wettability at 0.06 surface coverage is 0.0099 or less, and the wettability at 0.08 surface coverage is 0.0111 or less, and the wettability at 0.10 surface coverage is 0.0113 or less, as measured by reverse gas chromatography (IGC) according to the wettability test method.

4. The semiconductor composite of any one of claims 1 to 3, wherein the (B) ULW-CB is characterized by any one of the limitations (i) to (vii): (i) a BET nitrogen surface area of 40 to 180m as measured by the BET nitrogen surface area test method²(ii)/g; (ii) a water absorption of 400 to 2400 parts per million (ppm, weight) as measured by the moisture absorption test method; (iii) surface wettability profiles characterized by: a wettability at 0.02 surface coverage of ≦ 0.0058, and a wettability at 0.04 surface coverage of ≦ 0.0070, and a wettability at 0.06 surface coverage of ≦ 0.0075, and a wettability at 0.08 surface coverage of ≦ 0.0086, and a wettability at 0.10 surface coverage of ≦ 0.0091, measured by IGC according to the wettability test method; (iv) both (i) and (ii); (v) (ii) both (i) and (iii); (vi) both (ii) and (iii); (vii) (iv) a combination of (i), (ii), and (iii).

5. The semiconducting composite of any of claims 1-4, free of any carbon black other than the ultra-low wettability carbon black.

6. The semiconductor composite according to any one of claims 1 to 5, characterized in that any one of (i) to (v): (i) (ii) comprises, based on the total weight of the semiconductive composite, from 61.0 wt% to 99.0 wt% of the combination of the (a) non-polar polyolefin polymer and the (AA) polar vinyl polymer; and 39.0 wt% to 1.0 wt% of said (B) ULW-CB; wherein the combination of (A) and (AA) has from 5 wt% to 95 wt% (A) and from 95 wt% to 5 wt% (AA), based on the combined weight of (A) and (AA); (ii) the non-polar polyolefin polymer (A) is a non-polar vinyl polymer; (iii) both (i) and (ii); (iv) the non-polar polyolefin polymer (A) is a non-polar propylene-based polymer; and (v) both (i) and (iv).

7. The semiconducting composite of any of claims 1-6, further comprising at least one additive selected from the group consisting of: (c) a plastomer; (D) an antioxidant; (E) an organic peroxide; (F) a scorch retarder; (G) an alkenyl functional coagent; (H) a nucleating agent; (I) a processing aid; (J) an extender oil; (K) stabilizers (e.g., compounds that inhibit Ultraviolet (UV) light-related degradation).

8. The semiconductor composite of any one of claims 1 to 7, characterized in that the log (volume resistivity) at 10.0 wt% electrically conductive effective amount is < 3.0log (Ohm-cm), or < 4.0log (Ohm-cm) at 7 wt% electrically conductive effective amount, or < 10.0log (Ohm-cm) at 5 wt% electrically conductive effective amount, or < 15.5log (Ohm-cm) at 2.0 wt% electrically conductive effective amount, as measured by volume resistivity test method, wherein the electrically conductive effective amount of (B) ULW-CB is based on the total weight of the semiconductor composite.

9. The semiconducting composite according to any of claims 1-8, characterized by the following log (volume resistivity): at 5.0 to 10.0m²(ii) a total BET N2 surface area of ≦ 10Log (Ohm-cm) for carbon black in the composite; or between 2.0 and 5.0m ²(ii) total BET N2 surface area of ≦ 12Log (Ohm-cm) for carbon black in the composite; or in the range of 0.5 to 2.0m²The total BET N2 surface area of the carbon black in the composite is ≦ 15Log (Ohm-cm).

10. A method of making the semiconductive composite according to any of claims 1 to 9, comprising mixing the (B) ultra-low wettability carbon black (ULW-CB) into a melt of the (a) non-polar polyolefin polymer and (AA) polar vinyl copolymer, resulting in the semiconductive composite as a molten blend comprising ingredients (a), (AA) and (B).

11. A crosslinked polyethylene product which is the product of curing the semiconducting composite of any of claims 1 to 9.

12. An article comprising a semiconductive composite according to any of claims 1 to 9 or made by the process according to claim 10, or a crosslinked polyethylene product according to claim 11, in shaped form.

13. An electrical conductor device comprising a conductive core and a semiconducting layer at least partially covering the conductive core, wherein at least a portion of the semiconducting layer comprises a semiconducting composite according to any of claims 1 to 9 or made by the process of claim 10, or a crosslinked polyethylene product according to claim 11.

14. A method of conducting electricity, the method comprising applying a voltage across a conductive core of an electrical conductor device according to claim 13 so as to generate a current through the conductive core.

15. A thermally cycled semiconductor composite made by subjecting the semiconductor composite of any one of claims 1 to 9 to thermal cycling comprising heating the semiconductor composite to 170 ℃ to 190 ℃ for 1 to 5 minutes and subsequently cooling to 30 ℃ resulting in a cooled thermally cycled semiconductor composite.

Technical Field

Composites of organic polymers and carbon black and related aspects.

Introduction to the word

Patents in the field include US6,277,303B 1; US6,284,832B 1; US6,331,586B 1; and US 7,767,910B 2. US6,277,303B 1 and US6,284,832B 1 examples use Vulcan XC 72 carbon black. The US6,331,586B 1 example uses one of the following: printex XE2 carbon Black (Degussa), BlackPearls 1000 carbon Black (Cabot Corp.), Vulcan XC 72 carbon Black (Cabot Corp.), Ketjenblack EC600JD carbon Black (Akzo), Vulcan P carbon Black (Cabot), United120 carbon Black (Cabot) or Denka Black carbon Black (Denka). US 7,767,910B 2 examples use Vulcan XC 500 carbon black. Cabot corp. Cabot corporation of birerica, ma (Cabot corporation, Billerica, Massachusetts, USA). Another carbon black is acetylene black AB 100% -01 (Soltex, Inc., Houston, Texas, USA). Each of the foregoing carbon blacks does not have the ultra-low wettability characteristics.

Disclosure of Invention

We believe that the high content of carbon black in existing semiconductive composites used in the semiconductive layers of medium to extra high voltage power cables may cause undesirable problems. These problems include undesirably high moisture absorption in the semiconductive layers during operational use of the power cable. It is also believed that too low a content of carbon black in these semiconductive composites may lead to other undesirable problems in the power cable, such as too high a volume resistivity or lack of electro-percolation (electro-percolation). One challenge is to reduce the carbon black content in the semiconductor composite without destroying the desired electrical properties of the material.

Prior attempts to solve these problems have combined partially immiscible polar and non-polar polymers with existing carbon blacks to form semiconductive composites having at least one continuous polymeric phase. Some of the existing carbon blacks are located in one of the continuous phases or at the interface between the two phases, and some of the carbon blacks are located in the discontinuous phase. The results are generally unsatisfactory because the carbon black is only partially isolated and/or the carbon black is poorly dispersed in its major separate phase. We provide here an alternative simplified technical solution that overcomes the negative effects of both too high and too low carbon black content. Embodiments of the technical solution include those described below.

A semiconductor composite comprising or consisting essentially of: a non-polar organic polymer, a polar organic polymer, and a conductively effective amount of ultra-low wettability carbon black.

A method of manufacturing a semiconductor composite material.

An electrical conductor device comprising a conductor core and a semiconductor layer disposed thereon, the semiconductor layer comprising a semiconductor composite.

A method of transmitting electricity through a conductor core of an electrical conductor device.

Detailed Description