CN101440180B - Polyolefin based non-linear dielectric material with non-linear dielectric constant and non-linear conductivity - Google Patents
Polyolefin based non-linear dielectric material with non-linear dielectric constant and non-linear conductivity Download PDFInfo
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- CN101440180B CN101440180B CN2008102098028A CN200810209802A CN101440180B CN 101440180 B CN101440180 B CN 101440180B CN 2008102098028 A CN2008102098028 A CN 2008102098028A CN 200810209802 A CN200810209802 A CN 200810209802A CN 101440180 B CN101440180 B CN 101440180B
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Abstract
The invention discloses polyolefin based dielectric materials with the nonlinear dielectric constant and the nonlinear conductance, and relates to nonlinear dielectric materials. The polyolefin nonlinear dielectric materials solve the problems of poor physical-mechanical property and processability caused by single variety of functional filler and large mixing amount of the prior polyolefin based nonlinear dielectric material. A first polyolefin based nonlinear dielectric material is prepared from polyolefin base materials, functional compositions and an antioxidant; and a second polyolefin based nonlinear dielectric material is prepared from low density polyethylene, the functional compositions, the antioxidant and a crosslinking agent. The polyolefin based nonlinear dielectric materials have good electrical conductivity and/or dielectric constant nonlinear characteristic, physical-mechanical property and processability and strong capacity of automatically homogenizing electric field distribution in a non-uniform electric field.
Description
Technical field
The present invention relates to non-linear dielectric material.
Background technology
Nonlinear dielectric is meant the dielectric that specific conductivity and/or relative permittivity change with strength of electric field.Non-linear dielectric material often is applied to electric insulation and goods.And existing non-linear dielectric material comprises ceramic base nonlinear resistance material, epoxy resin-matrix anticorona varinish (band) and rubber-based resistance strain gage; Ceramic base nonlinear resistance material needs through high temperature sintering, its manufacturing process complexity; Epoxy resin-matrix anticorona varinish (band) and rubber-based resistance strain gage are because of only containing a kind of function ingredients silicon carbide, and the silicon carbide volume is bigger, so the adjustable scope of non-linear resistance coefficient of matrix material is little, and its physical-mechanical property and poor processability.
Summary of the invention
The present invention has the physical-mechanical property that polyolefin based non-linear dielectric material is single because of the functional stuffing kind, volume causes greatly, the problem of poor processability now in order to solve, and the polyolefin-based dielectric substance with nonlinear dielectric constant and non-linear conductance is provided.
First kind of polyolefin-based dielectric substance with nonlinear dielectric constant and non-linear conductance made by 30～99 parts polyolefin substrate material, 1～70 part function ingredients and 0.1～1 part oxidation inhibitor by ratio of weight and the number of copies; Wherein the polyolefin substrate material is made up of in polypropylene, high density polyethylene(HDPE), new LDPE (film grade) and the linear low density polyethylene one or more; Function ingredients is made up of zinc oxide, barium titanate and carbon black, perhaps is made up of silicon carbide, barium titanate and carbon black, perhaps is made up of aluminum oxide, zirconia titanate and carbon nanotube, perhaps is made up of zinc oxide, strontium titanate, zirconia titanate, carbon fiber and carbon nanotube; Oxidation inhibitor is made up of primary antioxidant, is that 1～3: 1 ratio is formed by primary antioxidant and auxiliary antioxidant in mass ratio perhaps; Wherein primary antioxidant is 4,4`-thiobis (the 6-tertiary butyl-3-methylphenol), four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester and/or 2,6 ditertiary butyl p cresol; Auxiliary antioxidant is Tyox B, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters and/or three (nonyl phenyl) phosphorous acid esters.
Second kind of polyolefin-based dielectric substance with nonlinear dielectric constant and non-linear conductance made by 30～99 parts new LDPE (film grade), 1～70 part function ingredients, 0.1～1 part oxidation inhibitor and 1～2.5 part linking agent by ratio of weight and the number of copies; Wherein function ingredients is made up of zinc oxide, barium titanate, zirconia titanate and carbon nanotube, perhaps is made up of silicon carbide, barium titanate, carbon fiber and carbon nanotube, perhaps is made up of zinc oxide, barium titanate, graphite and carbon nanotube; Oxidation inhibitor is made up of primary antioxidant, is that 1～3: 1 ratio is formed by primary antioxidant and auxiliary antioxidant in mass ratio perhaps; Wherein primary antioxidant is 4,4`-thiobis (the 6-tertiary butyl-3-methylphenol), four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester and/or 2,6 ditertiary butyl p cresol; Auxiliary antioxidant is Tyox B, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters and/or three (nonyl phenyl) phosphorous acid esters; Linking agent is dicumyl peroxide or 1, the 1-cyclohexane di-tert-butyl peroxide.
The polyolefin based non-linear dielectric material that the present invention obtains has that good electricity is led and/or nonlinear dielectric constant characteristic, physical-mechanical property (mainly show as have bigger tensile strength and elongation at break, toughness) preferably and processing characteristics, have stronger in non-uniform electric field the ability of homogenizing electric field distribution voluntarily.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the present embodiment polyolefin based non-linear dielectric material is made by 30～99 parts polyolefin substrate material, 1～70 part function ingredients and 0.1～1 part oxidation inhibitor by ratio of weight and the number of copies; Wherein the polyolefin substrate material is made up of in polypropylene, high density polyethylene(HDPE), new LDPE (film grade) and the linear low density polyethylene one or more; Function ingredients is made up of in silicon carbide, zinc oxide, aluminum oxide, barium titanate, strontium titanate, zirconia titanate, carbon black, graphite, carbon fiber and the carbon nanotube two or more; Oxidation inhibitor is made up of primary antioxidant, is that 1～3: 1 ratio is formed by primary antioxidant and auxiliary antioxidant in mass ratio perhaps; Wherein primary antioxidant is 4,4`-thiobis (the 6-tertiary butyl-3-methylphenol), four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester and/or 2,6 ditertiary butyl p cresol; Auxiliary antioxidant is Tyox B, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters and/or three (nonyl phenyl) phosphorous acid esters.
Employed raw material market can be buied in the present embodiment.
When function ingredients is mixed by two or more in the present embodiment, mix according to arbitrary proportion.
Embodiment two: the difference of present embodiment and embodiment one is that polyolefin based non-linear dielectric material is made by 40～80 parts polyolefin substrate material, 10～60 parts function ingredients and 0.2～0.8 part oxidation inhibitor by ratio of weight and the number of copies.Other is identical with embodiment one.
Embodiment three: the difference of present embodiment and embodiment one is that polyolefin based non-linear dielectric material is made by 50～70 parts polyolefin substrate material, 20～50 parts function ingredients and 0.3～0.7 part oxidation inhibitor by ratio of weight and the number of copies.Other is identical with embodiment one.
Embodiment four: the difference of present embodiment and embodiment one is that polyolefin based non-linear dielectric material is made by 55～65 parts polyolefin substrate material, 30～40 parts function ingredients and 0.4～0.6 part oxidation inhibitor by ratio of weight and the number of copies.Other is identical with embodiment one.
Embodiment five: the difference of present embodiment and embodiment one is that polyolefin based non-linear dielectric material is made by 60 parts polyolefin substrate material, 35 parts function ingredients and 0.5 part oxidation inhibitor by ratio of weight and the number of copies.Other is identical with embodiment one.
Embodiment six: the difference of present embodiment and embodiment one is that the polyolefin substrate material is made up of polypropylene, high density polyethylene(HDPE) and new LDPE (film grade).Other is identical with embodiment one.
Polypropylene, high density polyethylene(HDPE) and new LDPE (film grade) are pressed the arbitrary proportion mixing in the present embodiment.
Embodiment seven: the difference of present embodiment and embodiment one is that the polyolefin substrate material is made up of polypropylene and high density polyethylene(HDPE).Other is identical with embodiment one.
Polypropylene and high density polyethylene(HDPE) can mix by arbitrary proportion in the present embodiment.
Embodiment eight: the difference of present embodiment and embodiment one is that the polyolefin substrate material is made up of polypropylene and new LDPE (film grade).Other is identical with embodiment one.
Polypropylene and new LDPE (film grade) can mix by arbitrary proportion in the present embodiment.
Embodiment nine: the difference of present embodiment and embodiment one is that the polyolefin substrate material is made up of polypropylene and linear low density polyethylene.Other is identical with embodiment one.
Polypropylene and linear low density polyethylene can mix by arbitrary proportion in the present embodiment.
Embodiment ten: the difference of present embodiment and embodiment one is that the polyolefin substrate material is made up of polypropylene, high density polyethylene(HDPE), new LDPE (film grade) and linear low density polyethylene.Other is identical with embodiment one.
Can mix by arbitrary proportion between polypropylene, high density polyethylene(HDPE), new LDPE (film grade) and the linear low density polyethylene in the present embodiment.
Embodiment 11: the difference of present embodiment and embodiment one is that function ingredients is made up of zinc oxide, barium titanate and carbon black.Other is identical with embodiment one.
Zinc oxide, barium titanate and carbon black can mix by arbitrary proportion in the present embodiment.
Embodiment 12: the difference of present embodiment and embodiment one is that function ingredients is made up of silicon carbide, barium titanate and carbon black.Other is identical with embodiment one.
Silicon carbide, barium titanate and carbon black can mix by arbitrary proportion in the present embodiment.
Embodiment 13: the difference of present embodiment and embodiment one is that function ingredients is made up of aluminum oxide, zirconia titanate and carbon nanotube.Other is identical with embodiment one.
Aluminum oxide, zirconia titanate and carbon nanotube can mix by arbitrary proportion in the present embodiment.
Embodiment 14: the difference of present embodiment and embodiment one is that function ingredients is made up of zinc oxide, strontium titanate, zirconia titanate, carbon fiber and carbon nanotube.Other is identical with embodiment one.
Zinc oxide, strontium titanate, zirconia titanate, carbon fiber and carbon nanotube can mix by arbitrary proportion in the present embodiment.
Embodiment 15: the difference of present embodiment and embodiment one is that oxidation inhibitor is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester.Other is identical with embodiment one.
Embodiment 16: the difference of present embodiment and embodiment one is that oxidation inhibitor is 2,6 ditertiary butyl p cresol and three (nonyl phenyl) phosphorous acid ester.Other is identical with embodiment one.
Embodiment 17: the difference of present embodiment and embodiment one is that oxidation inhibitor is 4,4`-thiobis (the 6-tertiary butyl-3-methylphenol) and four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester.Other is identical with embodiment one.
In the present embodiment 4,4`-thiobis (the 6-tertiary butyl-3-methylphenol) and four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester can mix by arbitrary proportion.
Embodiment 18: the difference of present embodiment and embodiment one is that oxidation inhibitor is 4,4`-thiobis (the 6-tertiary butyl-3-methylphenol) and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.Other is identical with embodiment one.
Embodiment 19: the difference of present embodiment and embodiment one is that primary antioxidant and auxiliary antioxidant are 2: 1 ratio composition in mass ratio.Other is identical with embodiment one.
Embodiment 20: the present embodiment polyolefin based non-linear dielectric material is by ratio of weight and the number of copies by 40 parts new LDPE (film grade), 20 parts silicon carbide and graphite, and four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester of 0.4 part is made.
Silicon carbide and graphite can mix by arbitrary proportion in the present embodiment.
Be that melting mixing can obtain polyolefin based non-linear dielectric material under 150～200 ℃ the condition with four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester of 40 parts new LDPE (film grade) in the present embodiment, 20 parts silicon carbide and graphite and 0.4 part in temperature.
The polyolefin based non-linear dielectric material that present embodiment obtains is cross-linked polyolefin based non-linear dielectric material not; be used to make voltage stabilizing, overvoltage protection and demagnetization components and parts more; the foil gauge of homogenizing electric field distribution in cable terminal end and the connecting box, and the non-linear insulating layer that is used for the homogenizing electric field distribution in the insulation system of other various electric installations, goods.
The gained polyolefin based non-linear dielectric material becomes all to be optimized and mainly shows as through recording physical-mechanical property, processing characteristics in the present embodiment: tensile strength is 12～20MPa, and elongation at break is 200%～1000%, and nonlinear factor is 1～20.
Embodiment 21: the present embodiment polyolefin based non-linear dielectric material is made by 30～99 parts new LDPE (film grade), 1～70 part function ingredients, 0.1～1 part oxidation inhibitor and 1～2.5 part linking agent by ratio of weight and the number of copies; Wherein function ingredients is made up of in silicon carbide, zinc oxide, aluminum oxide, barium titanate, strontium titanate, zirconia titanate, carbon black, graphite, carbon fiber and the carbon nanotube two or more; Oxidation inhibitor is made up of primary antioxidant, is that 1～3: 1 ratio is formed by primary antioxidant and auxiliary antioxidant in mass ratio perhaps; Wherein primary antioxidant is 4,4`-thiobis (the 6-tertiary butyl-3-methylphenol), four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester and/or 2,6 ditertiary butyl p cresol; Auxiliary antioxidant is Tyox B, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters and/or three (nonyl phenyl) phosphorous acid esters; Linking agent is dicumyl peroxide or 1, the 1-cyclohexane di-tert-butyl peroxide.
Employed raw material market can be buied in the present embodiment.
When function ingredients is mixed by two or more in the present embodiment, mix according to arbitrary proportion.
Embodiment 22: the difference of present embodiment and embodiment 21 is that polyolefin based non-linear dielectric material is made by 40～80 parts new LDPE (film grade), 10～60 parts function ingredients, 0.3～0.7 part oxidation inhibitor and 1.4～2.0 parts linking agent by ratio of weight and the number of copies.Other is identical with embodiment 21.
Embodiment 23: the difference of present embodiment and embodiment 21 is that polyolefin based non-linear dielectric material is made by 50～70 parts new LDPE (film grade), 20～50 parts function ingredients, 0.4～0.6 part oxidation inhibitor and 1.6～1.8 parts linking agent by ratio of weight and the number of copies.Other is identical with embodiment 21.
Embodiment 24: the difference of present embodiment and embodiment 21 is that polyolefin based non-linear dielectric material is made by 60 parts new LDPE (film grade), 30 parts function ingredients, 0.5 part oxidation inhibitor and 1.5 parts linking agent by ratio of weight and the number of copies.Other is identical with embodiment 21.
Embodiment 25: the difference of present embodiment and embodiment 21 is that primary antioxidant and auxiliary antioxidant are 2: 1 ratio composition in mass ratio.Other is identical with embodiment 21.
Embodiment 26: the difference of present embodiment and embodiment 21 is that function ingredients is made up of zinc oxide, barium titanate, zirconia titanate and carbon nanotube.Other is identical with embodiment 21.
Zinc oxide, barium titanate, zirconia titanate and carbon nanotube can mix by arbitrary proportion in the present embodiment.
Embodiment 27: the difference of present embodiment and embodiment 21 is: functional group is made up of silicon carbide, barium titanate, carbon fiber and carbon nanotube.Other is identical with embodiment 21.
Silicon carbide, barium titanate, carbon fiber and carbon nanotube are pressed the arbitrary proportion mixing in the present embodiment.
Embodiment 28: the difference of present embodiment and embodiment 21 is that function ingredients is made up of zinc oxide, barium titanate, graphite and carbon nanotube.Other is identical with embodiment 21.
Zinc oxide, barium titanate, graphite and carbon nanotube are pressed the arbitrary proportion mixing in the present embodiment.
Embodiment 29: the difference of present embodiment and embodiment 21 is that oxidation inhibitor is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester and 2,6 ditertiary butyl p cresol.Other is identical with embodiment 21.
Embodiment 30: the difference of present embodiment and embodiment 21 is that oxidation inhibitor is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.Other is identical with embodiment 21.
The embodiment hentriaconta-: the difference of present embodiment and embodiment 21 is that linking agent is a dicumyl peroxide.Other is identical with embodiment 21.
Embodiment 32: the present embodiment polyolefin based non-linear dielectric material is made by 40 parts new LDPE (film grade), 20 parts silicon carbide and graphite, 0.4 part four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol esters and 1.0 parts dicumyl peroxide by ratio of weight and the number of copies.
Silicon carbide and graphite can mix by arbitrary proportion in the present embodiment.
Be that melting mixing can obtain polyolefin based non-linear dielectric material under 120～125 ℃ the condition with the dicumyl peroxide of 40 parts new LDPE (film grade) in the present embodiment, 20 parts silicon carbide and graphite, 0.4 part four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol esters and 1.0 parts in temperature.
The polyolefin based non-linear dielectric material that present embodiment obtains is the cross-linked polyolefin based non-linear dielectric material; can be used for making voltage stabilizing, overvoltage protection and demagnetization components and parts; the foil gauge of homogenizing electric field distribution in cable terminal end and the connecting box, and the non-linear insulating layer that is used for the homogenizing electric field distribution in the insulation system of other various electric installations, goods.
The gained polyolefin based non-linear dielectric material becomes all to be optimized and mainly shows as through recording physical-mechanical property, processing characteristics in the present embodiment: tensile strength is 10～20MPa, elongation at break is 150%～1000%, and nonlinear factor is 0.5～20.
Claims (8)
1. the polyolefin-based dielectric substance that has nonlinear dielectric constant and non-linear conductance is characterized in that the polyolefin-based dielectric substance with nonlinear dielectric constant and non-linear conductance made by 30～99 parts polyolefin substrate material, 1～70 part function ingredients and 0.1～1 part oxidation inhibitor by ratio of weight and the number of copies; Wherein the polyolefin substrate material is made up of in polypropylene, high density polyethylene(HDPE), new LDPE (film grade) and the linear low density polyethylene one or more; Function ingredients is made up of zinc oxide, barium titanate and carbon black, perhaps is made up of silicon carbide, barium titanate and carbon black, perhaps is made up of aluminum oxide, zirconia titanate and carbon nanotube, perhaps is made up of zinc oxide, strontium titanate, zirconia titanate, carbon fiber and carbon nanotube; Oxidation inhibitor is made up of primary antioxidant, is that 1～3: 1 ratio is formed by primary antioxidant and auxiliary antioxidant in mass ratio perhaps; Wherein primary antioxidant is 4,4`-thiobis (the 6-tertiary butyl-3-methylphenol), four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester and/or 2,6 ditertiary butyl p cresol; Auxiliary antioxidant is Tyox B, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters and/or three (nonyl phenyl) phosphorous acid esters.
2. the polyolefin-based dielectric substance with nonlinear dielectric constant and non-linear conductance according to claim 1 is characterized in that the polyolefin substrate material is made up of polypropylene, high density polyethylene(HDPE) and new LDPE (film grade).
3. the polyolefin-based dielectric substance with nonlinear dielectric constant and non-linear conductance according to claim 1 and 2 is characterized in that oxidation inhibitor is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester.
4. the polyolefin-based dielectric substance with nonlinear dielectric constant and non-linear conductance according to claim 1 and 2 is characterized in that oxidation inhibitor is 2,6 ditertiary butyl p cresol and three (nonyl phenyl) phosphorous acid ester.
5. the polyolefin-based dielectric substance that has nonlinear dielectric constant and non-linear conductance is characterized in that the polyolefin-based dielectric substance with nonlinear dielectric constant and non-linear conductance made by 30～99 parts new LDPE (film grade), 1～70 part function ingredients, 0.1～1 part oxidation inhibitor and 1～2.5 part linking agent by ratio of weight and the number of copies; Wherein function ingredients is made up of zinc oxide, barium titanate, zirconia titanate and carbon nanotube, perhaps is made up of silicon carbide, barium titanate, carbon fiber and carbon nanotube, perhaps is made up of zinc oxide, barium titanate, graphite and carbon nanotube; Oxidation inhibitor is made up of primary antioxidant, is that 1～3: 1 ratio is formed by primary antioxidant and auxiliary antioxidant in mass ratio perhaps; Wherein primary antioxidant is 4,4`-thiobis (the 6-tertiary butyl-3-methylphenol), four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester and/or 2,6 ditertiary butyl p cresol; Auxiliary antioxidant is Tyox B, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid esters and/or three (nonyl phenyl) phosphorous acid esters; Linking agent is dicumyl peroxide or 1, the 1-cyclohexane di-tert-butyl peroxide.
6. the polyolefin-based dielectric substance with nonlinear dielectric constant and non-linear conductance according to claim 5 is characterized in that the polyolefin-based dielectric substance with nonlinear dielectric constant and non-linear conductance made by 40～80 parts new LDPE (film grade), 10～60 parts function ingredients, 0.3～0.7 part oxidation inhibitor and 1.4～2.0 parts linking agent by ratio of weight and the number of copies.
7. according to claim 5 or 6 described polyolefin-based dielectric substances with nonlinear dielectric constant and non-linear conductance, it is characterized in that oxidation inhibitor is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester and 2,6 ditertiary butyl p cresol.
8. according to claim 5 or 6 described polyolefin-based dielectric substances with nonlinear dielectric constant and non-linear conductance, it is characterized in that oxidation inhibitor is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) pentaerythritol ester and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester propionic acid).
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