CN103865158B - A kind of for overhead line black wear well polythene Insulating Material and Preparation Method - Google Patents
A kind of for overhead line black wear well polythene Insulating Material and Preparation Method Download PDFInfo
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- CN103865158B CN103865158B CN201410127193.7A CN201410127193A CN103865158B CN 103865158 B CN103865158 B CN 103865158B CN 201410127193 A CN201410127193 A CN 201410127193A CN 103865158 B CN103865158 B CN 103865158B
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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
- 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
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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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
- H01B3/44—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 vinyl resins; acrylic resins
- H01B3/441—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 vinyl resins; acrylic resins from alkenes
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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
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L2023/40—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds changing molecular weight
- C08L2023/44—Coupling; Molecular weight increase
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The present invention relates to a kind of preparation method for overhead line black wear well polythene Insulation Material, the mass percent of its raw material is: modified poly ester is 1 ~ 5%, and auxiliary agent is 0.1 ~ 0.5%, and carbon black is 1 ~ 5%, modified low-density polyethylene is 10 ~ 40%, and organosilane crosslinked polyethylene is surplus; Its concrete steps are: by modified poly ester, auxiliary agent, carbon black, modified low-density polyethylene, and organosilane crosslinked polyethylene mixes according to proportioning, and then melt pelletization can obtain black wear well polythene Insulation Material.The present invention adopts low-temperature carbonization to rice husk stalk, saves cost on the one hand, keeps the original function of rice husk in addition on the one hand, and can play rice husk stalk effect as the carrier of absorption, the temperature of charing is too high and long, will destroy original performance of rice husk stalk.
Description
[technical field]
The present invention relates to electric power field of material technology, specifically, is a kind of for overhead line black wear well polythene Insulating Material and Preparation Method.
[background technology]
The insulation layer of plastic insulating power cable is plastics, and conventional plastics have polyvinyl chloride, polyethylene, crosslinked polyethylene.Plastic cable structure is simple, manufactures easy to process, lightweight, and laying installation is convenient, is not laid drop and limits.Therefore mesolow cable is made in widespread use, and has the trend replacing viscosity impregnation oils paper cable.Its disadvantage there is poplar bundles punch-through, which has limited it in more high-tension use.
China's economic growth continuously and healthily, for cable products provides the huge market space, the incentive that Chinese market is strong, makes the world all sight be focused on Chinese market, in the decades that reform and opening-up is short, the huge throughput that Chinese cable manufacturing industry is formed allows the world regard with special esteem.
In November, 2008, China is the crisis of reply world financial, and government decided drops into 4 trillion yuan promote domestic demands, wherein has about more than 40% for urban and rural power grids construction and upgrading.Whole nation wires and cables industry has had again the good market opportunity, and various places electric wire enterprise seizes the opportunity, and meets the construction and upgrading of new round urban and rural power grids.
Wires and cables industry is the second largest industry that China is only second to automobile industry, and range of product Service Efficiency and domestic market occupation rate are all more than 90%.Worldwide, the Chinese electric wire gross output value exceedes the U.S., becomes first electric wire producing country in the world.Along with Chinese wires and cables industry high speed development, creation of new enterprise quantity constantly rises, and industry overall technology level is largely increased.
Along with the continuous expansion of the industry sizes such as China electric power industry, data corresponding industry, urban track traffic industry, car industry and shipbuilding, also will increase rapidly the demand of electric wire, following electric wire industry also has huge development potentiality.
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of for overhead line black wear well polythene Insulating Material and Preparation Method.
The object of the invention is to be achieved through the following technical solutions:
A kind of for overhead line black wear well polythene Insulation Material, it is characterized in that, the mass percent of its raw material is:
The massfraction of described modified poly ester is preferably 2 ~ 4%; The best is 3%.
The massfraction of described modified low-density polyethylene is preferably 20 ~ 30%; The best is 25%.
Described auxiliary agent is SAG compatilizer, purchased from Nantong Zhi Sheng company.
Described Masterbatch is commercially available prod, purchased from Shanghai Chemical Co., Ltd. in midsummer.
A kind of preparation method for overhead line black wear well polythene Insulation Material, its concrete steps are: by modified poly ester, auxiliary agent, Masterbatch, modified low-density polyethylene, organosilane crosslinked polyethylene mixes according to proportioning, and then melt pelletization can obtain black wear well polythene Insulation Material.
The present invention also provides another one technical scheme, namely
For a multi-functional polyethylene Insulation Material for cable, it is characterized in that, the mass percent of its raw material is:
The present invention reoffers another one technical scheme, namely
For a polyethylene composite insulation material for power cable, it is characterized in that, the mass percent of its raw material is:
SBS is writing a Chinese character in simplified form of styrene-butadiene-styrene block copolymer.
PBT be polybutylene terephthalate write a Chinese character in simplified form.
Described SBS particle can be replaced by PBT particle, can obtain a kind of poly-ethylene cable material for power domain.
A preparation method for modified poly ester, its concrete steps are:
(1) functionalization of inorganic particle:
Dispersed inorganic particles under alcohol is solvent condition, described alcoholic solution is ethanol, methyl alcohol or aqueous isopropanol; Then in the basic conditions, add amino triethoxyl silane, after reaction, carry out centrifugation, vacuum-drying is carried out to solid and prepares surface-functionalized inorganic particle;
Described inorganic particle concentration in alcoholic solution is 5 ~ 35kg/m
3, it is 8.5 ~ 9.5 that system pH controls, and temperature of reaction is 60 ~ 75 DEG C, and the reaction times is 150 ~ 240min;
Described inorganic particle is nano-indium stannum oxide, nano indium oxide antimony and nano zine oxide, and the mass ratio of three is 1: 1: 3, and median size is 10 ~ 50nm, adopts ultrasonic disperse 50min in alcoholic solution dispersion process;
(2) then under nitrogen protection, with surface-functionalized inorganic particle, terephthalic acid; ethylene glycol is raw material; carry out the first step esterification, and then in second step prepolymerization reaction process, add polyvalent alcohol carry out copolycondensation, then prepare modified poly ester through the whole polycondensation of the 3rd step.
In described the first step esterification, the molar ratio of raw material terephthalic acid and ethylene glycol is 1: 1.4 ~ 1.55, and inorganic particle addition is 1.0 ~ 2wt% of terephthalic acid massfraction.
Described the first step esterification is under nitrogen protection, inorganic particle first dispersion making beating in ethylene glycol solution, and then under pressure is 0.3 ~ 0.4MPa condition, polyprotonic acid and ethylene glycol carry out esterification, and temperature of reaction, at 220 ~ 250 DEG C, reacts 3 ~ 4h.
Described second step prepolymerization reaction, polyol starting material is sorbyl alcohol or tetramethylolmethane; In raw material, the mol ratio of terephthalic acid and polyvalent alcohol is 1: 0.001 ~ 0.003.
Described second step prepolymerization reaction, controls temperature of reaction at 260 ~ 280 DEG C, keeps 2 ~ 3h.
The whole polycondensation of the 3rd described step, control low vacuum in 60Pa, temperature of reaction is at 270 ~ 290 DEG C, and the reaction times is 2 ~ 4h.
A preparation method for modified low-density polyethylene, its concrete steps are:
(1) functionalization of inorganic particle:
Dispersed inorganic particles under alcohol is solvent condition, described alcoholic solution is ethanol, methyl alcohol or aqueous isopropanol; Then in the basic conditions, add amino triethoxyl silane, after reaction, carry out centrifugation, vacuum-drying is carried out to solid and prepares surface-functionalized inorganic particle;
Described inorganic particle concentration in alcoholic solution is 5 ~ 35kg/m
3, it is 8.5 ~ 9.5 that system pH controls, and temperature of reaction is 60 ~ 75 DEG C, and the reaction times is 150 ~ 240min;
Described inorganic particle is nano-indium stannum oxide, nano indium oxide antimony and nano zine oxide, and the mass ratio of three is 1: 1: 3, and median size is 10 ~ 50nm, adopts ultrasonic disperse 50min in alcoholic solution dispersion process;
(2) rice husk stalk and acidifying:
Raw rice husk stalk is carbonized, obtains the powdered rice hulls after carbonizing, then the powdered rice hulls after charing is dissolved in the vitriol oil, obtains the powdered rice hulls after acidifying;
Described charring process is the segmentation charing adopting quartz tube furnace to carry out coconut husk: rise to 150 DEG C with the temperature rise rate of 10 DEG C/min, coconut husk carbonizes 50min at 150 DEG C, then 300 DEG C are risen to the temperature rise rate of 10 DEG C/min, again at 300 DEG C of charing 50min, finally rise to 400 DEG C with the temperature rise rate of 5 DEG C/min, and carbonize process 2 ~ 3h at such a temperature; Ground at high energy ball mill by obtained product after charing, until finely powdered, namely obtain the powdered rice hulls after carbonizing, the particle diameter of powdered rice hulls is 0.01 ~ 2 μm; Adopt low-temperature carbonization, save cost on the one hand, keep the original function of rice husk in addition on the one hand, rice husk stalk effect can be played as the carrier of absorption, the temperature of charing is too high and long, will destroy original performance of rice husk stalk, Here it is low temperature and the slow feature carbonized.
(3) preparation of black properties-correcting agent:
The surface-functionalized inorganic particle that step (1) obtains is joined step (2) and obtains the powdered rice hulls after acidifying, carry out ultrasonic disperse 40min; Carry out centrifugation after dispersion to carry out drying again and can obtain black properties-correcting agent;
The mass ratio of the powdered rice hulls after the charing of described surface-functionalized inorganic particle and step (2) is 1: 8;
(4) preparation of modified low-density polyethylene:
Step (3) is obtained black properties-correcting agent to be joined in Low Density Polyethylene particle, carries out mixing and melt pelletization, obtains modified low-density polyethylene, and wherein black properties-correcting agent accounts for the massfraction of modified low-density polyethylene is 2 ~ 4%.
Compared with prior art, positively effect of the present invention is:
The present invention is in the method by chemical graft copolymerization, polyester backbone is introduced uvioresistant function nano particle, realize polyester flame-retardant performance, adopt the method for in-situ polymerization modification simultaneously, surface modified granules and polymer raw is made to add in poly-unit, for the dispersion of physics nanoparticle, improve the homogeneity of fire-retardant particle in polymerization rear copolymer.
The present invention carries out the effect of chemical bond by the powdered rice hulls of amidized inorganic particle and acidifying, utilizes the adsorption of powdered rice hulls self simultaneously, makes the combination of inorganic particle and powdered rice hulls more tight, is conducive to the flame retardant efficiency slowly playing inorganic particle.
Technical process of the present invention is simple, is easy to large-scale production.
[embodiment]
The present invention is below provided a kind of embodiment for overhead line black wear well polythene Insulating Material and Preparation Method.
Embodiment 1
A kind of for overhead line black wear well polythene Insulation Material, it is characterized in that, the mass percent of its raw material is:
The preparation method of described modified poly ester, its concrete steps are:
(1) dispersed inorganic particles under alcohol is solvent condition, described alcoholic solution is ethanol, methyl alcohol or aqueous isopropanol; Then in the basic conditions, add amino triethoxyl silane, after reaction, carry out centrifugation, vacuum-drying is carried out to solid and prepares surface-functionalized inorganic particle;
Described inorganic particle concentration in alcoholic solution is 5 ~ 35kg/m
3, it is 8.5 ~ 9.5 that system pH controls, and temperature of reaction is 60 ~ 75 DEG C, and the reaction times is 150 ~ 240min;
Described inorganic particle is nano-indium stannum oxide, nano indium oxide antimony and nano zine oxide, and the mass ratio of three is 1: 1: 3, and median size is 10 ~ 50nm, adopts ultrasonic disperse 50min in alcoholic solution dispersion process;
(2) then under nitrogen protection, with surface-functionalized inorganic particle, terephthalic acid; ethylene glycol is raw material; carry out the first step esterification, and then in second step prepolymerization reaction process, add polyvalent alcohol carry out copolycondensation, then prepare modified poly ester through the whole polycondensation of the 3rd step.
In described the first step esterification, the molar ratio of raw material terephthalic acid and ethylene glycol is 1: 1.4, and inorganic particle addition is the 1.0wt% of terephthalic acid massfraction.
Described the first step esterification is under nitrogen protection, inorganic particle first dispersion making beating in ethylene glycol solution, and then under pressure is 0.3 ~ 0.4MPa condition, polyprotonic acid and ethylene glycol carry out esterification, and temperature of reaction, at 220 ~ 250 DEG C, reacts 3 ~ 4h.
Described second step prepolymerization reaction, polyol starting material is sorbyl alcohol or tetramethylolmethane; In raw material, the mol ratio of terephthalic acid and polyvalent alcohol is 1: 0.001.
Described second step prepolymerization reaction, controls temperature of reaction at 260 ~ 280 DEG C, keeps 2 ~ 3h.
The whole polycondensation of the 3rd described step, control low vacuum in 60Pa, temperature of reaction is at 270 ~ 290 DEG C, and the reaction times is 2 ~ 4h.
The preparation method of described modified low-density polyethylene, its concrete steps are:
(1) dispersed inorganic particles under alcohol is solvent condition, described alcoholic solution is ethanol, methyl alcohol or aqueous isopropanol; Then in the basic conditions, add amino triethoxyl silane, after reaction, carry out centrifugation, vacuum-drying is carried out to solid and prepares surface-functionalized inorganic particle;
(2) raw rice husk stalk is carbonized, obtain the powdered rice hulls after carbonizing, then the powdered rice hulls after charing is dissolved in the vitriol oil, obtains the powdered rice hulls after acidifying;
Described charring process is the segmentation charing adopting quartz tube furnace to carry out coconut husk: rise to 150 DEG C with the temperature rise rate of 10 DEG C/min, coconut husk carbonizes 50min at 150 DEG C, then 300 DEG C are risen to the temperature rise rate of 10 DEG C/min, again at 300 DEG C of charing 50min, finally rise to 400 DEG C with the temperature rise rate of 5 DEG C/min, and carbonize process 2 ~ 3h at such a temperature; Ground at high energy ball mill by obtained product after charing, until finely powdered, namely obtain the powdered rice hulls after carbonizing, the particle diameter of powdered rice hulls is 0.01 ~ 2 μm; Adopt low-temperature carbonization, save cost on the one hand, keep the original function of rice husk in addition on the one hand, rice husk stalk effect can be played as the carrier of absorption, the temperature of charing is too high and long, will destroy original performance of rice husk stalk, Here it is low temperature and the slow feature carbonized.
(3) the surface-functionalized inorganic particle that step (1) obtains is joined step (2) and obtain the powdered rice hulls after acidifying, carry out ultrasonic disperse 40min; Carry out centrifugation after dispersion to carry out drying again and can obtain black properties-correcting agent;
The mass ratio of the powdered rice hulls after the charing of described surface-functionalized inorganic particle and step (2) is 1: 8;
(4) step (3) being obtained black properties-correcting agent joins in Low Density Polyethylene particle, carries out mixing and melt pelletization, obtains modified low-density polyethylene, and wherein black properties-correcting agent accounts for the massfraction of modified low-density polyethylene is 2%.
A kind of preparation method for overhead line black wear well polythene Insulation Material, its concrete steps are: by modified poly ester, auxiliary agent, Masterbatch, modified low-density polyethylene, organosilane crosslinked polyethylene mixes according to proportioning, and then melt pelletization can obtain black wear well polythene Insulation Material.
Embodiment 2
A kind of for overhead line black wear well polythene Insulation Material, it is characterized in that, the mass percent of its raw material is:
The preparation method of described modified poly ester, its concrete steps are:
(1) dispersed inorganic particles under alcohol is solvent condition, described alcoholic solution is ethanol, methyl alcohol or aqueous isopropanol; Then in the basic conditions, add amino triethoxyl silane, after reaction, carry out centrifugation, vacuum-drying is carried out to solid and prepares surface-functionalized inorganic particle;
Described inorganic particle concentration in alcoholic solution is 5 ~ 35kg/m
3, it is 8.5 ~ 9.5 that system pH controls, and temperature of reaction is 60 ~ 75 DEG C, and the reaction times is 150 ~ 240min;
Described inorganic particle is nano-indium stannum oxide, nano indium oxide antimony and nano zine oxide, and the mass ratio of three is 1: 1: 3, and median size is 10 ~ 50nm, adopts ultrasonic disperse 50min in alcoholic solution dispersion process;
(2) then under nitrogen protection, with surface-functionalized inorganic particle, terephthalic acid; ethylene glycol is raw material; carry out the first step esterification, and then in second step prepolymerization reaction process, add polyvalent alcohol carry out copolycondensation, then prepare modified poly ester through the whole polycondensation of the 3rd step.
In described the first step esterification, the molar ratio of raw material terephthalic acid and ethylene glycol is 1: 1.5, and inorganic particle addition is the 1.5wt% of terephthalic acid massfraction.
Described the first step esterification is under nitrogen protection, inorganic particle first dispersion making beating in ethylene glycol solution, and then under pressure is 0.3 ~ 0.4MPa condition, polyprotonic acid and ethylene glycol carry out esterification, and temperature of reaction, at 220 ~ 250 DEG C, reacts 3 ~ 4h.
Described second step prepolymerization reaction, polyol starting material is sorbyl alcohol or tetramethylolmethane; In raw material, the mol ratio of terephthalic acid and polyvalent alcohol is 1: 0.002.
Described second step prepolymerization reaction, controls temperature of reaction at 260 ~ 280 DEG C, keeps 2 ~ 3h.
The whole polycondensation of the 3rd described step, control low vacuum in 60Pa, temperature of reaction is at 270 ~ 290 DEG C, and the reaction times is 2 ~ 4h.
The preparation method of described modified low-density polyethylene, its concrete steps are:
(1) dispersed inorganic particles under alcohol is solvent condition, described alcoholic solution is ethanol, methyl alcohol or aqueous isopropanol; Then in the basic conditions, add amino triethoxyl silane, after reaction, carry out centrifugation, vacuum-drying is carried out to solid and prepares surface-functionalized inorganic particle;
Described inorganic particle concentration in alcoholic solution is 5 ~ 35kg/m
3, it is 8.5 ~ 9.5 that system pH controls, and temperature of reaction is 60 ~ 75 DEG C, and the reaction times is 150 ~ 240min;
Described inorganic particle is nano-indium stannum oxide, nano indium oxide antimony and nano zine oxide, and the mass ratio of three is 1: 1: 3, and median size is 10 ~ 50nm, adopts ultrasonic disperse 50min in alcoholic solution dispersion process;
(2) raw rice husk stalk is carbonized, obtain the powdered rice hulls after carbonizing, then the powdered rice hulls after charing is dissolved in the vitriol oil, obtains the powdered rice hulls after acidifying;
Described charring process is the segmentation charing adopting quartz tube furnace to carry out coconut husk: rise to 150 DEG C with the temperature rise rate of 10 DEG C/min, coconut husk carbonizes 50min at 150 DEG C, then 300 DEG C are risen to the temperature rise rate of 10 DEG C/min, again at 300 DEG C of charing 50min, finally rise to 400 DEG C with the temperature rise rate of 5 DEG C/min, and carbonize process 2 ~ 3h at such a temperature; Ground at high energy ball mill by obtained product after charing, until finely powdered, namely obtain the powdered rice hulls after carbonizing, the particle diameter of powdered rice hulls is 0.01 ~ 2 μm; Adopt low-temperature carbonization, save cost on the one hand, keep the original function of rice husk in addition on the one hand, rice husk stalk effect can be played as the carrier of absorption, the temperature of charing is too high and long, will destroy original performance of rice husk stalk, Here it is low temperature and the slow feature carbonized.
(3) the surface-functionalized inorganic particle that step (1) obtains is joined step (2) and obtain the powdered rice hulls after acidifying, carry out ultrasonic disperse 40min; Carry out centrifugation after dispersion to carry out drying again and can obtain black properties-correcting agent;
The mass ratio of the powdered rice hulls after the charing of described surface-functionalized inorganic particle and step (2) is 1: 8;
(4) step (3) being obtained black properties-correcting agent joins in Low Density Polyethylene particle, carries out mixing and melt pelletization, obtains modified low-density polyethylene, and wherein black properties-correcting agent accounts for the massfraction of modified low-density polyethylene is 3%.
A kind of preparation method for overhead line black wear well polythene Insulation Material, its concrete steps are: by modified poly ester, auxiliary agent, Masterbatch, modified low-density polyethylene, organosilane crosslinked polyethylene mixes according to proportioning, and then melt pelletization can obtain black wear well polythene Insulation Material.
Embodiment 3
A kind of for overhead line black wear well polythene Insulation Material, it is characterized in that, the mass percent of its raw material is:
The preparation method of described modified poly ester, its concrete steps are:
(1) dispersed inorganic particles under alcohol is solvent condition, described alcoholic solution is ethanol, methyl alcohol or aqueous isopropanol; Then in the basic conditions, add amino triethoxyl silane, after reaction, carry out centrifugation, vacuum-drying is carried out to solid and prepares surface-functionalized inorganic particle;
Described inorganic particle concentration in alcoholic solution is 5 ~ 35kg/m
3, it is 8.5 ~ 9.5 that system pH controls, and temperature of reaction is 60 ~ 75 DEG C, and the reaction times is 150 ~ 240min;
Described inorganic particle is nano-indium stannum oxide, nano indium oxide antimony and nano zine oxide, and the mass ratio of three is 1: 1: 3, and median size is 10 ~ 50nm, adopts ultrasonic disperse 50min in alcoholic solution dispersion process;
(2) then under nitrogen protection, with surface-functionalized inorganic particle, terephthalic acid; ethylene glycol is raw material; carry out the first step esterification, and then in second step prepolymerization reaction process, add polyvalent alcohol carry out copolycondensation, then prepare modified poly ester through the whole polycondensation of the 3rd step.
In described the first step esterification, the molar ratio of raw material terephthalic acid and ethylene glycol is 1: 1.55, and inorganic particle addition is the 2wt% of terephthalic acid massfraction.
Described the first step esterification is under nitrogen protection, inorganic particle first dispersion making beating in ethylene glycol solution, and then under pressure is 0.3 ~ 0.4MPa condition, polyprotonic acid and ethylene glycol carry out esterification, and temperature of reaction, at 220 ~ 250 DEG C, reacts 3 ~ 4h.
Described second step prepolymerization reaction, polyol starting material is sorbyl alcohol or tetramethylolmethane; In raw material, the mol ratio of terephthalic acid and polyvalent alcohol is 1: 0.003.
Described second step prepolymerization reaction, controls temperature of reaction at 260 ~ 280 DEG C, keeps 2 ~ 3h.
The whole polycondensation of the 3rd described step, control low vacuum in 60Pa, temperature of reaction is at 270 ~ 290 DEG C, and the reaction times is 2 ~ 4h.
The preparation method of described modified low-density polyethylene, its concrete steps are:
(1) dispersed inorganic particles under alcohol is solvent condition, described alcoholic solution is ethanol, methyl alcohol or aqueous isopropanol; Then in the basic conditions, add amino triethoxyl silane, after reaction, carry out centrifugation, vacuum-drying is carried out to solid and prepares surface-functionalized inorganic particle;
Described inorganic particle concentration in alcoholic solution is 5 ~ 35kg/m
3, it is 8.5 ~ 9.5 that system pH controls, and temperature of reaction is 60 ~ 75 DEG C, and the reaction times is 150 ~ 240min;
Described inorganic particle is nano-indium stannum oxide, nano indium oxide antimony and nano zine oxide, and the mass ratio of three is 1: 1: 3, and median size is 10 ~ 50nm, adopts ultrasonic disperse 50min in alcoholic solution dispersion process;
(2) raw rice husk stalk is carbonized, obtain the powdered rice hulls after carbonizing, then the powdered rice hulls after charing is dissolved in the vitriol oil, obtains the powdered rice hulls after acidifying;
Described charring process is the segmentation charing adopting quartz tube furnace to carry out coconut husk: rise to 150 DEG C with the temperature rise rate of 10 DEG C/min, coconut husk carbonizes 50min at 150 DEG C, then 300 DEG C are risen to the temperature rise rate of 10 DEG C/min, again at 300 DEG C of charing 50min, finally rise to 400 DEG C with the temperature rise rate of 5 DEG C/min, and carbonize process 2 ~ 3h at such a temperature; Ground at high energy ball mill by obtained product after charing, until finely powdered, namely obtain the powdered rice hulls after carbonizing, the particle diameter of powdered rice hulls is 0.01 ~ 2 μm; Adopt low-temperature carbonization, save cost on the one hand, keep the original function of rice husk in addition on the one hand, rice husk stalk effect can be played as the carrier of absorption, the temperature of charing is too high and long, will destroy original performance of rice husk stalk, Here it is low temperature and the slow feature carbonized.
(3) the surface-functionalized inorganic particle that step (1) obtains is joined step (2) and obtain the powdered rice hulls after acidifying, carry out ultrasonic disperse 40min; Carry out centrifugation after dispersion to carry out drying again and can obtain black properties-correcting agent;
The mass ratio of the powdered rice hulls after the charing of described surface-functionalized inorganic particle and step (2) is 1: 8;
(4) step (3) being obtained black properties-correcting agent joins in Low Density Polyethylene particle, carries out mixing and melt pelletization, obtains modified low-density polyethylene, and wherein black properties-correcting agent accounts for the massfraction of modified low-density polyethylene is 4%.
A kind of preparation method for overhead line black wear well polythene Insulation Material, its concrete steps are: by modified poly ester, auxiliary agent, Masterbatch, modified low-density polyethylene, organosilane crosslinked polyethylene mixes according to proportioning, and then melt pelletization can obtain black wear well polythene Insulation Material.
Embodiment 4
A kind of for overhead line black wear well polythene Insulation Material, it is characterized in that, the mass percent of its raw material is:
The preparation method of described modified poly ester, with embodiment 1;
The preparation method of described modified low-density polyethylene, with embodiment 1;
For a preparation method for overhead line black wear well polythene Insulation Material, with embodiment 1.
Embodiment 5
A kind of for overhead line black wear well polythene Insulation Material, it is characterized in that, the mass percent of its raw material is:
The preparation method of described modified poly ester, with embodiment 1;
The preparation method of described modified low-density polyethylene, with embodiment 1;
For a preparation method for overhead line black wear well polythene Insulation Material, with embodiment 1; .
Embodiment 6
For a multi-functional polyethylene Insulation Material for cable, it is characterized in that, the mass percent of its raw material is:
The preparation method of modified poly ester is with embodiment 1;
The preparation method of modified low-density polyethylene is with embodiment 1.
Embodiment 7
For a multi-functional polyethylene Insulation Material for cable, it is characterized in that, the mass percent of its raw material is:
The preparation method of modified poly ester is with embodiment 2;
The preparation method of modified low-density polyethylene is with embodiment 2.
Embodiment 8
For a multi-functional polyethylene Insulation Material for cable, it is characterized in that, the mass percent of its raw material is:
The preparation method of modified poly ester is with embodiment 3;
The preparation method of modified low-density polyethylene is with embodiment 3.
Embodiment 9
Electric power is used for a polyethylene composite insulation material for cable, and it is characterized in that, the mass percent of its raw material is:
The preparation method of modified poly ester is with embodiment 1;
The preparation method of modified low-density polyethylene is with embodiment 1.
SBS particle in the present embodiment can be replaced by PBT particle, can obtain a kind of poly-ethylene cable material for power domain.
Embodiment 10
Electric power is used for a polyethylene composite insulation material for cable, and it is characterized in that, the mass percent of its raw material is:
The preparation method of modified poly ester is with embodiment 2;
The preparation method of modified low-density polyethylene is with embodiment 2.
SBS particle in the present embodiment can be replaced by PBT particle, can obtain a kind of poly-ethylene cable material for power domain.
Embodiment 11
For a polyethylene composite insulation material for power cable, it is characterized in that, the mass percent of its raw material is:
The preparation method of modified poly ester is with embodiment 3;
The preparation method of modified low-density polyethylene is with embodiment 3.
SBS particle in the present embodiment can be replaced by PBT particle, can obtain a kind of poly-ethylene cable material for power domain.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (5)
1. for an overhead line black wear well polythene Insulation Material, it is characterized in that, the mass percent of its raw material is:
Modified poly ester 1 ~ 5%
Auxiliary agent 0.1 ~ 0.5%
Carbon black 1 ~ 5%
Modified low-density polyethylene 10 ~ 40%
Organosilane crosslinked polyethylene surplus
The concrete steps of the preparation method of described modified low-density polyethylene are:
(1) functionalization of inorganic particle: dispersed inorganic particles under alcohol is solvent condition, described alcoholic solution is ethanol, methyl alcohol or aqueous isopropanol; Then in the basic conditions, add amino triethoxyl silane, after reaction, carry out centrifugation, vacuum-drying is carried out to solid and prepares surface-functionalized inorganic particle;
(2)
the acidifying of rice husk stalk: raw rice husk stalk is carbonized, obtains the powdered rice hulls after carbonizing, then the powdered rice hulls after charing is dissolved in the vitriol oil, obtains the powdered rice hulls after acidifying;
Described inorganic particle is nano-indium stannum oxide, nano indium oxide antimony and nano zine oxide, and the mass ratio of three is 1:1:3, and median size is 10 ~ 50nm, adopts ultrasonic disperse 50min in alcoholic solution dispersion process;
(3) preparation of black properties-correcting agent: the surface-functionalized inorganic particle that step (1) obtains is joined step (2) and obtains the powdered rice hulls after acidifying, carry out ultrasonic disperse 40min; Carry out centrifugation after dispersion to carry out drying again and can obtain black properties-correcting agent;
(4) preparation of modified low-density polyethylene: step (3) is obtained black properties-correcting agent and joins in Low Density Polyethylene particle, carry out mixing and melt pelletization, obtain modified low-density polyethylene, wherein black properties-correcting agent accounts for the massfraction of modified low-density polyethylene is 1 ~ 3%;
The preparation method of described modified poly ester, its concrete steps are:
(1) functionalization of inorganic particle: dispersed inorganic particles under alcohol is solvent condition, described alcoholic solution is ethanol, methyl alcohol or aqueous isopropanol; Then in the basic conditions, add amino triethoxyl silane, after reaction, carry out centrifugation, vacuum-drying is carried out to solid and prepares surface-functionalized inorganic particle;
Described inorganic particle is nano-indium stannum oxide, nano indium oxide antimony and nano zine oxide, and the mass ratio of three is 1:1:3, and median size is 10 ~ 50nm, adopts ultrasonic disperse 50min in alcoholic solution dispersion process;
(2) preparation of modified poly ester: under nitrogen protection; with surface-functionalized inorganic particle; terephthalic acid; ethylene glycol is raw material; carry out the first step esterification; and then in second step prepolymerization reaction process, add polyvalent alcohol carry out copolycondensation, then prepare modified poly ester through the whole polycondensation of the 3rd step.
2. as claimed in claim 1 a kind of for overhead line black wear well polythene Insulation Material, it is characterized in that, the massfraction of described modified poly ester is 2 ~ 4%.
3. as claimed in claim 1 a kind of for overhead line black wear well polythene Insulation Material, it is characterized in that, the massfraction of described modified poly ester is 3%.
4. as claimed in claim 1 a kind of for overhead line black wear well polythene Insulation Material, it is characterized in that, the massfraction of described modified low-density polyethylene is 20 ~ 30%.
5. as claimed in claim 1 a kind of for overhead line black wear well polythene Insulation Material, it is characterized in that, the massfraction of described modified low-density polyethylene is 25%.
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| CN107123458A (en) * | 2017-06-20 | 2017-09-01 | 上海南大集团有限公司 | A kind of high-strength anti-flaming environment protection light aerial insulated cable |
| CN109331788B (en) * | 2018-10-29 | 2021-09-28 | 山东省农业科学院农业质量标准与检测技术研究所 | Adsorbent for removing aflatoxin in peanut oil and preparation method thereof |
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