CN106566038A - Modified enzymolysis lignin synergistic molybdenum-based compound flame-retardant reinforced anti-breakdown polyethylene electric cable material - Google Patents
Modified enzymolysis lignin synergistic molybdenum-based compound flame-retardant reinforced anti-breakdown polyethylene electric cable material Download PDFInfo
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- CN106566038A CN106566038A CN201610902006.7A CN201610902006A CN106566038A CN 106566038 A CN106566038 A CN 106566038A CN 201610902006 A CN201610902006 A CN 201610902006A CN 106566038 A CN106566038 A CN 106566038A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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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
- C08L23/02—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
- C08L23/06—Polyethene
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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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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- 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
- 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
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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Abstract
The present invention discloses a modified enzymolysis lignin synergistic molybdenum-based compound flame-retardant reinforced anti-breakdown polyethylene electric cable material, which is prepared from the following raw materials by weight: 100-105 parts of low density polyethylene, a proper amount of anhydrous ethanol, 1.5-2 parts of nanometer magnesium oxide, 0.1-0.12 part of a silane coupling agent KH550, 20-22 parts of enzymolysis lignin, 400-420 parts of a sodium hydroxide solution with a concentration of 2 wt%, 6-7 parts of a formaldehyde aqueous solution with a concentration of 45 wt%, 15-16 parts of melamine, a proper amount of 0.1 mol/L hydrochloric acid , 4-5 parts of sodium pyrophosphate, 5-6 parts of microencapsulated red phosphorus, a proper amount of deionized water, 3-4 parts of diocty phthalate, 3-4 parts of ammonium molybdate, 6-7 parts of a silicone-acrylic emulsion, 2-2.5 parts of molybdenum oxide, and 0.3-0.4 part of stearic acid. The prepared modified enzymolysis lignin synergistic molybdenum-based compound flame-retardant reinforced anti-breakdown polyethylene electric cable material of the present invention has good breakdown resistance, can be used as the direct current transmission electric cable, has excellent mechanical property, and can meet electric cable development requirements.
Description
Technical field
The present invention relates to CABLE MATERIALS technical field, more particularly to a kind of modified enzymolysis lignin collaboration molybdenum system compound is fire-retardant
Poly-ethylene cable material is worn in enhanced resistance.
Background technology
Polyethylene because with excellent electrical property, mechanical property, chemical-resistance and good processing characteristics, extensively should
For making the daily living articles such as thin film, tubing, electric wire, plastic, packaging material and other high-grade, precision and advanced engineering skills
Art field.Wherein Low Density Polyethylene has a prominent pliability and insulating properties, nontoxic and be easy to coloring, is largely used to cable
Material, replaces halogen-containing polrvinyl chloride.Electric wire can constantly be subject to electricity, heat and mechanical stress etc. various in application process
Conductor can inject electronics and hole to insulating barrier during the comprehensive function, such as overcurrent of factor, and insulating barrier easily occurs electronics
Or hole accumulation, Space-charge effect is formed, cause electric field distortion, there is electrical breakdown when serious, cause transmission of electricity accident；Therefore, seek
Effective way is looked for suppress space charge accumulation, homogenizing insulating barrier Electric Field Distribution to suppress electric branch growth, extend the use longevity of cable
Life, is to prepare high-performance electric wire problem demanding prompt solution.
《The preparation of multi-layer mesoporous nano-MgO/LDPE Composite and its insulating properties》Using low in one text
Boiling point solvent method prepares multi-layer mesoporous structure nano magnesium oxide, realizes uniform point of nano magnesia in Low Density Polyethylene
Dissipate, space charge accumulation is restrained effectively under the Low Density Polyethylene 70KV/mm electric fields for adding 1% nano magnesia, improve
Dc breakdown intensity, reduces dielectric constant, at the same high field by force under effectively inhibit electronics and hole injection, prevent tunnel
The generation of channel effect, it is suppressed that the generation of Space-charge effect, the dielectric properties of composite are met as High Performance Insulation material
Use condition.But because the oxygen index (OI) of polythene material is than relatively low, belong to combustible material, in addition it is also necessary to which fire-retardant changing is carried out to it
Property after could further meet the use demand of CABLE MATERIALS, the combination property of cable insulation material determines that wire is used safely
Property, therefore it is required that carrying out carrying out its anti-flammability, heat stability, mechanical property etc. while Dielectric Properties to insulant
Further investigation.
The content of the invention
The object of the invention is exactly to make up the defect of prior art, there is provided a kind of modified enzymolysis lignin cooperates with molybdenum system
Poly-ethylene cable material is worn in the fire-retardant enhanced resistance of compound.
The present invention is achieved by the following technical solutions：
A kind of modified enzymolysis lignin cooperates with the fire-retardant enhanced resistance of molybdenum system compound to wear poly-ethylene cable material, by following weight portion
Raw material make：Low Density Polyethylene 100-105, appropriate dehydrated alcohol, nano magnesia 1.5-2, silane coupler
Sodium hydroxide solution 400-420, the first that concentration is 45wt% of KH5500.1-0.12, enzymolysis xylogen 20-22, concentration for 2wt%
Aldehyde aqueous solution 6-7, tripolycyanamide 15-16,0.1mol/L hydrochloric acid is appropriate, sodium pyrophosphate 4-5, microencapsulated powder oil 5-6, go from
Sub- appropriate amount of water, dibutyl ester 3-4, ammonium molybdate 3-4, silicone acrylic emulsion 6-7, molybdenum oxide 2-2.5, stearic acid 0.3-0.4.
Poly-ethylene cable material is worn in a kind of fire-retardant enhanced resistance of the modified enzymolysis lignin collaboration molybdenum system compound, by with
Lower concrete steps are made：
（1）By nano magnesia ultrasonic disperse in the 4-5 times of dehydrated alcohol measured, it is centrifuged, is dried, will be dried nano oxidized
Magnesium is put in Muffle furnace, and with the heating rate of 3-5 DEG C/min 200-220 DEG C is warming up to, and is incubated 30-40 minutes, is taken out after cooling
It is stand-by；Silane coupling agent KH550 is dissolved in the 10-12 times of dehydrated alcohol measured, is then mixed with the nano magnesia after calcining,
It is centrifuged after ultrasonic disperse 30-40 minutes, filters, is dried, obtains modified Nano magnesium oxide；
（2）The sodium hydroxide solution of enzymolysis xylogen and concentration for 2wt% is mixed, with 300-400 rev/min of speed stir to
It is completely dissolved, is heated to 90-95 DEG C, adds concentration for the formalin of 45wt%, continuation after stirring reaction 100-120 minute
Tripolycyanamide is added, continues to be slowly added dropwise in the hydrochloric acid of 0.1mol/L after reacting 90-120 minutes and rear stand-by；By sodium pyrophosphate
In being dissolved in the 18-20 times of deionized water measured, in being subsequently adding above-mentioned reaction, continue stirring reaction 60-90 minute, precipitation is generated,
Stand, filter, deionized water is cleaned 2-3 time, being then placed in vacuum drying oven being dried with 80-90 DEG C of temperature, final powder
It is broken, 200 mesh sieves are crossed, obtain modified enzymolysis lignin；
（3）Ammonium molybdate, Firebrake ZB, molybdenum oxide are put in ball mill, deionized water and Hard Fat that addition total amount 2-3 times is measured
Acid, wet ball grinding is poured in batch mixer after 40-50 minutes, to add silicon after the speed stirring 8-10 minutes of 800-1000 turn/part
Acrylic emulsion, then with the speed stirring 20-30 minutes of 300-400 turn/part, be finally spray-dried, obtain mixed fillers；
（4）By step（1）（2）（3）The product for obtaining is put into mixed at a high speed jointly with Low Density Polyethylene and remaining residual components
In material machine, to send in double roller open mill after the speed stirring mixing 10-12 minutes of 800-1000 turn/part, control is warm
150-160 DEG C of degree is kneaded, in being then fed into double screw extruder, 150-170 DEG C of temperature control, and extruding pelletization is obtained final product.
It is an advantage of the invention that：The present invention using Mannich reaction principle by formaldehyde, tripolycyanamide, sodium pyrophosphate etc. into
Point it is modified reaction to enzymolysis xylogen, generation modified enzymolysis lignin, as a kind of carbon source in thermal decomposition process, can be with
Thermal decomposition to macromolecular material plays inhibitory action, is compounded with microencapsulated powder oil, is added to Low Density Polyethylene cable
In the preparation of material, synergism has obvious flame-retardant smoke inhibition effect, while the flame-retardant composition of addition is not halogen, by natural materials
Generate, those non-renewable resources, safety and environmental protection can be substituted, while flame retardant effect is excellent；The present invention also system of CABLE MATERIALS again
With the addition of modified Nano magnesium oxide in standby, with meso-hole structure, be uniformly dispersed in Low Density Polyethylene by batch mixing, compared with
Electronics and hole injection are effectively inhibited under high field intensity, the generation of tunnel-effect is prevented, it is suppressed that the generation of Space-charge effect, is carried
High dc breakdown intensity, improves the anti-breakdown performance and insulation stability of CABLE MATERIALS of the present invention.
The present invention is also coordinated the compositions such as ammonium molybdate, molybdenum oxide and silicone acrylic emulsion by a series of PROCESS FOR TREATMENT, is made
Mixed fillers are added in CABLE MATERIALS system, the addition of modified synergic enzymolysis xylogen, further enhancing smoke suppressing effect so that
Smoke density grade reach it is minimum, while silicone acrylic emulsion enhances the toughness of product, weather resistance；CABLE MATERIALS tool made by the present invention
There is good anti-breakdown performance, can be used in galvanic handling cable, and flame-retardant smoke inhibition excellent, fire retardant raw material is adopted
With natural materials, safety and environmental protection, and made by CABLE MATERIALS excellent in mechanical performance, meet the demand of cable development.
Specific embodiment
A kind of modified enzymolysis lignin cooperates with the fire-retardant enhanced resistance of molybdenum system compound to wear poly-ethylene cable material, by following heavy
Amount part（Kilogram）Raw material make：Low Density Polyethylene 100, appropriate dehydrated alcohol, nano magnesia 1.5, silane coupler
KH5500.1, enzymolysis xylogen 20, concentration are the formalin 6, three of the sodium hydroxide solution 400, concentration for 45wt% of 2wt%
The hydrochloric acid of poly cyanamid 15,0.1mol/L is appropriate, sodium pyrophosphate 4, microencapsulated powder oil 5, appropriate deionized water, dibutyl ester 3, molybdic acid
Ammonium 3, silicone acrylic emulsion 6, molybdenum oxide 2, stearic acid 0.3.
Poly-ethylene cable material is worn in a kind of fire-retardant enhanced resistance of the modified enzymolysis lignin collaboration molybdenum system compound, by with
Lower concrete steps are made：
（1）By nano magnesia ultrasonic disperse in the dehydrated alcohol of 4 times of amounts, it is centrifuged, is dried, by dried nano magnesia
In being put into Muffle furnace, 200 DEG C are warming up to the heating rate of 3 DEG C/min, are incubated 30 minutes, taken out after cooling stand-by；By silane
Coupling agent KH550 is dissolved in the dehydrated alcohol of 10 times of amounts, is then mixed with the nano magnesia after calcining, ultrasonic disperse 30 minutes
It is centrifuged afterwards, filters, is dried, obtains modified Nano magnesium oxide；
（2）The sodium hydroxide solution of enzymolysis xylogen and concentration for 2wt% is mixed, is stirred to complete with 300 revs/min of speed
Dissolving, is heated to 90 DEG C, adds the formalin that concentration is 45wt%, stirring reaction to continuously add melamine after 100 minutes
Amine, continues to be slowly added dropwise in the hydrochloric acid of 0.1mol/L after reacting 90 minutes and rear stand-by；By sodium pyrophosphate be dissolved in 18 times amount go
In ionized water, in being subsequently adding above-mentioned reaction, continue stirring reaction 60 minutes, precipitation is generated, standing, filtration, deionized water
Cleaning 2 times, is then placed in vacuum drying oven being dried with 80 DEG C of temperature, finally crushes, and crosses 200 mesh sieves, obtains modified enzymolysis
Lignin；
（3）Ammonium molybdate, Firebrake ZB, molybdenum oxide are put in ball mill, the deionized water and stearic acid of 2 times of amounts of total amount is added,
Wet ball grinding is poured in batch mixer after 40 minutes, and after stirring 8 minutes with the speed of 800 turns/part silicone acrylic emulsion is added, then with 300
Turn/speed of part stirs 20 minutes, is finally spray-dried, and obtains mixed fillers；
（4）By step（1）（2）（3）The product for obtaining is put into mixed at a high speed jointly with Low Density Polyethylene and remaining residual components
In material machine, send in double roller open mill after being mixed 10 minutes with the speed stirring of 800 turns/part, 150 DEG C of temperature of control is entered
Row mixing, in being then fed into double screw extruder, 150 DEG C of temperature control, extruding pelletization is obtained final product.
CABLE MATERIALS of the present invention is applied to into the production of cable, after testing, the index for reaching is as follows for cable product：Tensile strength
For 17.5MPa, elongation at break is 289%, and oxygen index (OI) is 28.5%, and dielectric strength is 31.8MV/m.
Claims (2)
1. poly-ethylene cable material is worn in the fire-retardant enhanced resistance of a kind of modified enzymolysis lignin collaboration molybdenum system compound, and its feature exists
In being prepared by the raw materials in：Low Density Polyethylene 100-105, appropriate dehydrated alcohol, nano magnesia 1.5-2, silicon
Alkane coupling agent KH5500.1-0.12, enzymolysis xylogen 20-22, concentration are the sodium hydroxide solution 400-420 of 2wt%, concentration is
The formalin 6-7 of 45wt%, the hydrochloric acid of tripolycyanamide 15-16,0.1mol/L are appropriate, sodium pyrophosphate 4-5, micro encapsulation are red
Phosphorus 5-6, appropriate deionized water, dibutyl ester 3-4, ammonium molybdate 3-4, silicone acrylic emulsion 6-7, molybdenum oxide 2-2.5, stearic acid 0.3-0.4.
2. according to claim 1 polyethylene is worn in a kind of fire-retardant enhanced resistance of modified enzymolysis lignin collaboration molybdenum system compound
CABLE MATERIALS, it is characterised in that be made up of step in detail below：
（1）By nano magnesia ultrasonic disperse in the 4-5 times of dehydrated alcohol measured, it is centrifuged, is dried, will be dried nano oxidized
Magnesium is put in Muffle furnace, and with the heating rate of 3-5 DEG C/min 200-220 DEG C is warming up to, and is incubated 30-40 minutes, is taken out after cooling
It is stand-by；Silane coupling agent KH550 is dissolved in the 10-12 times of dehydrated alcohol measured, is then mixed with the nano magnesia after calcining,
It is centrifuged after ultrasonic disperse 30-40 minutes, filters, is dried, obtains modified Nano magnesium oxide；
（2）The sodium hydroxide solution of enzymolysis xylogen and concentration for 2wt% is mixed, with 300-400 rev/min of speed stir to
It is completely dissolved, is heated to 90-95 DEG C, adds concentration for the formalin of 45wt%, continuation after stirring reaction 100-120 minute
Tripolycyanamide is added, continues to be slowly added dropwise in the hydrochloric acid of 0.1mol/L after reacting 90-120 minutes and rear stand-by；By sodium pyrophosphate
In being dissolved in the 18-20 times of deionized water measured, in being subsequently adding above-mentioned reaction, continue stirring reaction 60-90 minute, precipitation is generated,
Stand, filter, deionized water is cleaned 2-3 time, being then placed in vacuum drying oven being dried with 80-90 DEG C of temperature, final powder
It is broken, 200 mesh sieves are crossed, obtain modified enzymolysis lignin；
（3）Ammonium molybdate, Firebrake ZB, molybdenum oxide are put in ball mill, deionized water and Hard Fat that addition total amount 2-3 times is measured
Acid, wet ball grinding is poured in batch mixer after 40-50 minutes, to add silicon after the speed stirring 8-10 minutes of 800-1000 turn/part
Acrylic emulsion, then with the speed stirring 20-30 minutes of 300-400 turn/part, be finally spray-dried, obtain mixed fillers；
（4）By step（1）（2）（3）The product for obtaining is put into mixed at a high speed jointly with Low Density Polyethylene and remaining residual components
In material machine, to send in double roller open mill after the speed stirring mixing 10-12 minutes of 800-1000 turn/part, control is warm
150-160 DEG C of degree is kneaded, in being then fed into double screw extruder, 150-170 DEG C of temperature control, and extruding pelletization is obtained final product.
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| CN201610902006.7A CN106566038A (en) | 2016-10-18 | 2016-10-18 | Modified enzymolysis lignin synergistic molybdenum-based compound flame-retardant reinforced anti-breakdown polyethylene electric cable material |
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| CN201610902006.7A CN106566038A (en) | 2016-10-18 | 2016-10-18 | Modified enzymolysis lignin synergistic molybdenum-based compound flame-retardant reinforced anti-breakdown polyethylene electric cable material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110012938A (en) * | 2019-05-24 | 2019-07-16 | 刘建飞 | Vegetable cold chain logistics ecology preservation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110012938A (en) * | 2019-05-24 | 2019-07-16 | 刘建飞 | Vegetable cold chain logistics ecology preservation method |
| CN110012938B (en) * | 2019-05-24 | 2022-04-29 | 猫眼品牌管理(上海)有限公司 | Vegetable cold-chain logistics ecological preservation method |
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Application publication date: 20170419 |