CN109111674A - There is halogen flame-retardant polyethylene sheathing material - Google Patents
There is halogen flame-retardant polyethylene sheathing material Download PDFInfo
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- CN109111674A CN109111674A CN201810763378.5A CN201810763378A CN109111674A CN 109111674 A CN109111674 A CN 109111674A CN 201810763378 A CN201810763378 A CN 201810763378A CN 109111674 A CN109111674 A CN 109111674A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- 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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2003/026—Phosphorus
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/068—Ultra high molecular weight polyethylene
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Abstract
The present invention, which provides one kind, halogen flame-retardant polyethylene sheathing material, and the raw material for preparing for having halogen flame-retardant polyethylene sheathing material includes at least: polyethylene kind mixture, inorganic fire retardants, has halogen fire retardant, lubricant and color masterbatch at antioxidant.It is provided by the invention to have halogen flame-retardant polyethylene sheathing material that there are excellent dielectric properties, the performances such as resistance to low temperature and anti-stress cracking, and finished product is processed into after medium and high voltage cable also with good flexility, flame retardant property is examined by cable bunched burning test, by burning 40 minutes up to 31.8 meters length determine grade be B class.
Description
Technical field
The present invention relates to protective cover material technical fields, more particularly it relates to which one kind has halogen flame-retardant polyethylene sheathing material
And preparation method thereof.
Background technique
With the raising of countries in the world environmental protection and awareness of safety, the CABLE MATERIALS of anti-flaming environment-friendly be widely applied and
With very big development potentiality.Flame-proof polyethylene is because of its light weight, mechanical property is good, has extraordinary lower temperature resistance simultaneously
The prominent feature such as energy, good environmental stress cracking resistance, good processability, outstanding electrical insulation capability, fire-retardant
Field of cables has a very wide range of applications.
Wire cable insulating and sheath are commonly called as CABLE MATERIALS with plastics, and which includes rubber, polyvinyl chloride, polyethylene, poly-
A variety of kinds such as alkene, nylon.Existing CABLE MATERIALS is generally polyvinyl chloride and polyethylene kind high molecular material, this is a kind of easy
Combustible material.After fire occurs for ambient enviroment, flame can spread to rapidly entire route along cable, lead to the expansion of flame.
For reduce cable fire caused by spot fire, flame retardant cable using more and more common.Present flame retardant cable mainly has
Halogen is fire-retardant, meanwhile, while guaranteeing flame retardant property, it is also necessary to guarantee its mechanical performance and insulation performance.
But due to the characteristic of itself, joined halogen fire retardant, mechanical performance because the addition of fire retardant is declined,
If fire retardant poor dispersion, it is easier to lead to the decline of fire-retardant polyethylene cable material mechanical performance and data are unstable.It stretches strong
Degree and elongation at break than plus before fire retardant not reducing about 40% and 35% respectively.
In addition to mechanical performance, environmental stress cracking resistance is especially prominent by being influenced, since extra-high-tension cable protects
Set needs to guarantee certain degree of hardness and mechanical performance, must add more high-density polyethylene resin in formula, and high-density polyethylene
The environmental stress cracking resistance of olefine resin is poor, especially after having received a large amount of fire retardants, this performance it is worse.
For above situation, the present invention is provided with halogen flame-retardant polyethylene sheathing material.
Summary of the invention
First aspect present invention provides one kind a halogen flame-retardant polyethylene sheathing material, described to have halogen flame-retardant polyethylene sheathing material
Raw material is prepared to include at least:
Polyethylene kind mixture, inorganic fire retardants, has halogen fire retardant, lubricant and color masterbatch at antioxidant.
As one embodiment of the present invention, by weight, the preparation for having halogen flame-retardant polyethylene sheathing material is former
Material includes at least:
40-60 parts of polyethylene kind mixture, 25-40 parts of inorganic fire retardants, has halogen fire retardant 10-20 at 0.1-3 parts of antioxidant
Part, 0.1-2 parts of lubricant and 5-20 parts of color masterbatch.
As one embodiment of the present invention, by weight, the preparation for having halogen flame-retardant polyethylene sheathing material is former
Material includes at least:
54 parts of polyethylene kind mixture, 31 parts of inorganic fire retardants, has 14 parts of halogen fire retardant, lubricant at 0.5 part of antioxidant
0.5 part and 16 parts of color masterbatch.
As one embodiment of the present invention, the polyethylene kind mixture refers to the mixed of polyethylene and modified poly ethylene
Close object.
As one embodiment of the present invention, the polyethylene refers to ultra-high molecular weight polyethylene, medium density polyethylene
With the mixture of low density polyethylene (LDPE).
As one embodiment of the present invention, the ultra-high molecular weight polyethylene is branching type superhigh molecular weight polyethylene
Alkene.
As one embodiment of the present invention, the raw material for preparing for having halogen flame-retardant polyethylene sheathing material also includes modification
Polyacrylic acid and nano-inorganic substance.
As one embodiment of the present invention, the fire retardant for thering is halogen fire retardant to be selected from the element containing Br.
It is described to have halogen fire retardant for decabrominated dipheny alkane as one embodiment of the present invention.
The second aspect of the present invention provides the above-mentioned method for having halogen flame-retardant polyethylene sheathing material, and steps are as follows:
S01, which will prepare raw material by weight and be added in high-speed mixer, mixes 5min, obtains mixture；
Said mixture is added in adding pressure type mixer S02, and mixing molding obtains substance A；
S03 is squeezed out substance A by twin-screw extruder, wherein the processing temperature of twin-screw are as follows: conveying section 100~120
DEG C, 125~140 DEG C of melt zone, 140~155 DEG C of mixing section, 150~160 DEG C of exhaust section, 150~160 DEG C of homogenizing zone, head
165~175 DEG C；Single screw rod temperature are as follows: the first 125~140 DEG C of area, the second 125~140 DEG C of area, 125~140 DEG C of third area, machine
First 145~150 DEG C, obtain substance B；
Substance B is added in pelletizer S04, is granulated into particle, packaging after pelletizing is air-cooled.
The utility model has the advantages that
1, provided by the invention to there is halogen flame-retardant polyethylene sheathing material to be added to fire retardant in polyethylene sheath material, not only protect
The advantages of having stayed polyethylene also improves flame retardant property, increases the flame retardant property index oxygen index (OI) 17.4% of product to 30%；
2, provided by the invention to have halogen flame-retardant polyethylene sheathing material that there are excellent dielectric properties, it resistance to low temperature and anti-answers
The performances such as power cracking, and finished product is processed into after medium and high voltage cable also has good flexility, and flame retardant property passes through cable
Bunched burning test examination, by burning 40 minutes up to 31.8 meters length determine grade be B class.
Detailed description of the invention
Fig. 1: breakdown test pressuring method.
Horizontal axis indicates the time, and number axis indicates electric field strength (MV/m).
Specific embodiment
For the purpose of following detailed description, it should be understood that the present invention can be used various substitutions variation and step it is suitable
Sequence, unless specifically stated on the contrary.In addition, being indicated in the case where in addition in any operational instances or otherwise pointing out
Such as all numbers of the amount of ingredient used in description and claims should be understood in all cases by term
" about " it modifies.Therefore, unless indicated to the contrary, the numerical parameter otherwise illustrated in the following description and appended dependent claims is root
The approximation changed according to the expected performance of the invention to be obtained.It is at least not intended to for the applicable of doctrine of equivalents being limited in
In the scope of the claims, each numerical parameter should at least be given up according to the number of the effective digital of report and by the way that application is common
Enter technology to explain.
Although illustrating that broad range of numberical range and parameter of the invention are approximations, listed in specific example
Numerical value is reported as accurately as possible.However, any numerical value inherently includes the standard deviation by finding in its each self-test measurement
The certain errors necessarily led to.
In addition, it should be understood that any numberical range as described herein, which is intended to include, is included into all subranges therein.Example
Such as, the range of " 1 to 10 " is intended to include all sub- models between (and including) described minimum value 1 and the maximum value 10
It encloses, that is, there is the minimum value equal to or more than 1 and the maximum value equal to or less than 10.
The present invention, which provides one kind, halogen flame-retardant polyethylene sheathing material, which is characterized in that described to have halogen flame-proof polyethylene sheath
The raw material for preparing of material includes at least:
Polyethylene kind mixture, inorganic fire retardants, has halogen fire retardant, lubricant and color masterbatch at antioxidant.
As one embodiment of the present invention, the raw material for preparing for having halogen flame-retardant polyethylene sheathing material also includes modification
Polyacrylic acid and nano-inorganic substance.
Polyethylene kind mixture
In the present invention, the polyethylene kind mixture refers to the mixture of polyethylene and modified poly ethylene.
Polyethylene: in the present invention, the polyethylene refers to that ultra-high molecular weight polyethylene, medium density polyethylene and low-density are poly-
The mixture of ethylene.
As one embodiment of the present invention, the ultra-high molecular weight polyethylene is branching type superhigh molecular weight polyethylene
Alkene.
In the present invention, the ultra-high molecular weight polyethylene the preparation method is as follows:
1. replacing three times in 0.5L stainless steel stirring polymeric kettle nitrogen, ethylene is replaced twice, will be containing cocatalyst
180mL hexane solution is added in kettle, starts stirring, catalyst is added to polymeric kettle under nitrogen protection by revolving speed 150rpm
In, pressure in kettle is then shed, 40 DEG C is risen to temperature in the kettle, is passed through ethylene gas, pressure is made in kettle to reach 0.6MPa, five points
Speed of agitator is risen to 250rpm by Zhong Hou；Stop being passed through ethylene after polymerization 1 hour, differs and be no more than with room temperature to temperature in the kettle
After 20 DEG C, gas and discharging in emptying system obtain granulated polymer after dry.
Wherein, catalyst charge 10mg, co-catalyst MMAO.
Catalyst the preparation method is as follows:
0.1g metal complex is added in 10mL methylene chloride, until completely dissolved, is added to what chemical activation was crossed
In spherical magnesium chloride SMC-11.0g, mechanical stirring 2h (100 revs/min of revolving speed) under nitrogen atmosphere, decompressing and extracting is washed with 50mL hexane
Wash the catalyst for being dried under reduced pressure to obtain good fluidity twice.
It is described, metal complex the preparation method is as follows: in the reaction flask of 100mL, 2.82g (10.0mmol) 1- is added
(2,6- 3,5-dimethylphenyl) -3- (2- methoxyphenyl) propanedione, 0.91g (10.0mmol) 2- sulfidomethyl ethamine, 0.5mL ice vinegar
Acid, 30mL dehydrated alcohol stop reaction after being heated to reflux 12h, make to be cooled to room temperature, -30 DEG C of freezings are to get product is arrived, with cold
Ethanol washing for several times, obtains yellow crystals after dry.By the 10mL tetrahydrofuran solution of 710mg (2.0mmol) ligand at -78 DEG C
It is added dropwise in the 10mL tetrahydrofuran of 79mg (2.0mmol) KH, 2h is stirred in continuation at room temperature.Vacuum removes solvent, and 40mL is added
This negative solution is added dropwise to TiCl at room temperature by toluene4In the 10mL toluene solution of 379mg (2.0mmol), it is added dropwise,
12h is stirred in continuation at room temperature.Centrifugation, supernatant remove solvent and obtain crude product, obtain metal combination with re crystallization from toluene
Object.
The ligand the preparation method is as follows: in the reaction flask of 100mL, 3.06g (10.0mmol) 2- methyl-1 is added,
3- bis- (rubigan) propanedione, 1.47g (10.0mmol) 2- ethyl -3- sulfidomethyl butylamine, 0.5mL glacial acetic acid, 30mL are anhydrous
Ethyl alcohol stops reaction after being heated to reflux 12h, makes to be cooled to room temperature, -30 DEG C of freezings are to get product is arrived, with cold ethanol washing number
It is secondary, ligand is obtained after dry.
The spherical shape magnesium chloride SMC-1's the preparation method is as follows: taking spherical chlorination magnesium alcoholate 10.0g, wherein ethyl alcohol contains
Amount 52%, volume average particle size D [4,3] are 48um, and 50mL hexane is added, triethyl aluminum 18mL is slowly added dropwise under nitrogen atmosphere,
After dripping, mechanical stirring (100 revs/min of revolving speed) the reaction was continued 2h is filtered, is washed twice with 50mL hexane, done under reduced pressure
The dry spherical magnesium chloride activated, is denoted as SMC-1.
As one embodiment of the present invention, the ultra-high molecular weight polyethylene, medium density polyethylene and low-density are poly-
The weight ratio of ethylene is 1:8:2.
Modified poly ethylene: in the present invention, the modified poly ethylene is organic acid anhydride grafted polyethylene.
Heretofore described organic acid anhydride grafted polyethylene is to be grafted by the double bond in organic acid anhydride by radical reaction
In polyethylene, polar group is added in nonpolar polyethylene, improves the work between protective cover material system and inorganic filler
Firmly, reduce two alternate interface energy.
In one embodiment, the organic acid anhydride grafted polyethylene the preparation method comprises the following steps: first accurately weigh polyethylene,
Organic acid anhydride, initiator, additive；By most of polyethylene in N2Under protection, 100r/ is placed in higher than 10~20 DEG C of reaction temperature
In the Brabende plasticizing instrument that min adds, reduces plasticization temperature and make it below required reaction temperature.5min or so is heated to poly- second
After alkene melts completely, 215~250 DEG C of reaction temperature are warming up to, then stops logical N2, and by organic acid anhydride, initiator, additive
Divide quarter to be separately added into 2min, can discharge obtain organic acid anhydride grafted polyethylene.
In one embodiment, in the organic acid anhydride grafted polyethylene containing organic acid anhydride grafting rate be 25%~
55%；It preferably, is 30%~45% containing organic acid anhydride grafting rate in the organic acid anhydride grafted polyethylene；It is highly preferred that
It is described containing in organic acid anhydride grafted polyethylene contain organic acid anhydride grafting rate be 35%.
In one embodiment, the organic acid anhydride be selected from maleic anhydride, acrylic anhydride, hex- 2- alkenyl succinic anhydride,
The combination of any one or more in 4- pentenoic acid anhydride；As a kind of preferred embodiment of the invention, the organic acid anhydride is horse
Carry out acid anhydrides CAS:108-31-6.
In one embodiment, the initiator is selected from two t-amyl peroxy compounds (DtAP), di-tert-butyl peroxide
In the tertiary fourth vinegar (tBPB) of object (tBCP), cumyl peroxide (DCP), dibenzoyl peroxide (BPO), perbenzoic acid
The combination of any one or more；Preferably, the initiator is cumyl peroxide.
In one embodiment, the additive be selected from dimethylformamide (DMF), dimethyl acetamide (DMAC),
Dimethyl sub-maple (DMSO), phosphorous acid three (nonyl benzene vinegar) (TNPP), stearmide, any one or more in caprolactam
Combination；Preferably, the additive is dimethyl acetamide.
Preferably, the organic acid anhydride grafted polyethylene the preparation method comprises the following steps: first accurately weigh 0.5mol polyethylene,
0.175mol maleic anhydride, 0.03mol cumyl peroxide, 0.15mol dimethyl acetamide；By most of polyethylene in N2
Under protection, it is placed in higher than 10~20 DEG C of reaction temperature in the Brabende plasticizing instrument that 100r/min adds, reducing plasticization temperature makes it
Lower than required reaction temperature.5min or so is heated after halogen-free polyolefin melts completely, is warming up to reaction temperature 215~250
DEG C, then stop logical N2, and by maleic anhydride, cumyl peroxide, dimethyl acetamide divides quarter to distinguish in 2min
Be added, can discharge obtain maleic anhydride grafted polyethylene.
As one embodiment of the present invention, the molecular weight of the polyethylene is 1000~10000；Preferably, described
The molecular weight of polyethylene is 8000.
Antioxidant
Antioxidant is a kind of chemical substance, in the presence of it is only a small amount of in polymeric system, so that it may delay or inhibit poly-
The progress for closing object oxidation process, to prevent the aging of polymer and prolong its service life.
In the present invention, the antioxidant is antioxidant 1010.
Inorganic fire retardants
Fire retardant is a kind of material can be prevented to light, control flame transmission and one kind of raising material fire-resistant characteristic helps
Agent.The polymer of fire retardant is typically contained, it is not easy to be ignited by external heat source first, and can control flame not after resuming
It broadcasts to cause the burning of other material, to greatly reduce a possibility that fire occurs.In general, fire retardant can be divided into it is organic
With two class of inorganic fire retardants.But it due to inorganic fire retardants no pollution to the environment characteristic, is studied by people always recent years.Nothing
Machine fire retardant, mainly include metal hydroxides, red phosphorus, ammonium polyphosphate, Sb system fire retardant, silicon-series five-retardant, boron flame retardant,
Nano-meter flame retardants and smoke suppressant.
Metal hydroxides: in the present invention, the metal hydroxides is added in cable sheath material, can to avoid due to
Add variety of problems caused by halogen or red phosphorus based flame retardant.
The metal hydroxides mainly includes two kinds of inorganic fire retardantss of aluminium hydroxide and magnesium hydroxide.
In one embodiment, the metal hydroxides is magnesium hydroxide.
Magnesium hydroxide dehydration when reaching certain temperature, absorbs heat and the vapor generated has diluting effect, decomposites
Oxide can promote polymer carbonization, to have fire retardation to polymer.Magnesium hydroxide decomposes between 340~490 DEG C,
Dehydration occurs for higher temperature, there is that material is inhibited to be carbonized well.
As one embodiment of the present invention, the inorganic fire retardants also includes red phosphorus and antimony oxide.
There is halogen fire retardant
There is halogen fire retardant to refer to the fire retardant containing elements such as Cl, Br, F, it is described to have as one embodiment of the present invention
Halogen fire retardant is decabrominated dipheny alkane.
Lubricant
In one embodiment, the lubricant is selected from polysiloxanes, polyethylene wax, zinc stearate, calcium stearate, double
Aluminum stearate, glycerin monostearate, stearic acid, any one or more in polytetrafluoroethylene (PTFE)；Preferably, the lubricant
For stearate.
Color masterbatch
The full name of color masterbatch is also color kind Masterbatch, is a kind of novel high polymer material special coloring agent, also known as pigment system
Standby object.Color masterbatch is used primarily on plastics.Color masterbatch is made of three kinds of pigments or dyes, carrier and additive fundamentals, is handle
The pigment of super quantity be uniformly attached among resin prepared by aggregation, condensed pigment can be claimed, so its tinting strength, tinting power is high
In pigment itself.It is blended when processing with a small amount of color masterbatch and uncolored resin, so that it may reach the pigmentary resin of design pigment concentration
Or product.
Modified polyacrylic acid
The raw material of modified polyacrylic acid of the present invention includes polyacrylic acid, melamine cyanurate, contains amino and carboxylic
The amide of base.It first will be acid amide-grafted in the side chain of polyacrylic acid then anti-with melamine cyanurate containing amino and carboxyl
Answer, it is specific the preparation method comprises the following steps:
(1) it takes polyacrylic acid soluble in water, after dropwise addition 0.1mol/L hydrochloric acid is adjusted to pH to 5.5, catalyst is added
0.6mmol L-11- ethyl-(3- dimethylaminopropyl) carbodiimides, 0.06mmol/L n-hydroxysuccinimide, room
The amide containing amino and carboxyl is added after temperature stirring 15min, reacts 4h, substance A can be obtained；
(2) substance A for taking step (1) to obtain is dissolved in ethyl alcohol/n,N-Dimethylformamide solution, and wherein ethyl alcohol is 60%
(volume fraction) adds catalyst 0.6mmol L-11- ethyl-(3- dimethylaminopropyl) carbodiimides, 0.06mmol
L-1N-hydroxysuccinimide is added melamine cyanurate after 30min is stirred at room temperature, reacts 4h, substance modification can be obtained
Polyacrylic acid.
In one embodiment, polyacrylic acid, melamine cyanurate and contain amino in the modified polyacrylic acid
Molar ratio with the amide of carboxyl is 1:(0.25~0.5): (0.5~1)；Preferably, polypropylene in the modified polyacrylic acid
The molar ratio of acid, melamine cyanurate and the amide containing amino and carboxyl is 1:(0.3~0.4): (0.6~0.9)；It is more excellent
Selection of land, the molar ratio of polyacrylic acid, melamine cyanurate and the amide containing amino and carboxyl in the modified polyacrylic acid
For 1:0.35:0.7.
In one embodiment, the amide containing amino and carboxyl is selected from [(Carboxvmethoxv) amino] (oxo)
Acetic acid, 2- amino -3- [(carboxycarbonyl) amino] butyric acid, 2- amino -4- (carboxycarbonyl amino) butyric acid, 3- ((carboxycarbonyl)
Amino) combination of any one or more in-l-Alanine, [(Carboxvmethoxv) amino] (oxo) the acetic acid CAS:
177902-90-8,2- amino -3- [(carboxycarbonyl) amino] butyric acid CAS:184646-39-7,2- amino -4- (carboxycarbonyl ammonia
Base) butyric acid CAS:5302-43-2,3- ((carboxycarbonyl) amino)-l-Alanine CAS:5302-45-4；Preferably, described to contain
The amide of amino and carboxyl is 2- amino -3- [(carboxycarbonyl) amino] butyric acid.
Preferably, the modified polyacrylic acid the preparation method comprises the following steps:
(1) it takes polyacrylic acid soluble in water, 0.1mol L is added dropwise-1After hydrochloric acid is adjusted to pH to 5.5, catalyst is added
0.6mmol L-11- ethyl-(3- dimethylaminopropyl) carbodiimides, 0.06mmol L-1N-hydroxysuccinimide, room
2- amino -3- [(carboxycarbonyl) amino] butyric acid is added after temperature stirring 15min, reacts 4h, substance A can be obtained；
(2) substance A for taking step (1) to obtain is dissolved in ethyl alcohol/n,N-Dimethylformamide solution, and wherein ethyl alcohol is 60%
(volume fraction) adds catalyst 0.6mmol L-11- ethyl-(3- dimethylaminopropyl) carbodiimides, 0.06mmol
L-1N-hydroxysuccinimide is added melamine cyanurate after 30min is stirred at room temperature, reacts 4h, substance modification can be obtained
Polyacrylic acid.
In one embodiment, the molecular weight of the polyacrylic acid in the modified polyacrylic acid is 2000~5000；It is excellent
Selection of land, the molecular weight of the polyacrylic acid are 3500.
In one embodiment, the parts by weight of the modified polyacrylic acid are 1-3 parts.
Nano-inorganic substance
In the present invention, the nano-inorganic substance is the inorganic matter of Nano grade.
In one embodiment, the parts by weight of the nano-inorganic substance are 0.1-0.5 parts.
As one embodiment of the present invention, in the present invention, the nano-inorganic substance is metal oxide.
As one embodiment of the present invention, the metal oxide is selected from titanium dioxide, zirconium dioxide, three oxidations two
One of aluminium, di-iron trioxide, stannic oxide, magnesia, aluminium oxide, zinc oxide.
As one embodiment of the present invention, the metal oxide is zinc oxide.
As one embodiment of the present invention, the zinc oxide is nano-sheet, the system of the nano-sheet zinc oxide
Preparation Method is as follows:
(1) it takes in zinc source solution, adjusts pH with ammonium hydroxide, after obtaining sediment, after sediment is stood 12 hours, centrifuging and taking
Filter residue, by filter residue, successively with distilled water, dehydrated alcohol, alternately washing is for several times neutral to sediment；Then baking is put the precipitate in
60 DEG C of dryings, obtain desciccate in case；
(2) it weighs 3g desciccate to be placed in autoclave, the sodium tripolyphosphate solution of the 0.1mol/L of 20mL is added
With the deionized water of 20mL, adjusting pH with concentrated ammonia liquor is about 9, then the hydro-thermal reaction 28h at 220 DEG C；It will produce after completion of the reaction
Object takes out from reaction kettle, cooling with room temperature, product centrifuge separation, and is successively washed for several times with distilled water, dehydrated alcohol respectively,
Product is placed in baking oven, and nano-sheet zinc oxide can be prepared.
Wherein, zinc source solution is the solution of zinc sulfate of 0.1mol/L.
The second aspect of the present invention provide it is a kind of prepare the above-mentioned method for having halogen flame-retardant polyethylene sheathing material, step is such as
Under:
S01, which will prepare raw material by weight and be added in high-speed mixer, mixes 5min, obtains mixture；
Said mixture is added in adding pressure type mixer S02, and mixing molding obtains substance A；
S03 is squeezed out substance A by twin-screw extruder, wherein the processing temperature of twin-screw are as follows: conveying section 100~120
DEG C, 125~140 DEG C of melt zone, 140~155 DEG C of mixing section, 150~160 DEG C of exhaust section, 150~160 DEG C of homogenizing zone, head
165~175 DEG C；Single screw rod temperature are as follows: the first 125~140 DEG C of area, the second 125~140 DEG C of area, 125~140 DEG C of third area, machine
First 145~150 DEG C, obtain substance B；
Substance B is added in pelletizer S04, is granulated into particle, packaging after pelletizing is air-cooled.
Mechanism is explained: high voltage power transmission has the advantages that long range, large capacity, low-loss, represents current technology of transmission of electricity
Highest level and development trend are increasingly subject to the concern of countries in the world.High voltage power transmission technology experienced from high pressure, superelevation in the world
Press to the course and trend of extra-high voltage development.Wire and cable is the critical component of electric power transport, and insulating materials therein is to determine
One of the key factor of cable voltage ability；The many because being known as of cable insulation space charge are influenced, it is provided by the invention described
CABLE MATERIALS can exclude the inhomogeneity for leading to crystal habit due to the temperature difference, and lead to the of different sizes of spherocrystal, so as to improve it
Influence to distribution of space charge, while using the ultra-high molecular weight polyethylene and nano-sheet inorganic matter of branching, with modification
The effect that polyacrylate is shown in can improve the accumulation situation of interface；Especially improve inorganic matter and modified polyacrylic acid
Between accumulation situation.
Embodiment 1. has a halogen flame-retardant polyethylene sheathing material, it is described have a halogen flame-retardant polyethylene sheathing material prepare raw material at least
Include:
Polyethylene kind mixture, inorganic fire retardants, has halogen fire retardant, lubricant and color masterbatch at antioxidant.
There is halogen flame-retardant polyethylene sheathing material described in 2. embodiment 1 of embodiment, it is by weight, described to have halogen fire-retardant
The raw material for preparing of polyethylene sheath material includes at least:
40-60 parts of polyethylene kind mixture, 25-40 parts of inorganic fire retardants, has halogen fire retardant 10-20 at 0.1-3 parts of antioxidant
Part, 0.1-2 parts of lubricant and 5-20 parts of color masterbatch.
There is halogen flame-retardant polyethylene sheathing material described in 3. embodiment 1 of embodiment, it is by weight, described to have halogen fire-retardant
The raw material for preparing of polyethylene sheath material includes at least:
54 parts of polyethylene kind mixture, 31 parts of inorganic fire retardants, has 14 parts of halogen fire retardant, lubricant at 0.5 part of antioxidant
0.5 part and 16 parts of color masterbatch.
There is halogen flame-retardant polyethylene sheathing material described in 4. embodiment 1 of embodiment, the polyethylene kind mixture refers to
The mixture of polyethylene and modified poly ethylene.
There is halogen flame-retardant polyethylene sheathing material described in 5. embodiment 4 of embodiment, the polyethylene refers to supra polymer
The mixture of weight northylen, medium density polyethylene and low density polyethylene (LDPE).
There is halogen flame-retardant polyethylene sheathing material described in 6. embodiment 5 of embodiment, the ultra-high molecular weight polyethylene is
Branching type ultra-high molecular weight polyethylene.
There is halogen flame-retardant polyethylene sheathing material described in 7. embodiment 7 of embodiment, it is described to have halogen flame-proof polyethylene sheath
The raw material for preparing of material also includes modified polyacrylic acid and nano-inorganic substance.
There is halogen flame-retardant polyethylene sheathing material described in 8. embodiment 1 of embodiment, described have halogen fire retardant to be selected to contain
The fire retardant of Br.
There is halogen flame-retardant polyethylene sheathing material described in 9. embodiment 8 of embodiment, it is described to have halogen fire retardant for ten bromines two
Benzene alkane.
Embodiment 10. is a kind of to prepare the described in any item methods for having halogen flame-retardant polyethylene sheathing material of embodiment 1-9,
Steps are as follows:
S01, which will prepare raw material by weight and be added in high-speed mixer, mixes 5min, obtains mixture；
Said mixture is added in adding pressure type mixer S02, and mixing molding obtains substance A；
S03 is squeezed out substance A by twin-screw extruder, wherein the processing temperature of twin-screw are as follows: conveying section 100~120
DEG C, 125~140 DEG C of melt zone, 140~155 DEG C of mixing section, 150~160 DEG C of exhaust section, 150~160 DEG C of homogenizing zone, head
165~175 DEG C；Single screw rod temperature are as follows: the first 125~140 DEG C of area, the second 125~140 DEG C of area, 125~140 DEG C of third area, machine
First 145~150 DEG C, obtain substance B；
Substance B is added in pelletizer S04, is granulated into particle, packaging after pelletizing is air-cooled.
There is halogen flame-retardant polyethylene sheathing material to be described in detail to provided by the invention combined with specific embodiments below.
Embodiment 1: the present embodiment provides one kind halogen flame-retardant polyethylene sheathing material, by weight, described to have halogen fire-retardant
The raw material for preparing of polyethylene sheath material includes at least:
54 parts of polyethylene kind mixture, 31 parts of inorganic fire retardants, has 14 parts of halogen fire retardant, lubricant at 0.5 part of antioxidant
0.5 part, 16 parts of color masterbatch, 2 parts of modified polyacrylic acid and 0.2 part of nano-inorganic substance.
The polyethylene kind mixture refers to the mixture of polyethylene and modified poly ethylene, and polyethylene and modified poly ethylene
Weight ratio be 1:2；
The polyethylene is to be according to weight ratio by ultra-high molecular weight polyethylene, medium density polyethylene and low density polyethylene (LDPE)
The mixture of 1:8:2.
The ultra-high molecular weight polyethylene the preparation method is as follows:
1. replacing three times in 0.5L stainless steel stirring polymeric kettle nitrogen, ethylene is replaced twice, will be containing cocatalyst
180mL hexane solution is added in kettle, starts stirring, catalyst is added to polymeric kettle under nitrogen protection by revolving speed 150rpm
In, pressure in kettle is then shed, 40 DEG C is risen to temperature in the kettle, is passed through ethylene gas, pressure is made in kettle to reach 0.6MPa, five points
Speed of agitator is risen to 250rpm by Zhong Hou；Stop being passed through ethylene after polymerization 1 hour, differs and be no more than with room temperature to temperature in the kettle
After 20 DEG C, gas and discharging in emptying system obtain granulated polymer after dry.
Wherein, catalyst charge 10mg, co-catalyst MMAO.
Catalyst the preparation method is as follows:
0.1g metal complex is added in 10mL methylene chloride, until completely dissolved, is added to what chemical activation was crossed
In spherical magnesium chloride SMC-11.0g, mechanical stirring 2h (100 revs/min of revolving speed) under nitrogen atmosphere, decompressing and extracting is washed with 50mL hexane
Wash the catalyst for being dried under reduced pressure to obtain good fluidity twice.
It is described, metal complex the preparation method is as follows: in the reaction flask of 100mL, 2.82g (10.0mmol) 1- is added
(2,6- 3,5-dimethylphenyl) -3- (2- methoxyphenyl) propanedione, 0.91g (10.0mmol) 2- sulfidomethyl ethamine, 0.5mL ice vinegar
Acid, 30mL dehydrated alcohol stop reaction after being heated to reflux 12h, make to be cooled to room temperature, -30 DEG C of freezings are to get product is arrived, with cold
Ethanol washing for several times, obtains yellow crystals after dry.By the 10mL tetrahydrofuran solution of 710mg (2.0mmol) ligand at -78 DEG C
It is added dropwise in the 10mL tetrahydrofuran of 79mg (2.0mmol) KH, 2h is stirred in continuation at room temperature.Vacuum removes solvent, and 40mL is added
This negative solution is added dropwise to TiCl at room temperature by toluene4In the 10mL toluene solution of 379mg (2.0mmol), it is added dropwise,
12h is stirred in continuation at room temperature.Centrifugation, supernatant remove solvent and obtain crude product, obtain metal combination with re crystallization from toluene
Object.
The ligand the preparation method is as follows: in the reaction flask of 100mL, 3.06g (10.0mmol) 2- methyl-1 is added,
3- bis- (rubigan) propanedione, 1.47g (10.0mmol) 2- ethyl -3- sulfidomethyl butylamine, 0.5mL glacial acetic acid, 30mL are anhydrous
Ethyl alcohol stops reaction after being heated to reflux 12h, makes to be cooled to room temperature, -30 DEG C of freezings are to get product is arrived, with cold ethanol washing number
It is secondary, ligand is obtained after dry.
The spherical shape magnesium chloride SMC-1's the preparation method is as follows: taking spherical chlorination magnesium alcoholate 10.0g, wherein ethyl alcohol contains
Amount 52%, volume average particle size D [4,3] are 48um, and 50mL hexane is added, triethyl aluminum 18mL is slowly added dropwise under nitrogen atmosphere,
After dripping, mechanical stirring (100 revs/min of revolving speed) the reaction was continued 2h is filtered, is washed twice with 50mL hexane, done under reduced pressure
The dry spherical magnesium chloride activated, as spherical magnesium chloride SMC-1.
The medium density polyethylene and low density polyethylene (LDPE) are commercially available.
The modified poly ethylene is organic acid anhydride grafted polyethylene, preparation method are as follows: first accurately weigh the poly- second of 0.5mol
Alkene, 0.175mol maleic anhydride, 0.03mol cumyl peroxide, 0.15mol dimethyl acetamide；By most of polyethylene
In N2Under protection, it is placed in higher than 10~20 DEG C of reaction temperature in the Brabende plasticizing instrument that 100r/min adds, reduces plasticization temperature
Make it below required reaction temperature.5min or so is heated after halogen-free polyolefin melts completely, be warming up to reaction temperature 215~
250 DEG C, then stop logical N2, and by maleic anhydride, cumyl peroxide, dimethyl acetamide divides quarter point in 2min
Be not added, can discharge obtain maleic anhydride grafted polyethylene；Wherein the molecular weight of polyethylene is 8000 in modified poly ethylene.
Antioxidant: the antioxidant is antioxidant 1010.
Inorganic fire retardants: it according to weight ratio is 6:1:2 that the inorganic fire retardants, which is magnesium hydroxide, red phosphorus and antimony oxide,
Mixture.
There is halogen fire retardant: described to have halogen fire retardant for decabrominated dipheny alkane.
Lubricant: the lubricant is calcium stearate.
Modified polyacrylic acid: preparation method is as follows: (1) taking polyacrylic acid soluble in water, 0.1mol L is added dropwise-1Hydrochloric acid tune
After section is to pH to 5.5, catalyst 0.6mmol L is added-11- ethyl-(3- dimethylaminopropyl) carbodiimides,
0.06mmol L-12- amino -3- [(carboxycarbonyl) amino] butyric acid is added after 15min is stirred at room temperature in n-hydroxysuccinimide,
4h is reacted, substance A can be obtained；
(2) substance A for taking step (1) to obtain is dissolved in ethyl alcohol/n,N-Dimethylformamide solution, and wherein ethyl alcohol is 60%
(volume fraction) adds catalyst 0.6mmol L-11- ethyl-(3- dimethylaminopropyl) carbodiimides, 0.06mmol
L-1N-hydroxysuccinimide is added melamine cyanurate after 30min is stirred at room temperature, reacts 4h, substance modification can be obtained
Polyacrylic acid.
Mole of polyacrylic acid, melamine cyanurate and the amide containing amino and carboxyl in the modified polyacrylic acid
Than for 1:0.35:0.7.The molecular weight of the polyacrylic acid is 3500.
Nano-inorganic substance: for nano-sheet zinc oxide, preparation method is as follows:
(1) it takes in zinc source solution, adjusts pH with ammonium hydroxide, after obtaining sediment, after sediment is stood 12 hours, centrifuging and taking
Filter residue, by filter residue, successively with distilled water, dehydrated alcohol, alternately washing is for several times neutral to sediment；Then baking is put the precipitate in
60 DEG C of dryings, obtain desciccate in case；
(2) it weighs 3g desciccate to be placed in autoclave, the sodium tripolyphosphate solution of the 0.1mol/L of 20mL is added
With the deionized water of 20mL, adjusting pH with concentrated ammonia liquor is about 9, then the hydro-thermal reaction 28h at 220 DEG C；It will produce after completion of the reaction
Object takes out from reaction kettle, cooling with room temperature, product centrifuge separation, and is successively washed for several times with distilled water, dehydrated alcohol respectively,
Product is placed in baking oven, and nano-sheet zinc oxide can be prepared.
Wherein, zinc source solution is the solution of zinc sulfate of 0.1mol/L.
The second aspect of the present embodiment provide it is a kind of prepare the above-mentioned method for having halogen flame-retardant polyethylene sheathing material, step is such as
Under:
S01, which will prepare raw material by weight and be added in high-speed mixer, mixes 5min, obtains mixture；
Said mixture is added in adding pressure type mixer S02, and mixing molding obtains substance A；
S03 is squeezed out substance A by twin-screw extruder, wherein the processing temperature of twin-screw are as follows: conveying section 100~120
DEG C, 125~140 DEG C of melt zone, 140~155 DEG C of mixing section, 150~160 DEG C of exhaust section, 150~160 DEG C of homogenizing zone, head
165~175 DEG C；Single screw rod temperature are as follows: the first 125~140 DEG C of area, the second 125~140 DEG C of area, 125~140 DEG C of third area, machine
First 145~150 DEG C, obtain substance B；
Substance B is added in pelletizer S04, is granulated into particle, packaging after pelletizing is air-cooled.
Embodiment 2: the specific embodiment of embodiment 2 is with embodiment 1, and difference, the present embodiment provides one kind halogen
Flame-retardant polyethylene sheathing material, by weight, the raw material for preparing for having halogen flame-retardant polyethylene sheathing material include at least:
40 parts of polyethylene kind mixture, 25 parts of inorganic fire retardants, has 10 parts of halogen fire retardant, lubricant at 0.1 part of antioxidant
0.1 part, 5 parts of color masterbatch, 1 part of modified polyacrylic acid and 0.1 part of nano-inorganic substance.
Embodiment 3: the specific embodiment of embodiment 3 is with embodiment 1, and difference, the present embodiment provides one kind halogen
Flame-retardant polyethylene sheathing material, by weight, the raw material for preparing for having halogen flame-retardant polyethylene sheathing material include at least:
60 parts of polyethylene kind mixture, 3 parts of antioxidant, 40 parts of inorganic fire retardants, have 20 parts of halogen fire retardant, 2 parts of lubricant,
20 parts of color masterbatch, 3 parts of modified polyacrylic acid and 0.5 part of nano-inorganic substance.
Embodiment 4: the specific embodiment of embodiment 4 is the same as embodiment 1, difference, the ultra-high molecular weight polyethylene
Parts by weight be 0.
Embodiment 5: the specific embodiment of embodiment 5 is the same as embodiment 1, difference, the ultra-high molecular weight polyethylene
It is commercially available.
Embodiment 6: the specific embodiment of embodiment 6 is the same as embodiment 1, difference, the weight of the nano-inorganic substance
Part is 0.
Embodiment 7: the specific embodiment of embodiment 7 is the same as embodiment 1, difference, the nanometer burl of the zinc oxide
Structure, partial size 40nm.
Embodiment 8: the specific embodiment of embodiment 8 is with embodiment 1, difference, the melamine cyanurate
Parts by weight replace with 0.
Embodiment 9: the specific embodiment of embodiment 9 is the same as embodiment 1, difference, 2- amino -3- [(the carboxyl carbonyl
Base) amino] parts by weight of butyric acid replace with 0.
Embodiment 10: the specific embodiment of embodiment 10 is with embodiment 1, difference, the modified polyacrylic acid
Parts by weight replace with 0.
Performance evaluation:
(1) oxygen index (OI): oxygen index (OI) is tested according to national standard GB406-80.
(2) elongation strengths: elongation strengths are tested according to national standard GB/T528.
(3) elongation at break: elongation at break is tested according to national standard GB/T528.
(4) smoke density: smoke density is tested according to national standard GB/T 8627-2007.
1 the performance test results of table
(5) space charge is tested
The CABLE MATERIALS that the present invention is prepared is prepared into film-form sample, sample thickness 0.2mm.
5.1 breakdown test pressuring method such as Fig. 1.
5.2 breakdown temperature tests: breakdown performance test is carried out at 75 DEG C, after maintaining 1 hour, sees whether puncture.
When 5.3 positive voltages puncture, the comparison of electric field strength (MV/m).
The relationship of average accumulation space charge density and temperature that 5.4 each embodiments are prepared, power plant's intensity are 30MV/
Pressurize 20min under m direct current power station.Test result is shown in Table 3.
2 the performance test results of table
By above-mentioned performance test it is found that the various dc breakdown electric field strengths of CABLE MATERIALS film that are prepared of embodiment 1 compared with
For equilibrium, when positive voltage punctures, breakdown minimum electric field strength improves 25% compared to remaining embodiment, highest in short-term.Meanwhile it protecting
Hold the anti-breakdown performance that can keep excellent at 75 DEG C.
Table 3 averagely accumulates the performance test of space charge density
It can be seen that after the 20min that pressurizes from above-mentioned test, the average accumulation space charge density of embodiment 1 is low, and with
The raising of temperature, averagely accumulation space charge density significantly reduce, have excellent sky compared to embodiments such as embodiments 10
Between charge accumulated characteristic.
Claims (10)
1. there is halogen flame-retardant polyethylene sheathing material, which is characterized in that it is described have a halogen flame-retardant polyethylene sheathing material prepare raw material at least
Include:
Polyethylene kind mixture, inorganic fire retardants, has halogen fire retardant, lubricant and color masterbatch at antioxidant.
2. described in claim 1 have halogen flame-retardant polyethylene sheathing material, which is characterized in that by weight, described to have halogen fire-retardant
The raw material for preparing of polyethylene sheath material includes at least:
40-60 parts of polyethylene kind mixture, 0.1-3 parts of antioxidant, 25-40 parts of inorganic fire retardants, have 10-20 parts of halogen fire retardant,
0.1-2 parts and color masterbatch 5-20 parts of lubricant.
3. described in claim 1 have halogen flame-retardant polyethylene sheathing material, which is characterized in that by weight, described to have halogen fire-retardant
The raw material for preparing of polyethylene sheath material includes at least:
54 parts of polyethylene kind mixture, 31 parts of inorganic fire retardants, has 14 parts of halogen fire retardant, 0.5 part of lubricant at 0.5 part of antioxidant
With 16 parts of color masterbatch.
4. described in claim 1 have halogen flame-retardant polyethylene sheathing material, which is characterized in that the polyethylene kind mixture refers to poly-
The mixture of ethylene and modified poly ethylene.
5. as claimed in claim 4 have halogen flame-retardant polyethylene sheathing material, which is characterized in that the polyethylene refers to super high molecular weight
The mixture of polyethylene, medium density polyethylene and low density polyethylene (LDPE).
6. there is halogen flame-retardant polyethylene sheathing material described in claim 5, which is characterized in that the ultra-high molecular weight polyethylene is branch
Change type ultra-high molecular weight polyethylene.
7. described in claim 1 have halogen flame-retardant polyethylene sheathing material, which is characterized in that described to have halogen flame-retardant polyethylene sheathing material
The raw material for preparing also include modified polyacrylic acid and nano-inorganic substance.
8. described in claim 1 have halogen flame-retardant polyethylene sheathing material, which is characterized in that it is described have halogen fire retardant be selected from contain Br
Fire retardant.
9. according to any one of claims 8 have halogen flame-retardant polyethylene sheathing material, which is characterized in that described to have halogen fire retardant for decabrominated dipheny
Alkane.
10. a kind of prepare the described in any item methods for having halogen flame-retardant polyethylene sheathing material of claim 1-9, which is characterized in that
Steps are as follows:
S01, which will prepare raw material by weight and be added in high-speed mixer, mixes 5min, obtains mixture；
Said mixture is added in adding pressure type mixer S02, and mixing molding obtains substance A；
S03 is squeezed out substance A by twin-screw extruder, wherein the processing temperature of twin-screw are as follows: 100~120 DEG C of conveying section,
125~140 DEG C of melt zone, 140~155 DEG C of mixing section, 150~160 DEG C of exhaust section, 150~160 DEG C of homogenizing zone, head 165~
175℃；Single screw rod temperature are as follows: the first 125~140 DEG C of area, the second 125~140 DEG C of area, 125~140 DEG C of third area, head 145
~150 DEG C, obtain substance B；
Substance B is added in pelletizer S04, is granulated into particle, packaging after pelletizing is air-cooled.
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| CN201810763378.5A CN109111674A (en) | 2018-07-12 | 2018-07-12 | There is halogen flame-retardant polyethylene sheathing material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116063767A (en) * | 2023-03-11 | 2023-05-05 | 广东安拓普聚合物科技有限公司 | Mining scratch-resistant sheath material |
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| CN102898703A (en) * | 2011-07-27 | 2013-01-30 | 上海凯波特种电缆料厂有限公司 | Flame retardant polyolefin cable material and preparation method thereof |
| CN104017267A (en) * | 2014-06-13 | 2014-09-03 | 深圳市沃尔核材股份有限公司 | Heat-conducting wire cable electric-insulation material or sheath material |
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| CN116063767A (en) * | 2023-03-11 | 2023-05-05 | 广东安拓普聚合物科技有限公司 | Mining scratch-resistant sheath material |
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