CN105153610B - A kind of small line footpath wire cable material of low-smoke bittern-free highly fire-proof and preparation method thereof - Google Patents
A kind of small line footpath wire cable material of low-smoke bittern-free highly fire-proof and preparation method thereof Download PDFInfo
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Abstract
The invention discloses small line footpath wire cable materials of a kind of low-smoke bittern-free highly fire-proof and preparation method thereof, 40 60 parts of vinyl acetate resin, 10 20 parts of polyethylene, 10 20 parts of ethylene octene resin, 10 20 parts of maleic anhydride grafted ethene octene copolymer, 80 120 parts of fire retardant, 48 parts of fire retarding synergist, processing aid 48,12 parts of crosslinking agent, 24 parts of antioxidant.First vinyl acetate resin, polyethylene, ethylene octene resin, maleic anhydride grafted ethene octene copolymer are respectively placed in baking oven dry, then vinyl acetate resin, polyethylene, ethylene octene resin, maleic anhydride grafted ethene octene copolymer are blended in mixer, then crosslinking agent, antioxidant, processing aid, fire retardant, fire retarding synergist are sequentially added, gained blend is again through being kneaded, being molded, cold pressing sizing.Prepared cable material is with high flame retardant simultaneously also with excellent electricity, mechanics and environmental-protecting performance.
Description
Technical field
The invention belongs to technical field of electric wires and cables, are related to a kind of small line footpath wire cable material of low-smoke bittern-free highly fire-proof, special
It is not related to a kind of low-smoke bittern-free highly fire-proof based on the miscellaneous phenanthrene compound of phosphine and the dual modified magnesium hydroxide of pentaerythritol triacrylate
Small line footpath wire cable material, the invention further relates to the preparation methods of the wire cable material.
Background technology
Electric wire occupies very important due to having the function of the conveying etc. of the transmission of information and the energy in national economy
Status.With the enhancing that people realize the concern of own health and environment-friendly type, prepared by low-smoke halogen-free flame-retardant electric wire and cable material
Product be more and more favored, demand is also increasing, especially avirulent polyolefins low-fume non-bittern flame-retardant electrical wire
CABLE MATERIALS is most by extensive concern.With the development of technology, in the demand under either various extreme conditions or daily life
It needs, the exploitation of the wire cable material of low-smoke bittern-free highly fire-proof becomes more and more important.
The small line footpath wire cable material of low-smoke bittern-free highly fire-proof is very high to the challenge of flame-retardancy requirements, mainly due to small line
Under the conditions of diameter, the thickness of sample is very thin, it is thinner mean it is higher to fire-retardant requirement.Simultaneously, it is necessary to meet it is fire-retardant before
The requirement of the mechanics that puts, hardness, environmental protection, processing etc..So the exploitation small line footpath wire cable material of low-smoke bittern-free highly fire-proof
It is the huge challenge to current industrial quarters and academia.Zhang Yujie is prepared for a kind of high resiliency and wear-resisting low-smoke non-halogen flame-retardant line
Cable material (patent of invention number：ZL201210395954.8), the high resiliency and wear-resisting low-smoke non-halogen flame-retardant cable material mobility, resistance
Combustion property, weatherability, resilience are preferable and wear-resisting.Zhao Qinkuan etc. has invented halogen-free flameproof TPE cables proprietary material and its preparation side
Method (application for a patent for invention number：2015100378749, publication date：On May 27th, 2015), the fire-retardant TPE of the low smoke, zero halogen soft
There is cable material high flame retardant property, shore hardness to reach 70~75A, and tensile strength reaches 12~14MPa, melt flow rate
MFR (230 DEG C, 2.16KG) can reach 6.2g/10min；While material chance water is not precipitated, anti-aging property is good, is suitable for production
The flame-resistant electronic electric appliance cable of all kinds of requirement softnesses.The development environmental-protection low-smoke halogen-free flame-retardant cable such as Liang Guilan material (rubber science and technology,
2014,07,37~41), the matrix of the material is low density polyethylene (LDPE) (LDPE)/ethylene-vinyl acetate copolymer (EVA)/tri-
First EP rubbers (EPDM) co-mixing system, blending ratio 36/54/10, fire retardant are aluminium hydroxide/inorganic filler Create-
E/ magnesium hydroxides (60/30/60) system, compatilizer are that maleic anhydride is grafted EVA (EVA-g-MAH), and dosage is 8 parts.The material
Physical property, flame retardant property, electrical property and environmental-protecting performance touch the mark requirement, and finished product cable performance is good.
Based on previous studies it is found that halogen-free high flame-retardant cable material has certain Research foundation, but this series of matches
(such as cable thickness 0.8mm or less) cannot all be tested by VW-1 under Fang little line footpaths, it is therefore necessary to carry out deeper into grind
Study carefully and develop, prepares a kind of small line footpath wire cable material of low-smoke bittern-free highly fire-proof.
Invention content
The object of the present invention is to provide a kind of small line footpath wire cable materials of low-smoke bittern-free highly fire-proof, solve in the prior art
There are the problem of, the wire cable material not only have high flame retardant, while also have excellent mechanical property and environmental-protecting performance.
It is a further object of the present invention to provide a kind of preparation methods of the small line footpath wire cable material of low-smoke bittern-free highly fire-proof.
The technical solution adopted in the present invention is a kind of small line footpath wire cable material of low-smoke bittern-free highly fire-proof, according to following
The quality parts ratio of raw material is made：40-60 parts of acetate-ethylene resin, 10-20 parts of polyethylene, 10-20 parts of ethylene-octene resin,
Maleic anhydride grafted ethene -10-20 parts of octene copolymer, 80-120 parts of fire retardant, 4-8 parts of fire retarding synergist, processing aid 4-
8,1-2 parts of crosslinking agent, 2-4 parts of antioxidant.
Further, the fire retarding synergist is zinc borate.
Further, the processing aid is that tripalmitin class synthesizes vegetable esters and silicone compounding, palmitin acid glycerol
It is 1 that esters, which synthesize vegetable esters with silicone mass ratio,：1.
Further, the crosslinking agent is cumyl peroxide.
Further, the antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters.
Another technical solution of the present invention is a kind of preparation of the small line footpath wire cable material of low-smoke bittern-free highly fire-proof
Method specifically follows the steps below：40-60 parts of acetate-ethylene resin, 10-20 parts of poly- second are weighed by mass fraction
Alkene, 10-20 parts of ethylene-octene resin, 10-20 parts of maleic anhydride grafted ethene-octene copolymer, 80-120 parts fire-retardant
Agent, 4-8 parts of fire retarding synergist, the processing aid of 4-8,1-2 parts of crosslinking agent, 2-4 parts of antioxidant；First by acetate-ethylene
Resin, polyethylene, ethylene-octene resin, maleic anhydride grafted ethene-octene copolymer are respectively placed in 40 DEG C -60 DEG C of baking oven
Acetate-ethylene resin, polyethylene, ethylene-octene resin, maleic anhydride are grafted second by middle dry 5-8h at 160-180 DEG C
Alkene-octene copolymer is blended in mixer, then rotating speed 90-110r/min sequentially adds crosslinking agent, antioxidant, processing
Auxiliary agent, fire retardant, fire retarding synergist, mixing time 15-25min；Mixing is obtained into material, is placed on mould in vulcanizing press
Pressure sets thickness of sample as 0.8mm, and molding temperature is 180-200 DEG C, clamp time 3-5min, then cold pressing sizing, cold pressing
Time is 3-5min.
Further, the fire retardant is the magnesium hydroxide of the DOPA modifications of UV crosslinking PETA claddings, passes through following step
It is rapid to prepare：Solvent is water, and temperature is 60 DEG C, weighs 25g 9, the miscellaneous phenanthrene -10- oxides of the miscellaneous -10- phosphinylidynes of 10- dihydro-9-oxies are put
Enter into 250mL three-necked flasks, 75mL hydrogen peroxide is added dropwise, is warming up to 60 DEG C, after dripping hydrogen peroxide, temperature is raised to
It 70-80 DEG C, reacting 7-8 hours, after the completion of reaction, solution is cooled to room temperature, normal pressure filters, and 3 filter cakes are washed with acetone, then
It is put into 50-60 DEG C of drying in oven, obtains DOPA；DOPA the and 100g magnesium hydroxides for weighing 15g are added in three-necked flask, amount
It is that 99.5% ethyl alcohol is added in three-necked flask to take 180mL purity, under nitrogen protection, is warming up to 70-80 DEG C, mechanical agitation
Reaction 10-12 hours；After the completion of reaction, white is presented in solution, and normal pressure filters, then is distinguished successively with acetone, deionized water, ethyl alcohol
Product for several times is washed, the solid matter of white is finally obtained；White solid matter is put into 70-90 DEG C of baking oven drying, is obtained
DOPA- magnesium hydroxides (DOPA-MH)；Be added in 500mL three-necked flasks PETA30g, by benzophenone and triethanolamine according to
Mass ratio is 1：1g photosensitizers made from 1 are dissolved in the ethyl alcohol that 32g purity is 99.5%, and 50g DOPA- magnesium hydroxides is uniform
It is scattered in above-mentioned solution, gained uniform suspension, which is coated on glass slide, forms about 1mm thick coatings, and it is solid to be sent into UV light room
To change, condition of cure is ultraviolet intensity of light 100%, and lamp is 3 minutes away from 10cm, irradiation time, scrapes coating after the completion of solidification,
Grinding, obtains PETA-DOPA-MH.
Beneficial effects of the present invention：Raw material is easy to get, of low cost, and processing method is simple, and fire retardant used is Halogen ring
It is pungent that maleic anhydride grafted ethene-is added by the compound of acetate-ethylene resin, polyethylene and ethylene-octene in guarantor's type fire retardant
Alkene copolymer increase-volume, in filling modified flame-retardant agent appropriate, fire retarding synergist, processing aid, antioxidant, crosslinking agent, to make
Prepared material has high tensile, high flame resistance, and low smoke and zero halogen environmental protection in the case where thickness of sample is very thin.
Description of the drawings
Fig. 1 is DOPO oxidation reactions signal formula figure.
Fig. 2 is the infrared figure of gained DOPA after DOPO oxidations prepared by the present invention.
The infrared figure of DOPA modified magnesium hydroxides prepared by Fig. 3 present invention.
The preparation process of Fig. 4 PETA-DOPA-MH.
The SEM of PETA-DOPA-MH prepared by Fig. 5 present invention schemes.
Specific implementation mode
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
A kind of small line footpath wire cable material of low-smoke bittern-free highly fire-proof is made according to the quality parts ratio of following raw material：
40-60 parts of acetate-ethylene resin
10-20 parts of polyethylene
10-20 parts of ethylene-octene resin
Maleic anhydride grafted ethene -10-20 parts of octene copolymer
80-120 parts of fire retardant
4-8 parts of fire retarding synergist
4-8 parts of processing aid
1-2 parts of crosslinking agent
2-4 parts of antioxidant
Wherein, in ethylene-vinyl acetate resin, the mass content of vinyl acetate is 16-28%, has higher fracture
Elongation, about 950% help to improve the elongation at break of the cable material, meanwhile, tensile strength is about 18MPa.In order to
Obtaining preferable elongation at break, tensile property is unlikely too low simultaneously, and it is 40-60 parts that this system, which selects addition number,.If content
Too low, then the elongation at break of final material is low；And too high levels, then the tensile property decline of final material is excessive.
Polyethylene has preferable tensile strength, and tensile strength values are about 25MPa, can improve the wire cable material
Tensile property, while polyethylene contributes to the raising of hot press performance.For prominent polyethylene to stretching and heat in substrate mixture
Press the contribution of performance, this system selection 10-20 parts of number of addition.If content is too low, final material cannot be effectively promoted
Stretching and hot press performance, and under too high polymerized ethylene content, poor inorganic fill performance will greatly damage final material
The elongation at break of material.
Ethylene-octene resin has preferable stretching and elongation at break, especially has lower hardness, shore hardness
Value is less than 80, can effectively reduce the hardness of wire cable material product.In order to obtain preferable material hardness, this system selection addition
10-20 parts of ethylene-octene, excessive ethylene-octene will make material hardness too low, and cannot meet thermal deformation requirement under high temperature.
Maleic anhydride grafted ethene-octene copolymer can effectively increase-volume acetate-ethylene resin, polyethylene and ethylene-be pungent
Alkene, so as to improve the wire cable material mechanical property.To improve the compatibility of organism material, this system selection addition maleic anhydride
Grafted ethene -10-20 parts of octene copolymer number.It, cannot the effective increase-volume blending matrix system if its content is too low；Contain
Measure excessively high, then the mechanical property of system can be decreased obviously, and viscosity will substantially reduce, and be unfavorable for the processability of material.
Fire retardant is the magnesium hydroxide (PETA-DOPA-MH) that the DOPA of UV crosslinking PETA claddings is modified, and DOPA changes
The flame retardant property of kind magnesium hydroxide and its compatibility with matrix, then coated by the crosslinking of PETA, further improve fire retardant
The compatibility of DOPA-MH and basis material, while also further improving its anti-flammability.
PETA-DOPA-MH prepares corresponding process analysis procedure analysis and sees attached drawing 1-5.
Fig. 1 is the schematic process that DOPO oxidations generate DOPA, and the solvent of this reaction is water, and temperature is 60 DEG C.Weigh 25g
Miscellaneous phenanthrene -10- the oxides (DOPO) of the miscellaneous -10- phosphinylidynes of (0.115mol) 9,10- dihydro-9-oxies, are put into 250mL three-necked flasks,
75mL (0.95mol) hydrogen peroxide is added dropwise, is warming up to 60 DEG C.After dripping hydrogen peroxide, temperature is raised to 70-80 DEG C, reaction
7-8 (embodiment 1-3 is selected respectively, 7,7.5,8 hours) hours.After the completion of reaction, solution is cooled to room temperature.Normal pressure filters,
3 filter cakes are washed with acetone, it is for use to place into 50-60 DEG C of (embodiment 1-3 is selected respectively, 50,55,60 DEG C) drying in oven.
Fig. 2 is the infrared spectrogram of DOPO and DOPA.DOPO generates DOPA by hydrolysis, can be with from DOPO curves
Find out, is the stretching vibration absworption peak of P-H keys at 2380 and 2402cm-1.In DOPA curves, the stretching vibration absworption peak of P-H
It dies down or even disappears, and occur apparent P-OH stretching vibration absworption peaks at 950-1000cm-1.DOPO and DOPA exist
The absorption vibration peak of other positions has almost no change, and thus proves that DOPO hydrolysis generates DOPA.
Fig. 3 is the infrared spectrogram of MH and DOPA-MH.It weighs 15gDOPA and 100g magnesium hydroxides (MH) and is added to three mouthfuls
In flask, the ethyl alcohol for measuring 180mL is added in three-necked flask, under nitrogen protection, is warming up to 70-80 DEG C, mechanical agitation is anti-
It answers 10-12 hours；After the completion of reaction, white is presented in solution, and normal pressure filters, then is distinguished successively with acetone, deionized water and ethyl alcohol
Product for several times is washed, the solid matter of white is finally obtained；White solid matter is put into 70-90 DEG C of baking oven drying, for use.
Product is analyzed to obtain the final grafting rates of DOPA to be about 70% through element test.Surface is carried out using DOPA to MH to change
Property, has obtained corresponding modified product DOPA-MH, wherein the variation of each major absorbance peak and being attributed to：1450-1650cm-1
(Ph-H), 1210cm-1 (P=O), 950-1000cm-1 (P-OH), 1050-1400cm-1 (P-O).Wherein 1050-1400cm-1
The appearance of the P-O vibration absorption peaks at place can tentatively be inferred to DOPA and MH and condensation reaction has occurred.
Fig. 4 is the preparation process schematic diagram of PETA-DOPA-MH.PETA30g, photosensitizer are added in 500mL three-necked flasks
(according to mass ratio it is 1 by benzophenone and triethanolamine：1 is made) 1g is dissolved in the absolute ethyl alcohol that 32g purity is 99.5%, and incites somebody to action
50g DOPA-MH are dispersed in above-mentioned solution, and gained uniform suspension, which is coated on glass slide, forms about 1mm thick coatings,
It is sent into the solidification of UV light room, condition of cure is ultraviolet intensity of light 100%, and for lamp away from 10cm, irradiation time is 3 minutes.Solidification
Coating is scraped after the completion, grinds, obtains PETA-DOPA-MH.
Fig. 5 shows that the surfaces PETA-DOPA-MH of gained are obviously more coarse, this should be the UV crosslinking due to PETA
It is caused.SEM proves that the surface cladding of PETA is successful.
Fire retarding synergist is zinc borate, and the synergist synergistic effect is good, and has industrialized maturation.Its usual additive amount is in matter
It is with obvious effects when amount score 2% or so, so this system has selected the additive amount of zinc borate for 4-8 parts.Its content is very few, cannot
Generate the effect of fire-retardant synergistic；Content is excessive, then so that flame retardant property is declined, while the mechanical property of material will also decline.
Processing aid is compounded using environment-friendly type macromolecule synthesis vegetable esters with silicone, i.e., does not influence flame retardant property, also environmentally friendly
Economy, and efficiently improve processing performance.The addition number of the processing aid is 4-8 parts.When additive amount is too low, processing performance changes
Kind unobvious, and when additive amount is too big, flame retardant property and mechanical property will be decreased obviously.
Crosslinking agent is peroxide, and crosslinking condition is simple.When heating, peroxide is decomposed into the very high trip of chemism
From base, these free radicals capture the hydrogen atom in molecular polyolefin, and it is reactive radical species to make certain carbon atoms of polyolefin backbone
And be combined with each other, that is, generate C-C cross-bonds, the webbed macromolecular structure of shape.It can effectively improve by the crosslinking of peroxide
Tensile strength.The addition number of the crosslinking agent is 1-2 parts.When usual peroxide deficiency, it cannot effectively make polymer network
It fully constitutes, causes mechanical property that cannot be obviously improved；When peroxide excess, the mechanical property of material will be also decreased obviously.
Antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters (1010), and the product is easy
It obtains, industrialization is ripe, cheap.With other antioxidant ratios, cost can be suitably reduced.The effect of antioxidant is to prevent from processing
Thermal degradation in the process, while promoting its Long-Term Properties.The addition number of the antioxidant is 2-4 parts.If its content is too low,
Then process will appear thermal decomposition, influence the color and mechanical property of final material；It, will as inorganic filler when too high levels
Material mechanical performance is set to decline.
A kind of preparation method of the small line footpath wire cable material of low-smoke bittern-free highly fire-proof, specifically follows the steps below：
Weigh 40-60 parts of acetate-ethylene resin by mass fraction, 10-20 parts of polyethylene, 10-20 parts of ethylene-is pungent
Olefine resin, 10-20 parts of maleic anhydride grafted ethene-octene copolymer, 80-120 parts of fire retardant, 4-8 parts of fire-retardant synergistic
Agent, the processing aid of 4-8,1-2 parts of crosslinking agent, 2-4 parts of antioxidant；
First by acetate-ethylene resin, polyethylene, ethylene-octene resin, maleic anhydride grafted ethene-octene copolymer point
Dry 5-8h is not placed in 40 DEG C -60 DEG C of baking oven, by acetate-ethylene resin, polyethylene, ethylene-octene at 160-180 DEG C
Resin, maleic anhydride grafted ethene-octene copolymer are blended in mixer, then rotating speed 90-110r/min is sequentially added
Crosslinking agent, antioxidant, processing aid, fire retardant, fire retarding synergist, mixing time 15-25min.Mixing is obtained into material, is put
It is molded in vulcanizing press, sets thickness of sample as 0.8mm, molding temperature is 180-200 DEG C, clamp time 3-5min
(being free of preheating time), then cold pressing sizing, cold pressing time are 3-5min.
Wherein, fire retardant is the magnesium hydroxide (PETA-DOPA-MH) of the DOPA modifications of UV crosslinking PETA claddings.
Fire retarding synergist is zinc borate.
Crosslinking agent is organic peroxide.The present invention has selected cumyl peroxide DCP as crosslinking agent.If using
Other organic peroxy objects, then last product electrical insulating property is bad.
Antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters.
Processing aid is that environment-friendly type macromolecule synthesizes vegetable esters and silicone compounding.It is by natural oil and alcohol to synthesize vegetable esters
The ester products of gained after progress ester exchange reaction mainly have glycerol stearate esters synthesis vegetable esters, tripalmitin class to close
Vegetable esters are synthesized at vegetable esters and oleic esters.What the present invention selected is tripalmitin class synthesis vegetable esters and silicone
Compounding.It is 1 that tripalmitin class, which synthesizes vegetable esters with silicone mass ratio,：1.
In above-mentioned steps, in 40 DEG C -60 DEG C of baking oven when dry 5-8h.If temperature is too low, then the moisture content in raw material
Cannot be cleared, and drying time is long, efficiency is low, and when the temperature is excessively high, raw material can be caused heated for a long time and certain journey occur
Heat ageing is spent, the final comprehensive performance of material, and high energy consumption when the temperature is excessively high are influenced.
Blending temperature is set in 160-180 DEG C.If mixing temperature is too low, blend melt viscosity is too high, is unfavorable for
It is final to influence material prepared for the full and uniform mixing of various ingredients, and temperature is too high, is easy to make some materials thermal degradation
Flame retardant property and mechanical property.
The time of molding cannot be too short, if too short, part pellet cannot be melted fully, and exhaust effect can be caused bad,
The defect for occurring similar crackle in plank, influences the quality of plank.Overlong time can cause to decompose under material at high temperature, necessarily affect
The comprehensive performance of material.
If order of addition of the material of the present invention in preparation process arbitrarily adjusts, the final items of material can be influenced
Energy.For example, if the order of addition of crosslinking agent and fire retardant exchanged, when adding crosslinking agent, polymer material, which decomposes, to be generated
Reactive radical species will be difficult to generate the crosslinking of carbon carbon due to the presence of a large amount of auxiliary agents of addition in advance, to which macromolecule cannot be formed
Network structure.Compared with not exchanging order of addition resulting materials, prepared composite materials property after exchange order of addition
It will substantially reduce.
Embodiment 1
40 parts of acetate-ethylene resin, 20 parts of polyethylene, 20 parts of ethylene-octene resin, maleic anhydride grafted ethene-octene
20 parts of copolymer, 80 parts of fire retardant, 4 parts of fire retarding synergist, processing aid 4,1 part of crosslinking agent, 4 parts of antioxidant.
First by acetate-ethylene resin, polyethylene, ethylene-octene resin, maleic anhydride grafted ethene-octene copolymer point
Dry 6h is not placed in 50 DEG C of baking oven, first by acetate-ethylene resin, polyethylene, ethylene-octene resin, Malaysia at 170 DEG C
Anhydride grafted ethylene-octene copolymer is blended in mixer, then rotating speed 100r/min sequentially adds peroxidating diisopropyl
Benzene, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, silicone processing aid, tripalmitin
Class synthesizes vegetable esters processing aid, PETA-DOPA-MH, zinc borate, mixing time 20min.Mixing is obtained into material, is placed on
It is molded in vulcanizing press, sets thickness of sample as 0.8mm, molding temperature is 190 DEG C, and clamp time is 3min (without preheating
Time), then cold pressing sizing, the cold pressing time is 3min.
Embodiment 2
60 parts of acetate-ethylene resin, 10 parts of polyethylene, 10 parts of ethylene-octene resin, maleic anhydride grafted ethene-octene
0 part of copolymer 1,120 parts of fire retardant, 8 parts of fire retarding synergist, processing aid 8,2 parts of crosslinking agent, 2 parts of antioxidant.
First by acetate-ethylene resin, polyethylene, ethylene-octene resin, maleic anhydride grafted ethene-octene copolymer point
Dry 8h is not placed in 40 DEG C of baking oven, first by acetate-ethylene resin, polyethylene, ethylene-octene resin, Malaysia at 160 DEG C
Anhydride grafted ethylene-octene copolymer is blended in mixer, then rotating speed 110r/min sequentially adds crosslinking agent, antioxygen
Agent, silicone processing aid synthesize plant esters processing aid, fire retardant, fire retarding synergist, mixing time 25min.It will mix
Refining obtains material, is placed in vulcanizing press and is molded, and sets thickness of sample as 0.8mm, molding temperature is 180 DEG C, clamp time
For 3min (being free of preheating time), then cold pressing sizing, the cold pressing time is 3min.
Embodiment 3
50 parts of acetate-ethylene resin, 15 parts of polyethylene, 15 parts of ethylene-octene resin, maleic anhydride grafted ethene-octene
5 parts of copolymer 1,100 parts of fire retardant, 6 parts of fire retarding synergist, processing aid 6,1.5 parts of crosslinking agent, 3 parts of antioxidant.
First by acetate-ethylene resin, polyethylene, ethylene-octene resin, maleic anhydride grafted ethene-octene copolymer point
Dry 5h is not placed in 60 DEG C of baking oven, first by acetate-ethylene resin, polyethylene, ethylene-octene resin, Malaysia at 180 DEG C
Anhydride grafted ethylene-octene copolymer is blended in mixer, then rotating speed 90r/min sequentially adds crosslinking agent, antioxygen
Agent, silicone processing aid synthesize plant esters processing aid, fire retardant, fire retarding synergist, mixing time 15min.It will mix
Refining obtains material, is placed in vulcanizing press and is molded, and sets thickness of sample as 0.8mm, molding temperature is 200 DEG C, clamp time
For 5min (being free of preheating time), then cold pressing sizing, the cold pressing time is 5min.
Embodiment 4
60 parts of acetate-ethylene resin, 10 parts of polyethylene, 20 parts of ethylene-octene resin, maleic anhydride grafted ethene-octene
0 part of copolymer 1,80 parts of fire retardant, 4 parts of fire retarding synergist, processing aid 4,1 part of crosslinking agent, 4 parts of antioxidant.
First by acetate-ethylene resin, polyethylene, ethylene-octene resin, maleic anhydride grafted ethene-octene copolymer point
Dry 6h is not placed in 50 DEG C of baking oven, first by acetate-ethylene resin, polyethylene, ethylene-octene resin, Malaysia at 170 DEG C
Anhydride grafted ethylene-octene copolymer is blended in mixer, then rotating speed 100r/min sequentially adds crosslinking agent, antioxygen
Agent, silicone processing aid synthesize plant esters processing aid, fire retardant, fire retarding synergist, mixing time 20min.It will mix
Refining obtains material, is placed in vulcanizing press and is molded, and sets thickness of sample as 0.8mm, molding temperature is 190 DEG C, clamp time
For 3min (being free of preheating time), then cold pressing sizing, the cold pressing time is 3min.
Embodiment 5
60 parts of acetate-ethylene resin, 10 parts of polyethylene, 20 parts of ethylene-octene resin, maleic anhydride grafted ethene-octene
0 part of copolymer 1,100 parts of fire retardant, 4 parts of fire retarding synergist, processing aid 4,1 part of crosslinking agent, 4 parts of antioxidant.
First by acetate-ethylene resin, polyethylene, ethylene-octene resin, maleic anhydride grafted ethene-octene copolymer point
Dry 6h is not placed in 50 DEG C of baking oven, first by acetate-ethylene resin, polyethylene, ethylene-octene resin, Malaysia at 170 DEG C
Anhydride grafted ethylene-octene copolymer is blended in mixer, then rotating speed 100r/min sequentially adds crosslinking agent, antioxygen
Agent, silicone processing aid synthesize plant esters processing aid, fire retardant, fire retarding synergist, mixing time 20min.It will mix
Refining obtains material, is placed in vulcanizing press and is molded, and sets thickness of sample as 0.8mm, molding temperature is 190 DEG C, clamp time
For 3min (being free of preheating time), then cold pressing sizing, the cold pressing time is 3min.
Embodiment 6
60 parts of acetate-ethylene resin, 10 parts of polyethylene, 20 parts of ethylene-octene resin, maleic anhydride grafted ethene-octene
0 part of copolymer 1,100 parts of fire retardant, 8 parts of fire retarding synergist, processing aid 4,1 part of crosslinking agent, 4 parts of antioxidant.
First by acetate-ethylene resin, polyethylene, ethylene-octene resin, maleic anhydride grafted ethene-octene copolymer point
Dry 6h is not placed in 50 DEG C of baking oven, first by acetate-ethylene resin, polyethylene, ethylene-octene resin, Malaysia at 170 DEG C
Anhydride grafted ethylene-octene copolymer is blended in mixer, then rotating speed 100r/min sequentially adds crosslinking agent, antioxygen
Agent, silicone processing aid synthesize plant esters processing aid, fire retardant, fire retarding synergist, mixing time 20min.It will mix
Refining obtains material, is placed in vulcanizing press and is molded, and sets thickness of sample as 0.8mm, molding temperature is 190 DEG C, clamp time
For 3min (being free of preheating time), then cold pressing sizing, the cold pressing time is 3min.
Embodiment 7
60 parts of acetate-ethylene resin, 10 parts of polyethylene, 20 parts of ethylene-octene resin, maleic anhydride grafted ethene-octene
0 part of copolymer 1,120 parts of fire retardant, 4 parts of fire retarding synergist, processing aid 4,1 part of crosslinking agent, 4 parts of antioxidant.
First by acetate-ethylene resin, polyethylene, ethylene-octene resin, maleic anhydride grafted ethene-octene copolymer point
Dry 6h is not placed in 50 DEG C of baking oven, first by acetate-ethylene resin, polyethylene, ethylene-octene resin, Malaysia at 170 DEG C
Anhydride grafted ethylene-octene copolymer is blended in mixer, then rotating speed 100r/min sequentially adds crosslinking agent, antioxygen
Agent, silicone processing aid synthesize plant esters processing aid, fire retardant, fire retarding synergist, mixing time 20min.It will mix
Refining obtains material, is placed in vulcanizing press and is molded, and sets thickness of sample as 0.8mm, molding temperature is 190 DEG C, clamp time
For 3min (being free of preheating time), then cold pressing sizing, the cold pressing time is 3min.
Embodiment 8
60 parts of acetate-ethylene resin, 10 parts of polyethylene, 20 parts of ethylene-octene resin, maleic anhydride grafted ethene-octene
0 part of copolymer 1,120 parts of fire retardant, 8 parts of fire retarding synergist, processing aid 4,1 part of crosslinking agent, 4 parts of antioxidant.
First by acetate-ethylene resin, polyethylene, ethylene-octene resin, maleic anhydride grafted ethene-octene copolymer point
Dry 6h is not placed in 50 DEG C of baking oven, first by acetate-ethylene resin, polyethylene, ethylene-octene resin, Malaysia at 170 DEG C
Anhydride grafted ethylene-octene copolymer is blended in mixer, then rotating speed 100r/min sequentially adds crosslinking agent, antioxygen
Agent, silicone processing aid synthesize plant esters processing aid, fire retardant, fire retarding synergist, mixing time 20min.It will mix
Refining obtains material, is placed in vulcanizing press and is molded, and sets thickness of sample as 0.8mm, molding temperature is 190 DEG C, clamp time
For 3min (being free of preheating time), then cold pressing sizing, the cold pressing time is 3min.
Embodiment 9
60 parts of acetate-ethylene resin, 10 parts of polyethylene, 20 parts of ethylene-octene resin, maleic anhydride grafted ethene-octene
0 part of copolymer 1,120 parts of fire retardant, 4 parts of fire retarding synergist, processing aid 8,1 part of crosslinking agent, 4 parts of antioxidant.
First by acetate-ethylene resin, polyethylene, ethylene-octene resin, maleic anhydride grafted ethene-octene copolymer point
Dry 6h is not placed in 50 DEG C of baking oven, first by acetate-ethylene resin, polyethylene, ethylene-octene resin, Malaysia at 170 DEG C
Anhydride grafted ethylene-octene copolymer is blended in mixer, then rotating speed 100r/min sequentially adds crosslinking agent, antioxygen
Agent, silicone processing aid synthesize plant esters processing aid, fire retardant, fire retarding synergist, mixing time 20min.It will mix
Refining obtains material, is placed in vulcanizing press and is molded, and sets thickness of sample as 0.8mm, molding temperature is 190 DEG C, clamp time
For 3min (being free of preheating time), then cold pressing sizing, the cold pressing time is 3min.
Embodiment 10
60 parts of acetate-ethylene resin, 10 parts of polyethylene, 20 parts of ethylene-octene resin, maleic anhydride grafted ethene-octene
0 part of copolymer 1,100 parts of fire retardant, 4 parts of fire retarding synergist, processing aid 4,2 parts of crosslinking agent, 4 parts of antioxidant.
First by acetate-ethylene resin, polyethylene, ethylene-octene resin, maleic anhydride grafted ethene-octene copolymer point
Dry 6h is not placed in 50 DEG C of baking oven, first by acetate-ethylene resin, polyethylene, ethylene-octene resin, Malaysia at 170 DEG C
Anhydride grafted ethylene-octene copolymer is blended in mixer, then rotating speed 100r/min sequentially adds crosslinking agent, antioxygen
Agent, silicone processing aid synthesize plant esters processing aid, fire retardant, fire retarding synergist, mixing time 20min.It will mix
Refining obtains material, is placed in vulcanizing press and is molded, and sets thickness of sample as 0.8mm, molding temperature is 190 DEG C, clamp time
For 3min (being free of preheating time), then cold pressing sizing, the cold pressing time is 3min.
Embodiment 11
60 parts of acetate-ethylene resin, 10 parts of polyethylene, 20 parts of ethylene-octene resin, maleic anhydride grafted ethene-octene
0 part of copolymer 1,100 parts of fire retardant, 4 parts of fire retarding synergist, processing aid 4,1 part of crosslinking agent, 2 parts of antioxidant.
First by acetate-ethylene resin, polyethylene, ethylene-octene resin, maleic anhydride grafted ethene-octene copolymer point
Dry 6h is not placed in 50 DEG C of baking oven, first by acetate-ethylene resin, polyethylene, ethylene-octene resin, Malaysia at 170 DEG C
Anhydride grafted ethylene-octene copolymer is blended in mixer, then rotating speed 100r/min sequentially adds crosslinking agent, antioxygen
Agent, silicone processing aid synthesize plant esters processing aid, fire retardant, fire retarding synergist, mixing time 20min.It will mix
Refining obtains material, is placed in vulcanizing press and is molded, and sets thickness of sample as 0.8mm, molding temperature is 190 DEG C, clamp time
For 3min (being free of preheating time), then cold pressing sizing, the cold pressing time is 3min.
Table 1 is testing of materials standard and results of property
As it can be seen from table 1 product good combination property of the present invention, wherein embodiment 7 show best comprehensive performance.
The example products obtained therefrom tensile strength is more than 11MPa, and elongation at break reaches 450%；Flame Retardancy is good, can pass through
The vertical burn test of 0.8mm thickness samples, and can be tested by VW-1, oxygen index (OI) 33.Material electric property is good, and dielectric is strong
Degree is about 25MV/m.In addition, the density of material is small, only 1.6g/cm3, high temperature anti-stress cracking is good, and shore hardness is also only
91A。
Claims (1)
1. a kind of small line footpath wire cable material of low-smoke bittern-free highly fire-proof, which is characterized in that according to the quality parts ratio of following raw material
It is made：
60 parts of ethylene-vinyl acetate resin, 10 parts of polyethylene, 20 parts of ethylene-octene resin, maleic anhydride grafted ethene-octene
0 part of copolymer 1,120 parts of fire retardant, 4 parts of fire retarding synergist, 4 parts of processing aid, 1 part of crosslinking agent, 4 parts of antioxidant；
The fire retarding synergist is zinc borate；
The processing aid is that tripalmitin class synthesizes vegetable esters and silicone compounding, and tripalmitin class synthesizes vegetable esters
It is 1 with silicone mass ratio：1；
The crosslinking agent is cumyl peroxide；
The antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters；
Specifically follow the steps below：
60 parts of ethylene-vinyl acetate resin, 10 parts of polyethylene, 20 parts of ethylene-octene resin, maleic anhydride are weighed by mass fraction
10 parts of grafted ethene-octene copolymer, 120 parts of fire retardant, 4 parts of fire retarding synergist, processing aid 4,1 part of crosslinking agent, antioxidant 4
Part；
First by ethylene-vinyl acetate resin, polyethylene, ethylene-octene resin, maleic anhydride grafted ethene-octene copolymer point
Be not placed in 50 DEG C of baking oven dry 6h, at 170 DEG C first by ethylene-vinyl acetate resin, polyethylene, ethylene-octene resin,
Maleic anhydride grafted ethene-octene copolymer is blended in mixer, then rotating speed 100r/min sequentially adds crosslinking agent,
Antioxidant, processing aid, fire retardant, fire retarding synergist, mixing time 20min；Mixing is obtained into material, is placed on compression molding
It is molded in machine, sets thickness of sample as 0.8mm, molding temperature is 190 DEG C, clamp time 3min, then cold pressing sizing, cold pressing
Time is 3min；
The fire retardant is the magnesium hydroxide that the DOPA of UV crosslinking PETA claddings is modified, and is prepared by following steps：
Solvent is water, and temperature is 60 DEG C, weighs 25g 9, the miscellaneous phenanthrene -10- oxides of the miscellaneous -10- phosphinylidynes of 10- dihydro-9-oxies are put into
In 250mL three-necked flasks, 75mL hydrogen peroxide is added dropwise, is warming up to 60 DEG C, after dripping hydrogen peroxide, temperature is raised to 70-80 DEG C,
Reaction 7-8 hours, after the completion of reaction, solution is cooled to room temperature, and normal pressure filters, and washs 3 filter cakes with acetone, places into 50-
60 DEG C of drying in oven, obtain DOPA；
DOPA the and 100g magnesium hydroxides for weighing 15g are added in three-necked flask, are measured the ethyl alcohol that 180mL purity is 99.5% and are added
Enter into three-necked flask, under nitrogen protection, is warming up to 70-80 DEG C, mechanic whirl-nett reaction 10-12 hours；It is molten after the completion of reaction
White is presented in liquid, and normal pressure filters, then washs product for several times respectively successively with acetone, deionized water, ethyl alcohol, finally obtains white
Solid matter；White solid matter is put into 70-90 DEG C of baking oven drying, obtains DOPA-MH；
PETA 30g is added in 500mL three-necked flasks, according to mass ratio is 1 by benzophenone and triethanolamine：1g made from 1
Photosensitizer is dissolved in 32g purity and is 99.5% ethyl alcohol, and 50g DOPA-MH are dispersed in above-mentioned solution, and gained suspends
Liquid is spread evenly across formation 1mm thick coatings on glass slide, is sent into the solidification of UV light room, and condition of cure is ultraviolet intensity of light
100%, lamp is 3 minutes away from 10cm, irradiation time, scrapes coating after the completion of solidification, is ground, and obtains PETA claddings
DOPA-MH, i.e. PETA-DOPA-MH.
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| CN108430550B (en) | 2016-01-25 | 2021-03-16 | 菲利普莫里斯生产公司 | Cartridge assembly having an actuating portion |
| CN105885188A (en) * | 2016-05-03 | 2016-08-24 | 山东泰开高分子材料有限公司 | Preparation and using method of chemical crosslinking low-smoke halogen-free flame-retardant polyolefin composite material |
| CN107189195A (en) * | 2017-05-08 | 2017-09-22 | 天长市通联焊业有限公司 | A kind of LSOH anti-flaming insulated cable material |
| CN112646260A (en) * | 2020-12-21 | 2021-04-13 | 四川东材科技集团股份有限公司 | Preparation method of flame-retardant antistatic ethylene-vinyl acetate copolymer composite material |
| CN113185796A (en) * | 2021-05-17 | 2021-07-30 | 江苏北化新橡新材料科技有限公司 | 125 ℃ halogen-free flame-retardant cable material capable of self-crosslinking at room temperature and preparation method thereof |
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| CN103087377A (en) * | 2011-11-08 | 2013-05-08 | 上海特缆电工科技有限公司 | Nuclear power 1E-grade K3-class heat-shrinkable tubing material and preparation thereof |
| CN103467832A (en) * | 2013-06-03 | 2013-12-25 | 公安部四川消防研究所 | Low temperature-resistant flexible crosslinkable halogen-free flame retardant cable material and preparation method thereof |
| CN103483670A (en) * | 2013-10-10 | 2014-01-01 | 长园集团股份有限公司 | 150 DEG C high-flame-retardant halogen-free red phosphorus-free modified material |
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| CN103087377A (en) * | 2011-11-08 | 2013-05-08 | 上海特缆电工科技有限公司 | Nuclear power 1E-grade K3-class heat-shrinkable tubing material and preparation thereof |
| CN103467832A (en) * | 2013-06-03 | 2013-12-25 | 公安部四川消防研究所 | Low temperature-resistant flexible crosslinkable halogen-free flame retardant cable material and preparation method thereof |
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