CN108690293A - A kind of high-low temperature resistant high strength PVC cable material - Google Patents
A kind of high-low temperature resistant high strength PVC cable material Download PDFInfo
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- CN108690293A CN108690293A CN201810623035.9A CN201810623035A CN108690293A CN 108690293 A CN108690293 A CN 108690293A CN 201810623035 A CN201810623035 A CN 201810623035A CN 108690293 A CN108690293 A CN 108690293A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- 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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Abstract
The present invention relates to a kind of cable material more particularly to a kind of high-low temperature resistant high strength PVC cable materials.The CABLE MATERIALS includes following components in parts by weight:1-3 parts of 100 parts of polyvinyl chloride resin, silicon rubber/30 ~ 45 parts of EPDM blended rubber, 25-40 parts of amido silicon oil, 20-45 parts of epoxy group polysilsesquioxane, 3-8 parts of silane coupling agent, 1-3 parts of lubricant and antioxidant.The present invention has the advantages that:(1)High and low temperature resistance and weatherability are good;(2)Obtained polyvinyl chloride resin CABLE MATERIALS excellent in mechanical performance;(3)Formula is simple of low cost, can be produced without changing existing equipment just, is suitble to large-scale production.
Description
Technical field
The present invention relates to a kind of cable material more particularly to a kind of high-low temperature resistant high strength PVC cable materials.
Background technology
It is basic resin, addition stabilizer, dioctyl phthalate, O-phthalic that PVC cable material, which is with polyvinyl chloride,
Sour diisodecyl ester, the inorganic fillers such as the plasticizer such as dioctyl terephthalate, trioctyl trimellitate (TOTM) and calcium carbonate, auxiliary agent
With the additives such as lubricant, the particle for squeezing out and preparing is mediated by mixture.
China's extremely frigid zones area accounts for about the 27.9% of territory total area, the areas such as northeast, Inner Mongol, northwest of energy abundance
High-cold regions are mostly in, and winter temperature is often less than -50 DEG C, how to improve the Low-Temperature Reliability of cable becomes urgently to be resolved hurrily
A key technical problem.The low-temperature impact brittle temperature of traditional PVC cable materials is much not achieved at -15 DEG C~-20 DEG C
Actual motion requirement.Cable insulate in the laid processes of extremely frigid zones and sheath suffers from damage, therefore these areas make
It is very necessary with low temperature resistant cable.With going deep into for upgrading urban and rural power grids, the demand of low temperature resistant PVC cable material can be got over
Come bigger.
In addition, polyvinyl chloride is poor to the stability of light, heat.Softening point is 80 DEG C, starts to decompose in 130 DEG C.It is being not added with
In the case of heat stabilizer, when 100 DEG C of polyvinyl chloride, starts to decompose, and 130 DEG C or more are decomposed faster.It is heated to decomposite releasing chlorine
Change hydrogen, (hydrogen chloride gas is toxic gas) makes its discoloration, by white → light yellow → red → brown → black.Sunlight
In ultraviolet light and oxygen can make polyvinyl chloride that photooxidation occur to decompose, thus the flexible of polyvinyl chloride is made to decline, last embrittlement.This
It is the reason of some PVC plastics will turn yellow, become fragile over time.
Such as a kind of a kind of low temperature resistant PVC cable material formula disclosed in Chinese patent literature, application publication number are
CN106519511A is made of the raw material below according to parts by weight:30~40 parts of polyvinyl chloride resin, ultra-low density polyethylene 10~
15 parts, 3~8 parts of β crystalline substances nucleating agent, 3~6 parts of polyolefin thermoplastic elastomer, 3~6 parts of octene ethylene copolymer, poly- glutaric acid the third two
5~8 parts of alcohol ester, 3~7 parts of POE elastic body toughenings agent, 1~3 part of antioxidant, 2~5 parts of silicon carbide fibre, nano barium sulfate 1~3
Part, 2~4 parts of zeolite with carrying silver, 2~5 parts of glass fibre, 4~10 parts of nano-titanium dioxide, 5~10 parts of magnesium hydroxide, toughener 1
~3 parts, 3~6 parts of paraffin, 3~5 parts of silane coupling agent, 1~4 part of plasticizer.Although the invention has resistance to low temperature,
Its specific resistance to low temperature does not have quantizating index, can not judge that it determines Applicable temperature, while the material in its formula is excessively
Complexity, cost is excessively high, good can not be used for practical application.
In another example a kind of one kind that disclosed flame-retardant modified polyvinyl chloride resin compound of light heat-resisting in Chinese patent literature is electric
Cable material and preparation method thereof, application publication number CN105482296A, the CABLE MATERIALS are made of the raw material of following parts by weight:
Polyvinyl chloride resin 55-65, ethylene-vinyl acetate copolymer 30-40, agate beautiful jade 0.01-0.02, expansible graphite 10-15, poly- four Asia are dragged
Propylene Glycol ether 5-8, alumina silicate 15-22, eleostearic acid 3-4, hexamethyl phenodiazine silane 3-4, cotton pulp 22-30, zinc stearate 2-
4, diethylene glycol dibenzoate 14-18, color masterbatch 8-10, auxiliary agent 2-3;Polyvinyl chloride resin and ethene-vinyl acetate are total to by the CABLE MATERIALS
Polymers, which is blended, is used as resin binder, and is used as filler using modified treated cotton pulp, in conjunction with improvement processing performance work(
The auxiliary agent of effect and other auxiliary materials so that the more traditional polyvinyl chloride resin of invention CABLE MATERIALS shows more excellent when in use
Heat-proof combustion-resistant performance.But it is added to more expansible graphite in resin binder, although its be provided with it is stronger fire-retardant
Performance, but since expansible graphite is electric conductor, its insulation performance can be greatly reduced by being added in CABLE MATERIALS as filler,
Lead to the generation of the danger such as electric leakage electric shock.
Invention content
The present invention is that can not have high and low temperature resistance in PVC cable material in the prior art simultaneously to overcome, formula group
Divide complicated defect with high costs, that decreasing insulating after fire-retardant filler is added, provides a kind of effective raising PVC cable material
High and low temperature resistance, formula is simple, and processing step of low cost is simple and a kind of high mechanics of high-low temperature resistant of good insulation preformance
Intensity PVC cable material.
In order to achieve the above objectives, the technical solution adopted by the present invention is as follows:
A kind of high-low temperature resistant high strength PVC cable material, the CABLE MATERIALS include following components in parts by weight:
It, can be effective using polyvinyl chloride resin and silicon rubber/EPDM blended rubber as basis material in the present invention
Improve the high and low temperature resistance and its processing performance of polyvinyl chloride resin.Addition amido silicon oil, can as plasticizer wherein simultaneously
The effective processability for improving whole resin.Epoxy group polysilsesquioxane can play the role of reinforcing filler, effectively
Enhancing CABLE MATERIALS mechanical property, ensure that its use intensity, while the epoxy group in epoxy group polysilsesquioxane can
Ring-opening reaction occurs with the amino in amido silicon oil, to be cured, forms network-like structure, further enhances its power
Learn performance.The addition of silane coupling agent enables to engage between each component more secured.
The silicon rubber used in the present invention/EPDM blended rubber, amido silicon oil and epoxy group polysilsesquioxane
Contain silicon oxygen bond in molecular backbone, there is characteristic:
(1) methyl sufficient on Si atoms gets up the polysiloxane backbone shielding of high-energy;
(2) C-H is nonpolarity, keeps intermolecular interaction very faint;
(3) Si-O bond distance is longer, and Si-O-Si key bond angles are big;
(4) Si-O keys are the covalent bonds with 50% ionic bond feature (for covalent bond with directionality, ionic bond is non-directional).
Therefore due to the unique structure of organosilicon, inorganic material and the performance of organic material have been had both, there is surface tension
The low, fundamental propertys such as viscosity-temperature coefficient is small, compressibility is high, gas permeability is high, and with high-low temperature resistant, electric insulation, resistance to oxidation
The excellent specific properties such as stability, weatherability, fire retardant, hydrophobic, corrosion-resistant, non-toxic and tasteless and physiological inertia, are widely used in aviation
The industries such as space flight, electric, building, transport, chemical industry, weaving, food, light industry, medical treatment.
Network-like structure is generated by the crosslinked action of amido silicon oil and epoxy group polysilsesquioxane in the present invention
There is silicone backbone network, can effectively improve mechanical property again while playing plasticization effect, while can incite somebody to action
Each component is fixedly connected in matrix resin, ensure that each component will not be lost in the variation of time and environment, is ensured
The stability in use of this CABLE MATERIALS.
Preferably, the melt index of the polyvinyl chloride resin is 1250~1450g/10min.
When the melt index of polyvinyl chloride resin is that 1250~1450g/10min its soft or hard degree is moderate, processability is good,
It is suitable as preparing the raw material of CABLE MATERIALS.
Preferably, the preparation method of the silicon rubber/EPDM blended rubber is as follows:
(a) synthesis of graft modification ethylene propylene diene rubber:100 parts of ethylene propylene diene rubber is taken in terms of parts by weight, is dissolved in 500 parts and is done
In dry toluene, 10-15 parts of maleic anhydride is added, is stirring evenly and then adding into 3 parts of BPO, increases temperature to 110 DEG C, flows back
Reaction 2-4 hours, is reduced to room temperature, reaction solution is poured into 1000 parts of methanol, separates out gum-like product, and drying obtains grafting and changes
Property ethylene propylene diene rubber;
(b) preparation of masterbatch:
(b1) preparation of EPDM masterbatch:It takes in 50 parts of ethylene propylene diene rubber and step (a) and obtains in parts by weight
To 50 parts of graft modification ethylene propylene diene rubber be placed in open mill and be kneaded, sequentially add methacryloxy trimethoxy
10 parts of 1.5 parts of base silane, 0.5 part of DCP, 0.5 part of antioxidant 264,20 parts of super abrasion furnace black and paraffin oil are kneaded into ternary
The preparation of the third masterbatch of second;
(b2) preparation of silicone master batch:40 parts of silicon rubber, 20 parts of super abrasion furnace black, zinc oxide 3 are taken in parts by weight
1.5 parts of part, 3 parts of iron oxide and methacryloxy trimethoxy silane are sequentially placed into open mill and are kneaded, and obtain
Silicone master batch;
(c) silicon rubber/EPDM blended rubber:It is 170 that the EPDM masterbatch obtained in step (b1), which is placed in roller temperature,
DEG C open mill in it is counter refine 3-4 times, be then added silicone master batch, logical 3-5 times thin after being kneaded uniformly, being subsequently placed in roller temperature is
2 parts of TMPTMA, thin logical 3-5 times rear slices of 3 parts of vulcanizer DCP and assistant crosslinking agent are added in 25-40 DEG C of open mill,
One step cure is carried out at 170 DEG C 10 minutes, be subsequently placed at 150 DEG C post vulcanization 60-120 minutes, obtain silicon rubber/ternary second
Third blended rubber.
Ethylene propylene diene rubber in silicon rubber/EPDM blended rubber have preferable ozone resistance, weatherability and write
Claim, be known as " free from flaw rubber ", other performances, such as heat-resisting, resistant to chemical media, UV resistant is also compared with other hydrocarbon rubber
It is excellent.In addition of low cost, price is cheap, thus in many departments, is especially had been widely used in automobile sector.At it
He needs in the rubber material of requirement high- and low-temperature resistance performance, and silicon rubber/EPDM blended rubber is because have both two kinds of rubber
Advantage and cost is relatively low shows its prosperous application prospect with its broad temperature in use and excellent mechanical property,
Widely paid attention to.
Preferably, the ammonia value of the amido silicon oil is 0.3-0.6, the amido silicon oil viscosity is 1000-
1500mm2/s。
Preferably, the preparation method of the epoxy group polysilsesquioxane is as follows:
1) 50 parts of vinyltrimethoxysilane under nitrogen protection, is taken in parts by weight, is dissolved in 200 parts of isopropanols,
Then 10-15 parts of sodium hydroxides are added, increase temperature to flowing back, back flow reaction 8-10 hours is obtained by filtration filter residue, is dissolved in
In tetrahydrofuran, glacial acetic acid is added dropwise thereto up to neutrality, tetrahydrofuran is evaporated off, obtains white powder, after washing 3-5 times, dries
It is dry to obtain eight vinyl polysilsesquioxanes;
2) it takes 10 parts of the eight vinyl polysilsesquioxane obtained in step 1) to be dissolved in 100 parts of chloroform, ice is added thereto
2 parts of 50 parts of acetic acid and the concentrated sulfuric acid increase temperature to after 70 DEG C, and 50-80 parts of Peracetic acid is added dropwise, and back flow reaction is after 4-8 hours,
It is washed to neutrality with saturated sodium carbonate solution and deionized water, revolving solvent obtains epoxy group polysilsesquioxane.
The first kind industrialized nanostructured chemicals when polysilsesquioxane nanostructured chemicals, it is believed that be
The most subtle particle of silica, but it and silica.Unlike organosilicon or other fillers, each poly- sesquialter silicon
Oxygen alkane nano molecular all has organo-functional group so that polysilsesquioxane nanostructure and polymer, biosystem and other
Surface is mutually compatible with, the mine that General polymeric objects system is mixed into using second generation nanometer composite technology occurred with early 1980s
Stone is compared with fillers such as clays, and it is good with polymeric system compatibility that polysilsesquioxane has, and processes simple advantage.
Polymer is modified by polysilsesquioxane, compared with matrix polymer, the infiltration of oxidation resistent susceptibility, gas
Property, glass transition temperature, thermal deformation and melt strength, modulus increase, it is especially the most notable with modulus increase, and it is stretched
Performance is basically unchanged, and can further expand the application range of resins for universal use and its plastic products, to generate objectively warp
Ji benefit.
Preferably, the silane coupling agent is vinyltriethoxysilane, methacryloxy trimethoxy
One kind in three tert-butyl peroxide silane of silane, methyl vinyl diethoxysilane or vinyl.
Preferably, the lubricant is one in magnesium stearate, calcium stearate, paraffin or cetomacrogol 1000
Kind.
Preferably, the antioxidant is in bisphenol-A, antioxidant CA, antioxidant 264 and triphenyl phosphite
It is a kind of.
Therefore, the present invention has the advantages that:(1) high and low temperature resistance and weatherability are good;(2) it obtains
Polyvinyl chloride resin CABLE MATERIALS excellent in mechanical performance;(3) formula is simple of low cost, can be produced without changing existing equipment just, is suitble to big
Large-scale production.
Specific implementation mode
Technical scheme of the present invention is made to further describe explanation below by specific embodiment.
If saying the raw material that the raw material of use is commonly used in the art without specified otherwise, in the embodiment of the present invention, implement
Method employed in example, is the conventional method of this field.
Embodiment 1
A kind of high-low temperature resistant high strength PVC cable material, the CABLE MATERIALS include following components in parts by weight:
Melt index is 100 parts of the polyvinyl chloride resin of 1250~1450g/10min;Silicon rubber/30 parts of EPDM blended rubber;Ammonia
25 parts of base silicone oil;20 parts of epoxy group polysilsesquioxane;3 parts of vinyltriethoxysilane;1 part of magnesium stearate;Bisphenol-A 1
Part.
Wherein, the preparation method of the silicon rubber/EPDM blended rubber is as follows:
(a) synthesis of graft modification ethylene propylene diene rubber:100 parts of ethylene propylene diene rubber is taken in terms of parts by weight, is dissolved in 500 parts and is done
In dry toluene, 10 parts of maleic anhydride is added, is stirring evenly and then adding into 3 parts of BPO, increases temperature to 110 DEG C, reflux is anti-
It answers 2 hours, is reduced to room temperature, reaction solution is poured into 1000 parts of methanol, separate out gum-like product, drying obtains graft modification three
First EP rubbers;
(b) preparation of masterbatch:
(b1) preparation of EPDM masterbatch:It takes in 50 parts of ethylene propylene diene rubber and step (a) and obtains in parts by weight
To 50 parts of graft modification ethylene propylene diene rubber be placed in open mill and be kneaded, sequentially add methacryloxy trimethoxy
10 parts of 1.5 parts of base silane, 0.5 part of DCP, 0.5 part of antioxidant 264,20 parts of super abrasion furnace black and paraffin oil are kneaded into ternary
The preparation of the third masterbatch of second;
(b2) preparation of silicone master batch:40 parts of silicon rubber, 20 parts of super abrasion furnace black, zinc oxide 3 are taken in parts by weight
1.5 parts of part, 3 parts of iron oxide and methacryloxy trimethoxy silane are sequentially placed into open mill and are kneaded, and obtain
Silicone master batch;
(c) silicon rubber/EPDM blended rubber:It is 170 that the EPDM masterbatch obtained in step (b1), which is placed in roller temperature,
DEG C open mill in it is counter refine 3 times, be then added silicone master batch, thin 3 times logical after being kneaded uniformly, it is 25 DEG C to be subsequently placed in roller temperature
Open mill in 3 parts of vulcanizer DCP and assistant crosslinking agent 2 parts of TMPTMA, thin logical 3-5 is added all over rear slices, at 170 DEG C
It carries out one step cure 10 minutes, is subsequently placed in post vulcanization 60 minutes at 150 DEG C, obtains silicon rubber/EPDM blended rubber.
The preparation method of the epoxy group polysilsesquioxane is as follows:
1) 50 parts of vinyltrimethoxysilane under nitrogen protection, is taken in parts by weight, is dissolved in 200 parts of isopropanols,
Then 10 parts of sodium hydroxides are added, increase temperature to flowing back, back flow reaction 8 hours is obtained by filtration filter residue, is dissolved in tetrahydrochysene furan
In muttering, glacial acetic acid is added dropwise thereto up to neutrality, tetrahydrofuran is evaporated off, obtains white powder, after washing 3 times, drying obtains eight
Vinyl polysilsesquioxane;
2) it takes 10 parts of the eight vinyl polysilsesquioxane obtained in step 1) to be dissolved in 100 parts of chloroform, ice is added thereto
2 parts of 50 parts of acetic acid and the concentrated sulfuric acid increase temperature to after 70 DEG C, 50 parts of Peracetic acid are added dropwise, back flow reaction is after 4 hours, with saturation
Sodium carbonate liquor and deionized water are washed to neutrality, and revolving solvent obtains epoxy group polysilsesquioxane.
Embodiment 2
A kind of high-low temperature resistant high strength PVC cable material, the CABLE MATERIALS include following components in parts by weight:
Melt index is 100 parts of the polyvinyl chloride resin of 1250~1450g/10min;Silicon rubber/45 parts of EPDM blended rubber;Ammonia
40 parts of base silicone oil;45 parts of epoxy group polysilsesquioxane;8 parts of methacryloxy trimethoxy silane;3 parts of calcium stearate;
3 parts of antioxidant CA.
Wherein, the preparation method of the silicon rubber/EPDM blended rubber is as follows:
(a) synthesis of graft modification ethylene propylene diene rubber:100 parts of ethylene propylene diene rubber is taken in terms of parts by weight, is dissolved in 500 parts and is done
In dry toluene, 15 parts of maleic anhydride is added, is stirring evenly and then adding into 3 parts of BPO, increases temperature to 110 DEG C, reflux is anti-
It answers 4 hours, is reduced to room temperature, reaction solution is poured into 1000 parts of methanol, separate out gum-like product, drying obtains graft modification three
First EP rubbers;
(b) preparation of masterbatch:
(b1) preparation of EPDM masterbatch:It takes in 50 parts of ethylene propylene diene rubber and step (a) and obtains in parts by weight
To 50 parts of graft modification ethylene propylene diene rubber be placed in open mill and be kneaded, sequentially add methacryloxy trimethoxy
10 parts of 1.5 parts of base silane, 0.5 part of DCP, 0.5 part of antioxidant 264,20 parts of super abrasion furnace black and paraffin oil are kneaded into ternary
The preparation of the third masterbatch of second;
(b2) preparation of silicone master batch:40 parts of silicon rubber, 20 parts of super abrasion furnace black, zinc oxide 3 are taken in parts by weight
1.5 parts of part, 3 parts of iron oxide and methacryloxy trimethoxy silane are sequentially placed into open mill and are kneaded, and obtain
Silicone master batch;
(c) silicon rubber/EPDM blended rubber:It is 170 that the EPDM masterbatch obtained in step (b1), which is placed in roller temperature,
DEG C open mill in it is counter refine 4 times, be then added silicone master batch, thin 5 times logical after being kneaded uniformly, it is 40 DEG C to be subsequently placed in roller temperature
Open mill in be added 3 parts of vulcanizer DCP and assistant crosslinking agent 2 parts of TMPTMA, it is thin it is 5 times logical after slice, at 170 DEG C into
Row one step cure 10 minutes is subsequently placed in post vulcanization 120 minutes at 150 DEG C, obtains silicon rubber/EPDM blended rubber.
The preparation method of the epoxy group polysilsesquioxane is as follows:
1) 50 parts of vinyltrimethoxysilane under nitrogen protection, is taken in parts by weight, is dissolved in 200 parts of isopropanols,
Then 15 parts of sodium hydroxides are added, increase temperature to flowing back, back flow reaction 10 hours is obtained by filtration filter residue, is dissolved in tetrahydrochysene
In furans, glacial acetic acid is added dropwise thereto up to neutrality, tetrahydrofuran is evaporated off, obtains white powder, after washing 5 times, drying obtains
Eight vinyl polysilsesquioxanes;
2) it takes 10 parts of the eight vinyl polysilsesquioxane obtained in step 1) to be dissolved in 100 parts of chloroform, ice is added thereto
2 parts of 50 parts of acetic acid and the concentrated sulfuric acid increase temperature to after 70 DEG C, 80 parts of Peracetic acid are added dropwise, back flow reaction is after 8 hours, with saturation
Sodium carbonate liquor and deionized water are washed to neutrality, and revolving solvent obtains epoxy group polysilsesquioxane.
Embodiment 3
A kind of high-low temperature resistant high strength PVC cable material, the CABLE MATERIALS include following components in parts by weight:
Melt index is 100 parts of the polyvinyl chloride resin of 1250~1450g/10min;Silicon rubber/40 parts of EPDM blended rubber;Ammonia
30 parts of base silicone oil;35 parts of epoxy group polysilsesquioxane;6 parts of three tert-butyl peroxide silane of vinyl;2 parts of paraffin;Antioxidant
264 2 parts.
Wherein, the preparation method of the silicon rubber/EPDM blended rubber is as follows:
(a) synthesis of graft modification ethylene propylene diene rubber:100 parts of ethylene propylene diene rubber is taken in terms of parts by weight, is dissolved in 500 parts and is done
In dry toluene, 12 parts of maleic anhydride is added, is stirring evenly and then adding into 3 parts of BPO, increases temperature to 110 DEG C, reflux is anti-
It answers 3 hours, is reduced to room temperature, reaction solution is poured into 1000 parts of methanol, separate out gum-like product, drying obtains graft modification three
First EP rubbers;
(b) preparation of masterbatch:
(b1) preparation of EPDM masterbatch:It takes in 50 parts of ethylene propylene diene rubber and step (a) and obtains in parts by weight
To 50 parts of graft modification ethylene propylene diene rubber be placed in open mill and be kneaded, sequentially add methacryloxy trimethoxy
10 parts of 1.5 parts of base silane, 0.5 part of DCP, 0.5 part of antioxidant 264,20 parts of super abrasion furnace black and paraffin oil are kneaded into ternary
The preparation of the third masterbatch of second;
(b2) preparation of silicone master batch:40 parts of silicon rubber, 20 parts of super abrasion furnace black, zinc oxide 3 are taken in parts by weight
1.5 parts of part, 3 parts of iron oxide and methacryloxy trimethoxy silane are sequentially placed into open mill and are kneaded, and obtain
Silicone master batch;
(c) silicon rubber/EPDM blended rubber:It is 170 that the EPDM masterbatch obtained in step (b1), which is placed in roller temperature,
DEG C open mill in it is counter refine 4 times, be then added silicone master batch, thin 4 times logical after being kneaded uniformly, it is 35 DEG C to be subsequently placed in roller temperature
Open mill in be added 3 parts of vulcanizer DCP and assistant crosslinking agent 2 parts of TMPTMA, it is thin it is 4 times logical after slice, at 170 DEG C into
Row one step cure 10 minutes is subsequently placed in post vulcanization 100 minutes at 150 DEG C, obtains silicon rubber/EPDM blended rubber.
The preparation method of the epoxy group polysilsesquioxane is as follows:
1) 50 parts of vinyltrimethoxysilane under nitrogen protection, is taken in parts by weight, is dissolved in 200 parts of isopropanols,
Then 12 parts of sodium hydroxides are added, increase temperature to flowing back, back flow reaction 9 hours is obtained by filtration filter residue, is dissolved in tetrahydrochysene furan
In muttering, glacial acetic acid is added dropwise thereto up to neutrality, tetrahydrofuran is evaporated off, obtains white powder, after washing 4 times, drying obtains eight
Vinyl polysilsesquioxane;
2) it takes 10 parts of the eight vinyl polysilsesquioxane obtained in step 1) to be dissolved in 100 parts of chloroform, ice is added thereto
2 parts of 50 parts of acetic acid and the concentrated sulfuric acid increase temperature to after 70 DEG C, 60 parts of Peracetic acid are added dropwise, back flow reaction is after 5 hours, with saturation
Sodium carbonate liquor and deionized water are washed to neutrality, and revolving solvent obtains epoxy group polysilsesquioxane.
Embodiment 4
A kind of high-low temperature resistant high strength PVC cable material, the CABLE MATERIALS include following components in parts by weight:
Melt index is 100 parts of the polyvinyl chloride resin of 1250~1450g/10min;Silicon rubber/35 parts of EPDM blended rubber;Ammonia
35 parts of base silicone oil;25 parts of epoxy group polysilsesquioxane;7 parts of three tert-butyl peroxide silane of vinyl;Cetomacrogol 1000
2.5 part;2.5 parts of triphenyl phosphite.
Wherein, the preparation method of the silicon rubber/EPDM blended rubber is as follows:
(a) synthesis of graft modification ethylene propylene diene rubber:100 parts of ethylene propylene diene rubber is taken in terms of parts by weight, is dissolved in 500 parts and is done
In dry toluene, 14 parts of maleic anhydride is added, is stirring evenly and then adding into 3 parts of BPO, increases temperature to 110 DEG C, reflux is anti-
It answers 2.5 hours, is reduced to room temperature, reaction solution is poured into 1000 parts of methanol, separate out gum-like product, drying obtains graft modification
Ethylene propylene diene rubber;
(b) preparation of masterbatch:
(b1) preparation of EPDM masterbatch:It takes in 50 parts of ethylene propylene diene rubber and step (a) and obtains in parts by weight
To 50 parts of graft modification ethylene propylene diene rubber be placed in open mill and be kneaded, sequentially add methacryloxy trimethoxy
10 parts of 1.5 parts of base silane, 0.5 part of DCP, 0.5 part of antioxidant 264,20 parts of super abrasion furnace black and paraffin oil are kneaded into ternary
The preparation of the third masterbatch of second;
(b2) preparation of silicone master batch:40 parts of silicon rubber, 20 parts of super abrasion furnace black, zinc oxide 3 are taken in parts by weight
1.5 parts of part, 3 parts of iron oxide and methacryloxy trimethoxy silane are sequentially placed into open mill and are kneaded, and obtain
Silicone master batch;
(c) silicon rubber/EPDM blended rubber:It is 170 that the EPDM masterbatch obtained in step (b1), which is placed in roller temperature,
DEG C open mill in it is counter refine 3 times, be then added silicone master batch, thin 5 times logical after being kneaded uniformly, it is 25 DEG C to be subsequently placed in roller temperature
Open mill in be added 3 parts of vulcanizer DCP and assistant crosslinking agent 2 parts of TMPTMA, it is thin it is 5 times logical after slice, at 170 DEG C into
Row one step cure 10 minutes is subsequently placed in post vulcanization 100 minutes at 150 DEG C, obtains silicon rubber/EPDM blended rubber.
The preparation method of the epoxy group polysilsesquioxane is as follows:
1) 50 parts of vinyltrimethoxysilane under nitrogen protection, is taken in parts by weight, is dissolved in 200 parts of isopropanols,
Then 10 parts of sodium hydroxides are added, increase temperature to flowing back, back flow reaction 10 hours is obtained by filtration filter residue, is dissolved in tetrahydrochysene
In furans, glacial acetic acid is added dropwise thereto up to neutrality, tetrahydrofuran is evaporated off, obtains white powder, after washing 4 times, drying obtains
Eight vinyl polysilsesquioxanes;
2) it takes 10 parts of the eight vinyl polysilsesquioxane obtained in step 1) to be dissolved in 100 parts of chloroform, ice is added thereto
2 parts of 50 parts of acetic acid and the concentrated sulfuric acid increase temperature to after 70 DEG C, 80 parts of Peracetic acid are added dropwise, back flow reaction is after 5 hours, with saturation
Sodium carbonate liquor and deionized water are washed to neutrality, and revolving solvent obtains epoxy group polysilsesquioxane.
Embodiment 5
A kind of high-low temperature resistant high strength PVC cable material, the CABLE MATERIALS include following components in parts by weight:
Melt index is 100 parts of the polyvinyl chloride resin of 1250~1450g/10min;Silicon rubber/35 parts of EPDM blended rubber;Ammonia
25 parts of base silicone oil;45 parts of epoxy group polysilsesquioxane;6 parts of vinyltriethoxysilane;2.5 parts of calcium stearate;Bis-phenol
A1.5 parts.
Wherein, the preparation method of the silicon rubber/EPDM blended rubber is as follows:
(a) synthesis of graft modification ethylene propylene diene rubber:100 parts of ethylene propylene diene rubber is taken in terms of parts by weight, is dissolved in 500 parts and is done
In dry toluene, 13 parts of maleic anhydride is added, is stirring evenly and then adding into 3 parts of BPO, increases temperature to 110 DEG C, reflux is anti-
It answers 3 hours, is reduced to room temperature, reaction solution is poured into 1000 parts of methanol, separate out gum-like product, drying obtains graft modification three
First EP rubbers;
(b) preparation of masterbatch:
(b1) preparation of EPDM masterbatch:It takes in 50 parts of ethylene propylene diene rubber and step (a) and obtains in parts by weight
To 50 parts of graft modification ethylene propylene diene rubber be placed in open mill and be kneaded, sequentially add methacryloxy trimethoxy
10 parts of 1.5 parts of base silane, 0.5 part of DCP, 0.5 part of antioxidant 264,20 parts of super abrasion furnace black and paraffin oil are kneaded into ternary
The preparation of the third masterbatch of second;
(b2) preparation of silicone master batch:40 parts of silicon rubber, 20 parts of super abrasion furnace black, zinc oxide 3 are taken in parts by weight
1.5 parts of part, 3 parts of iron oxide and methacryloxy trimethoxy silane are sequentially placed into open mill and are kneaded, and obtain
Silicone master batch;
(c) silicon rubber/EPDM blended rubber:It is 170 that the EPDM masterbatch obtained in step (b1), which is placed in roller temperature,
DEG C open mill in it is counter refine 4 times, be then added silicone master batch, thin 3 times logical after being kneaded uniformly, it is 40 DEG C to be subsequently placed in roller temperature
Open mill in be added 3 parts of vulcanizer DCP and assistant crosslinking agent 2 parts of TMPTMA, it is thin it is 5 times logical after slice, at 170 DEG C into
Row one step cure 10 minutes is subsequently placed in post vulcanization 80 minutes at 150 DEG C, obtains silicon rubber/EPDM blended rubber.
The preparation method of the epoxy group polysilsesquioxane is as follows:
1) 50 parts of vinyltrimethoxysilane under nitrogen protection, is taken in parts by weight, is dissolved in 200 parts of isopropanols,
Then 14 parts of sodium hydroxides are added, increase temperature to flowing back, back flow reaction 9 hours is obtained by filtration filter residue, is dissolved in tetrahydrochysene furan
In muttering, glacial acetic acid is added dropwise thereto up to neutrality, tetrahydrofuran is evaporated off, obtains white powder, after washing 4 times, drying obtains eight
Vinyl polysilsesquioxane;
2) it takes 10 parts of the eight vinyl polysilsesquioxane obtained in step 1) to be dissolved in 100 parts of chloroform, ice is added thereto
2 parts of 50 parts of acetic acid and the concentrated sulfuric acid increase temperature to after 70 DEG C, 75 parts of Peracetic acid are added dropwise, back flow reaction is after 6 hours, with saturation
Sodium carbonate liquor and deionized water are washed to neutrality, and revolving solvent obtains epoxy group polysilsesquioxane.
To the high-low temperature resistant high strength PVC cable material obtained by Examples 1 to 5, it is tested for the property, result is such as
Shown in following table.
High-low temperature resistant high strength PVC cable material performance obtained by 1 Examples 1 to 5 of table.
From the data in upper table it is found that obtained high-low temperature resistant high strength PVC cable material has outstanding resistance to height
Low-temperature flame retardant performance and good mechanical property, disclosure satisfy that the normal use under critical conditions.
Claims (8)
1. a kind of high-low temperature resistant high strength PVC cable material, which is characterized in that the CABLE MATERIALS is wrapped in parts by weight
Include following components:
100 parts of polyvinyl chloride resin;
Silicon rubber/30 ~ 45 parts of EPDM blended rubber
25-40 parts of amido silicon oil
20-45 parts of epoxy group polysilsesquioxane
3-8 parts of silane coupling agent
1-3 parts of lubricant
1-3 parts of antioxidant.
2. a kind of high-low temperature resistant high strength PVC cable material according to claim 1, which is characterized in that the PVC
The melt index of resin is 1250 ~ 1450 g/10min.
3. a kind of high-low temperature resistant high strength PVC cable material according to claim 1, which is characterized in that the silicon
The preparation method of rubber/EPDM blended rubber is as follows:
(a)The synthesis of graft modification ethylene propylene diene rubber:100 parts of ethylene propylene diene rubber is taken in terms of parts by weight, is dissolved in 500 parts and is done
In dry toluene, 10-15 parts of maleic anhydride is added, is stirring evenly and then adding into 3 parts of BPO, increases temperature to 110 DEG C, flows back
Reaction 2-4 hours, is reduced to room temperature, reaction solution is poured into 1000 parts of methanol, separates out gum-like product, and drying obtains grafting and changes
Property ethylene propylene diene rubber;
(b)The preparation of masterbatch:
(b1)The preparation of EPDM masterbatch:50 parts of ethylene propylene diene rubber and step are taken in parts by weight(a)In
To 50 parts of graft modification ethylene propylene diene rubber be placed in open mill and be kneaded, sequentially add methacryloxy trimethoxy
10 parts of 1.5 parts of base silane, 0.5 part of DCP, 0.5 part of antioxidant 264,20 parts of super abrasion furnace black and paraffin oil are kneaded into ternary
The preparation of the third masterbatch of second;
(b2)The preparation of silicone master batch:40 parts of silicon rubber, 20 parts of super abrasion furnace black, zinc oxide 3 are taken in parts by weight
1.5 parts of part, 3 parts of iron oxide and methacryloxy trimethoxy silane are sequentially placed into open mill and are kneaded, and obtain
Silicone master batch;
(c)Silicon rubber/EPDM blended rubber:By step(b1)In obtained EPDM masterbatch to be placed in roller temperature be 170
DEG C open mill in it is counter refine 3-4 times, be then added silicone master batch, logical 3-5 times thin after being kneaded uniformly, being subsequently placed in roller temperature is
2 parts of TMPTMA, thin logical 3-5 times rear slices of 3 parts of vulcanizer DCP and assistant crosslinking agent are added in 25-40 DEG C of open mill,
One step cure is carried out at 170 DEG C 10 minutes, be subsequently placed at 150 DEG C post vulcanization 60-120 minutes, obtain silicon rubber/ternary second
Third blended rubber.
4. a kind of high-low temperature resistant high strength PVC cable material according to claim 1, which is characterized in that the ammonia
The ammonia value of base silicone oil is 0.3-0.6, and the amido silicon oil viscosity is 1000-1500 mm2/s。
5. a kind of high-low temperature resistant high strength PVC cable material according to claim 1, which is characterized in that the ring
The preparation method of oxygroup polysilsesquioxane is as follows:
1)Under nitrogen protection, 50 parts of vinyltrimethoxysilane is taken in parts by weight, is dissolved in 200 parts of isopropanols,
Then 10-15 parts of sodium hydroxides are added, increase temperature to flowing back, back flow reaction 8-10 hours is obtained by filtration filter residue, is dissolved in
In tetrahydrofuran, glacial acetic acid is added dropwise thereto up to neutrality, tetrahydrofuran is evaporated off, obtains white powder, after washing 3-5 times, dries
It is dry to obtain eight vinyl polysilsesquioxanes;
2)Take step 1)In obtained 10 parts of eight vinyl polysilsesquioxane be dissolved in 100 parts of chloroform, ice is added thereto
2 parts of 50 parts of acetic acid and the concentrated sulfuric acid increase temperature to after 70 DEG C, and 50-80 parts of Peracetic acid is added dropwise, and back flow reaction is after 4-8 hours,
It is washed to neutrality with saturated sodium carbonate solution and deionized water, revolving solvent obtains epoxy group polysilsesquioxane.
6. a kind of high-low temperature resistant high strength PVC cable material according to claim 1, which is characterized in that the silicon
Alkane coupling agent is vinyltriethoxysilane, methacryloxy trimethoxy silane, methyl ethylene diethoxy silicon
One kind in three tert-butyl peroxide silane of alkane or vinyl.
7. a kind of high-low temperature resistant high strength PVC cable material according to claim 1, which is characterized in that the profit
Lubrication prescription is one kind in magnesium stearate, calcium stearate, paraffin or cetomacrogol 1000.
8. a kind of high-low temperature resistant high strength PVC cable material according to claim 1, which is characterized in that described is anti-
Oxidant is one kind in bisphenol-A, antioxidant CA, antioxidant 264 and triphenyl phosphite.
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CN110185713A (en) * | 2019-07-10 | 2019-08-30 | 贝德科技有限公司 | A kind of Diesel engine pump check shaft coupling |
CN111853652A (en) * | 2020-06-30 | 2020-10-30 | 圣晖***集成集团股份有限公司 | Emergency lamp and manufacturing method thereof |
CN118047999A (en) * | 2024-03-25 | 2024-05-17 | 广东弘山川电子科技有限公司 | High-temperature-resistant insulating rubber material and preparation method and application thereof |
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CN107266815A (en) * | 2017-06-30 | 2017-10-20 | 徐州苏牌高温新材料有限公司 | A kind of heat-resistant fireproof cable material |
CN107603074A (en) * | 2017-10-25 | 2018-01-19 | 浙江威思康塑胶有限公司 | A kind of moistureproof PVC insulating sheaths |
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CN107266815A (en) * | 2017-06-30 | 2017-10-20 | 徐州苏牌高温新材料有限公司 | A kind of heat-resistant fireproof cable material |
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Publication number | Priority date | Publication date | Assignee | Title |
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CN110185713A (en) * | 2019-07-10 | 2019-08-30 | 贝德科技有限公司 | A kind of Diesel engine pump check shaft coupling |
CN111853652A (en) * | 2020-06-30 | 2020-10-30 | 圣晖***集成集团股份有限公司 | Emergency lamp and manufacturing method thereof |
CN118047999A (en) * | 2024-03-25 | 2024-05-17 | 广东弘山川电子科技有限公司 | High-temperature-resistant insulating rubber material and preparation method and application thereof |
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