CN110194879A - A kind of MPP material of high intensity and preparation method thereof and cable protection pipe obtained - Google Patents
A kind of MPP material of high intensity and preparation method thereof and cable protection pipe obtained Download PDFInfo
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- CN110194879A CN110194879A CN201910364226.2A CN201910364226A CN110194879A CN 110194879 A CN110194879 A CN 110194879A CN 201910364226 A CN201910364226 A CN 201910364226A CN 110194879 A CN110194879 A CN 110194879A
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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
- 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
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02G—INSTALLATION OF ELECTRIC CABLES OR LINES, OR OF COMBINED OPTICAL AND ELECTRIC CABLES OR LINES
- H02G3/00—Installations of electric cables or lines or protective tubing therefor in or on buildings, equivalent structures or vehicles
- H02G3/02—Details
- H02G3/04—Protective tubing or conduits, e.g. cable ladders or cable troughs
- H02G3/0462—Tubings, i.e. having a closed section
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The present invention relates to cable protection pipe material technical fields; MPP material more particularly to a kind of high intensity and preparation method thereof and cable protection pipe obtained; the MPP material of the high intensity, the raw material including following parts by weight: 80-100 parts acrylic resin modified, 2-6 parts of graphene A, 4-8 parts of carbon black, 1-5 parts of coupling agent, 5-10 parts of toughener, 0.5-2 parts of antioxidant, 0.5-1.5 parts of nanometer calcium carbonate；The graphene A is few layer graphene oxide, oxygen content 20-40wt%.A kind of MPP material of high intensity of the invention has excellent intensity, high-fire resistance and shock resistance; so that MPP material obtained is had many advantages, such as weld strength high and low temperature good toughness, easy processing by using the filling of graphene B modified acrylic resin combination nanometer calcium carbonate and graphene A, there is excellent intensity, impact resistance and high heat resistance using the cable protection pipe that it is obtained.
Description
Technical field
The present invention relates to cable protection pipe material technical fields, and in particular to a kind of MPP material of high intensity and its preparation
Method and cable protection pipe obtained.
Background technique
With the development of China's urban construction, the laying of underground pipeline construction especially electric power protecting pipe has become city
Indispensable important link is built, wherein cable protection pipe also known as power cable protecting pipe, cement cable protection tube, electric power row
Pipe, power cable protecting pipe etc..Cable protection pipe is mostly installed at the location that communication cable intersects with power line, prevents power line
The case where broken string causes short circuit accident, communication cable and wirerope is caused to charge occurs.Cable protection pipe is for protecting electricity
Cable, interchanger, machine core board also function to certain buffer action to power line magnetic interference while must so that complete machine is not burned
There must be extremely strong antioxidation.
MPP power pipe is the plastic pipe for using modified polypropene to be prepared for main raw material(s), and MPP power pipe is mesh
It is preceding to lead one of most conventional electric power tubing to be applied in the market, but being gradually expanded with its application field and environment, it is insufficient
Place also increasingly highlights, and such as intensity, anti-flammability, electrical insulating property, antiacid caustic corrosion, anti-oxidant, sliding property, thermal stability etc. are comprehensive
The environment of high request can't be adapted to completely by closing aspect of performance, it is therefore desirable to improve polypropylene by more special modified technique
The comprehensive performance of electric power protection pipe, obtains that intensity is good, corrosion resistance is strong, electric insulating quality is good, high mechanical strength, coefficient of friction
Small, heat-resisting, cold-resistant, long service life, easy for construction, the superior electric power protection pipe of the ratio of performance to price are urgently to be solved at present ask
Topic.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of high intensity
MPP material, material intensity with higher, impact resistance, anti-flammability, electrical insulating property, antiacid caustic corrosion and inoxidizability etc.
Performance, the excellent easy processing of mechanical mechanics property.
Another object of the present invention is to provide a kind of preparation method of the MPP material of high intensity, preparation method operations
Simply, easy to control, high production efficiency, production cost is low, and MPP material obtained gathers intensity with higher, anti-flammability, electricity absolutely
The performances such as edge, antiacid caustic corrosion, inoxidizability and impact resistance, are applicable to be mass produced.
A further object of the present invention is to provide cable protection pipes made from a kind of MPP material of application high intensity, should
Cable protection pipe has excellent intensity, impact resistance, high-fire resistance and antioxygenic property, and load capacity and electromagnetic wave shielding
Can be good, have comprehensive performances, the mechanical mechanics properties such as preferable anti-flammability corrosion resistance excellent.
The purpose of the invention is achieved by the following technical solution: a kind of MPP material of high intensity, including following parts by weight
Raw material:
The graphene A is few layer graphene oxide, oxygen content 20-40wt%.
Addition nanometer calcium carbonate can improve material to a certain extent in the raw material of high-intensitive MPP material of the invention
Heat resistance, and graphene A has very excellent mechanical property, and breaking strength is up to 135GPa, the graphene A of addition
The crack of MPP and the inside in gap can be added in powder, can be good at the intensity and shock resistance that promote material, more excellent
Choosing, the present invention further limits graphene A used as few layer graphene oxide, and oxygen content 20-40wt% is because few
Layer graphene oxide graphene-structured can be introduced into MPP material by way of chemical bond, can be had excellent performance and
Uniform and stable modified product.Few layer graphene oxide is connected to functional acrylic monomer by the present invention by way of chemical bond
In to improving its impact resistance, anti-oxidant and antistatic property, can also supplement modified acrylic resin sliding property well
The feature of difference；The modified polypropylene material of the independent research wherein used meets MPP standard, has weld strength high and low temperature tough
The advantages that property is good, easy processing.
Preferably, every part of acrylic resin modified raw material including following parts by weight:
The partial size of the graphene B is 50-80nm；The monomer includes cross-linking monomer and soft monomer, the cross-linking monomer
For at least one of N hydroxymethyl acrylamide, N- isobutoxymethyl acrylic acid amide；The soft monomer is acrylic acid fourth
At least one of ester, ethyl acrylate or methyl acrylate.
Have in N hydroxymethyl acrylamide molecule in heretofore described acrylic resin modified raw material total with carbonyl
The double bond of yoke and rich in reactive methylol, and N- isobutoxymethyl acrylic acid amide can improve it is acrylic resin modified
Water resistance, solvent resistance, inoxidizability, adhesive force, tensile strength and the generation for reducing formaldehyde in cross-linking process, in addition it can
Improve impact resistance, flexibility and the inoxidizability that MPP material is made；Acrylamide can make suspended material by charge neutrality,
Bridge formation suction-operated can play flocculation, while it is effective can also play adhesive effect by mechanical, physics, chemical effect
Ground reduces the frictional resistance of fluid, in addition has thickening power under the conditions of neutral and acid；Graphene B is contained due to cross-linking monomer
Nitrogen can introduce after nitrogen-atoms the graphene for becoming N doping, the nitrogen-doped graphene performance of generation in graphene lattice
The performance of purer graphene more excellent impact resistances and intensity out forms multilayered structure, shows good cycle life；PP
A kind of semi-crystalline material of resin has lower hot torsion temperature (100C), low transparency, low-luster, low rigidity, but has
Stronger impact strength, higher additionally, due to crystallinity, the surface rigidity that can make MPP material obtained and anti-scratch characteristic are very
It is good；The adhesive that acrylic acid makees electrostatic spinning, plants hair, fastness and good hand touch can promote the antistatic of MPP material entirety
Performance, while also further improving the resistance to voltage that cable protection pipe is made by MPP material；Tert-butyl hydroperoxide is as poly-
The initiator for closing reaction can occur covalent bond homolysis in the preparation process of MPP material and generate two free radicals, can cause
Polymerization reaction improves the efficiency that the present invention prepares MPP material.
Preferably, described acrylic resin modified to be made by following steps:
1) graphene B, acrylamide, monomer, PP resin, acrylic acid and 40% deionized water are added according to weight part ratio and is stirred
Device is mixed, is heated to stirring 100-150min under conditions of temperature is 50-70 DEG C, obtains colostric fluid；
2) balance deionized water being added in reactor and being warming up to temperature is 80-100 DEG C, and tert-butyl hydroperoxide is added later
Colostric fluid obtained in step 1) is then slowly added to by hydrogen；
3) solution after reaction in step 2) is cooling, obtain acrylic resin modified first product；
4) acrylic resin modified first product obtained in step 3) is placed under the conditions of temperature is 100-130 DEG C and is dried
Dry, drying time 2-4h finally obtains acrylic resin modified finished product.
The present invention, which is made acrylic resin modified by the above method, has weld strength high and low temperature good toughness, easy processing
The advantages that.In step 1) whipping temp control is being belonged into compatibility maximum range between each raw material within the scope of 50-70 DEG C, had
It is mixed conducive to the ingredient of a raw material；And first being added in reactor to heat up by deionized water in step 2) can prevent due to reactor
Internal uneven heating and so that the tert-butyl hydroperoxide initiator being added is met variation on high temperature recurring structure suddenly, cause to prepare
The low efficiency of MPP material；In step 4) by obtained acrylic resin modified first product be placed on temperature be 100-130 DEG C under the conditions of into
Row drying, can further promote the stability for being made acrylic resin modified, antistatic, shock resistance and antioxygenic property.
Preferably, it according to weight ratio is 1.0-1.5:1.0 group that the coupling agent, which is silane coupling agent and titanate coupling agent,
At mixture.
Intensity, electrical, water resistant, anti-weather when silane coupling agent in the present invention can greatly improve MPP Material cladding
Etc. performances in addition can be in advance to stone even if its raising to composite material machinery performance, effect is also very significant in hygrometric state
Black alkene A is surface-treated, and can also be directly added into acrylic resin modified, can improve acrylic resin modified dispersibility and
Bonding force, improve each raw material and it is acrylic resin modified between compatibility, improve processing performance and improve MPP material machine
The performances such as tool, electricity and weatherability；The molecule of titanate coupling agent titanium can be divided into six functional areas, wherein the 4th functional areas
Due to improving the intermiscibility with PP resin system there are the carbon atom number of a large amount of long-chains, cause inorganic matter interface upper surface energy
Variation has the function of flexibility and stress transfer, generates self-lubricating function, leads to viscosity sharp fall, improves MPP material
Processing technology increases the elongation percentage and tearing strength of MPP material obtained, improves impact property.
Preferably, the toughener is at least one of POE, TPE and EPDM；The antioxidant is tetrapentaerythritol
At least one of ester, phosphorous acid, sulfuric acid and phenols.
Toughening agent of the present invention is not have unsaturated bond in POE molecular structure, with excellent ageing-resistant performance, preferably
Mobility, good with acrylic resin modified compatibility, good mobility can change the dispersion effect of nanometer calcium carbonate, mention simultaneously
The toughness of high product, cold resistance and impact resistance；And antioxidant employed in the present invention can make MPP material tool obtained
Have a good anti-oxidant, anti-aging and anticorrosive effect, the traditional cable protection pipe that cable protection pipe as made from it avoids by
It is easily oxidized or the drawbacks of aging in being exposed in various environment.
A kind of preparation method of the MPP material of high intensity, characterized by the following steps:
1) according to parts by weight will nanometer calcium carbonate be added mixing agitator in, be warming up to temperature be 80-100 DEG C when with
The rate of 100-150rpm/min carries out first time stirring, and mixing time 60-90min adds coupling agent later with 50-
The rate of 100rpm/min carries out second and stirs, and mixing time 120-150min, cooling and standings obtain mixture；
2) then according to parts by weight successively by acrylic resin modified, graphene A, carbon black, toughener, antioxidant and
Calcium stearate is added in the mixture of step 1), continues to stir, and discharges；
3) mixture obtained in step 2) is put into and is granulated by double screw extruder melting extrusion, high intensity is made
MPP material, area's temperature of the extrusion equipment are 200-220 DEG C, and two area's temperature are 215-230 DEG C, and three area's temperature are 235-
255 DEG C, four area's temperature are 230-255 DEG C, and five area's temperature are 250-265 DEG C, screw speed 200-400r/min.
A kind of MPP material of high intensity of the present invention is made by above-mentioned preparation method, and MPP material obtained is with higher
The performances such as intensity, anti-flammability, electrical insulating property, antiacid caustic corrosion, inoxidizability and impact resistance.Wherein preparing MPP material
Strict control heating can be such that the mobility of nanometer calcium carbonate reaches most preferably, after being conducive within the scope of 80-100 DEG C in step 1)
Continuous to fill with PP resin, the rate that in addition strictly control second of stirring is conducive to coupling agent within the scope of 50-100rpm/min
After addition in conjunction with nanometer calcium carbonate, the effect of fully dispersed combination is not achieved if rate is too fast, disperses if rate is too low
Unevenly；And the temperature in each region of strict control five is conducive to improve the shock resistance and anti-flammability of MPP material in step 3).
The present invention also provides a kind of cable protection pipe, the cable protection pipe is made by high-intensitive MPP material.
The present invention manufactures cable protection pipe, cable protection pipe tool obtained as the MPP material of the high intensity made from
Have excellent intensity, impact resistance, high-fire resistance and antioxygenic property, and load capacity and electromagnetic shielding performance are good, have compared with
The excellent mechanical mechanics property such as good anti-flammability corrosion resistance.
The beneficial effects of the present invention are: high-intensitive MPP material of the invention have excellent intensity, high-fire resistance and
Shock resistance, and make to make by using the filling of graphene B modified acrylic resin combination nanometer calcium carbonate and graphene A
The MPP material obtained has many advantages, such as weld strength high and low temperature good toughness, easy processing.
The preparation method operating procedure of high-intensitive MPP material of the invention is simple, easy to control, high production efficiency, production
At low cost, MPP quality of materials obtained is stablized, and is applicable to be mass produced.
The present invention using high intensity MPP material made from cable protection pipe with excellent intensity, impact resistance and
High heat resistance, and load capacity and electromagnetic shielding performance are good, have the excellent mechanical forces such as preferable anti-flammability corrosion resistance
Performance is learned, in addition also has comprehensive performances, the mechanical mechanics properties such as preferable anti-flammability, tensile strength and hardness excellent.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of MPP material of high intensity, the raw material including following parts by weight:
The graphene A is few layer graphene oxide, oxygen content 20wt%.
Every part of acrylic resin modified raw material including following parts by weight:
The partial size of the graphene B is 50nm, and the monomer includes cross-linking monomer and soft monomer, and the cross-linking monomer is N-
Hydroxymethyl acrylamide；The soft monomer is butyl acrylate.
It is described acrylic resin modified to be made by following steps:
1) graphene B, acrylamide, monomer, PP resin, acrylic acid and 40% deionized water are added according to weight part ratio and is stirred
Device is mixed, is heated to stirring 100min under conditions of temperature is 50 DEG C, obtains colostric fluid；
2) balance deionized water being added in reactor and being warming up to temperature is 80 DEG C, and tert-butyl hydroperoxide is added later,
Then colostric fluid obtained in step 1) is slowly added to；
3) solution after reaction in step 2) is cooling, obtain acrylic resin modified first product；
4) acrylic resin modified first product obtained in step 3) is placed under the conditions of temperature is 100 DEG C and is dried, dried
The dry time is 2h, finally obtains acrylic resin modified finished product.
The coupling agent is silane coupling agent and titanate coupling agent according to the mixture that weight ratio is that 1.0:1.0 is formed；
The toughener is POE；The antioxidant is tetrapentaerythritol ester.
A kind of preparation method of the MPP material of high intensity, includes the following steps:
1) according to parts by weight will nanometer calcium carbonate be added mixing agitator in, be warming up to temperature be 80 DEG C when with
The rate of 100rpm/min carries out first time stirring, and mixing time 60min adds coupling agent later with 50rpm/min's
Rate carries out second and stirs, and mixing time 120min, cooling and standings obtain mixture；
2) then according to parts by weight successively by acrylic resin modified, graphene A, carbon black, toughener, antioxidant and
Calcium stearate is added in the mixture of step 1), continues to stir, and discharges；
3) mixture obtained in step 2) is put into and is granulated by double screw extruder melting extrusion, high intensity is made
MPP material, area's temperature of the extrusion equipment are 200 DEG C, and two area's temperature are 215 DEG C, and three area's temperature are 235 DEG C, four Qu Wen
Degree is 230 DEG C, and five area's temperature are 250 DEG C, screw speed 200r/min.
A kind of cable protection pipe, the cable protection pipe are made by high-intensitive MPP material.
Embodiment 2
A kind of MPP material of high intensity, the raw material including following parts by weight:
The graphene A is few layer graphene oxide, oxygen content 25wt%.
Every part of acrylic resin modified raw material including following parts by weight:
The partial size of the graphene B is 60nm, and the monomer includes cross-linking monomer and soft monomer, and the cross-linking monomer is N-
Isobutoxymethyl acrylic acid amide；The soft monomer is ethyl acrylate.
It is described acrylic resin modified to be made by following steps:
1) graphene B, acrylamide, monomer, PP resin, acrylic acid and 40% deionized water are added according to weight part ratio and is stirred
Device is mixed, is heated to stirring 110min under conditions of temperature is 55 DEG C, obtains colostric fluid；
2) balance deionized water being added in reactor and being warming up to temperature is 85 DEG C, and tert-butyl hydroperoxide is added later,
Then colostric fluid obtained in step 1) is slowly added to；
3) solution after reaction in step 2) is cooling, obtain acrylic resin modified first product；
4) acrylic resin modified first product obtained in step 3) is placed under the conditions of temperature is 107 DEG C and is dried, dried
The dry time is 2.5h, finally obtains acrylic resin modified finished product.
The coupling agent is silane coupling agent and titanate coupling agent according to the mixture that weight ratio is that 1.1:1.0 is formed；
The toughener is TPE；The antioxidant is phosphorous acid.
A kind of preparation method of the MPP material of high intensity, includes the following steps:
1) according to parts by weight will nanometer calcium carbonate be added mixing agitator in, be warming up to temperature be 85 DEG C when with
The rate of 115rpm/min carries out first time stirring, and mixing time 67min adds coupling agent later with 63rpm/min's
Rate carries out second and stirs, and mixing time 128min, cooling and standings obtain mixture；
2) then according to parts by weight successively by acrylic resin modified, graphene A, carbon black, toughener, antioxidant and
Calcium stearate is added in the mixture of step 1), continues to stir, and discharges；
3) mixture obtained in step 2) is put into and is granulated by double screw extruder melting extrusion, high intensity is made
MPP material, area's temperature of the extrusion equipment are 205 DEG C, and two area's temperature are 220 DEG C, and three area's temperature are 240 DEG C, four Qu Wen
Degree is 238 DEG C, and five area's temperature are 254 DEG C, screw speed 250r/min.
A kind of cable protection pipe, the cable protection pipe are made by high-intensitive MPP material.
Embodiment 3
A kind of MPP material of high intensity, the raw material including following parts by weight:
The graphene A is few layer graphene oxide, oxygen content 30wt%.
Every part of acrylic resin modified raw material including following parts by weight:
The partial size of the graphene B is 65nm, and the monomer includes cross-linking monomer and soft monomer, and the cross-linking monomer is N-
Hydroxymethyl acrylamide and N- isobutoxymethyl acrylic acid amide are 0.8:1.0 composition mixture according to weight ratio；It is described soft
Monomer is methyl acrylate.
It is described acrylic resin modified to be made by following steps:
1) graphene B, acrylamide, monomer, PP resin, acrylic acid and 40% deionized water are added according to weight part ratio and is stirred
Device is mixed, is heated to stirring 125min under conditions of temperature is 60 DEG C, obtains colostric fluid；
2) balance deionized water being added in reactor and being warming up to temperature is 90 DEG C, and tert-butyl hydroperoxide is added later,
Then colostric fluid obtained in step 1) is slowly added to；
3) solution after reaction in step 2) is cooling, obtain acrylic resin modified first product；
4) acrylic resin modified first product obtained in step 3) is placed under the conditions of temperature is 115 DEG C and is dried, dried
The dry time is 3h, finally obtains acrylic resin modified finished product.
The coupling agent is the mixture that silane coupling agent and titanate coupling agent are 1.3 compositions according to weight ratio；It is described
Toughener is EPDM；The antioxidant is sulfuric acid.
A kind of preparation method of the MPP material of high intensity, includes the following steps:
1) according to parts by weight will nanometer calcium carbonate be added mixing agitator in, be warming up to temperature be 90 DEG C when with
The rate of 130rpm/min carries out first time stirring, and mixing time 75min adds coupling agent later with 75rpm/min's
Rate carries out second and stirs, and mixing time 135min, cooling and standings obtain mixture；
2) then according to parts by weight successively by acrylic resin modified, graphene A, carbon black, toughener, antioxidant and
Calcium stearate is added in the mixture of step 1), continues to stir, and discharges；
3) mixture obtained in step 2) is put into and is granulated by double screw extruder melting extrusion, high intensity is made
MPP material, area's temperature of the extrusion equipment are 210 DEG C, and two area's temperature are 225 DEG C, and three area's temperature are 245 DEG C, four Qu Wen
Degree is 245 DEG C, and five area's temperature are 257 DEG C, screw speed 300r/min.
A kind of cable protection pipe, the cable protection pipe are made by high-intensitive MPP material.
Embodiment 4
A kind of MPP material of high intensity, the raw material including following parts by weight:
The graphene A is few layer graphene oxide, oxygen content 35wt%.
Every part of acrylic resin modified raw material including following parts by weight:
The partial size of the graphene B is 75nm, and the monomer includes cross-linking monomer and soft monomer, and the cross-linking monomer is N-
Hydroxymethyl acrylamide and N- isobutoxymethyl acrylic acid amide are according to the mixture that weight ratio is that 1:1 is formed；The soft list
Body is butyl acrylate and ethyl acrylate according to the mixture that weight ratio is that 1:1 is formed.
It is described acrylic resin modified to be made by following steps:
1) graphene B, acrylamide, monomer, PP resin, acrylic acid and 40% deionized water are added according to weight part ratio and is stirred
Device is mixed, is heated to stirring 135min under conditions of temperature is 65 DEG C, obtains colostric fluid；
2) balance deionized water being added in reactor and being warming up to temperature is 95 DEG C, and tert-butyl hydroperoxide is added later,
Then colostric fluid obtained in step 1) is slowly added to；
3) solution after reaction in step 2) is cooling, obtain acrylic resin modified first product；
4) acrylic resin modified first product obtained in step 3) is placed under the conditions of temperature is 122 DEG C and is dried, dried
The dry time is 3.5h, finally obtains acrylic resin modified finished product.
The coupling agent is silane coupling agent and titanate coupling agent according to the mixture that weight ratio is that 1.4:1.0 is formed；
The toughener is POE and TPE is according to the mixture that weight ratio is that 0.8:1.0 is formed；The antioxidant is phenols.
A kind of preparation method of the MPP material of high intensity, includes the following steps:
1) according to parts by weight will nanometer calcium carbonate be added mixing agitator in, be warming up to temperature be 95 DEG C when with
The rate of 140rpm/min carries out first time stirring, and mixing time 82min adds coupling agent later with 87rpm/min's
Rate carries out second and stirs, and mixing time 143min, cooling and standings obtain mixture；
2) then according to parts by weight successively by acrylic resin modified, graphene A, carbon black, toughener, antioxidant and
Calcium stearate is added in the mixture of step 1), continues to stir, and discharges；
3) mixture obtained in step 2) is put into and is granulated by double screw extruder melting extrusion, high intensity is made
MPP material, area's temperature of the extrusion equipment are 215 DEG C, and two area's temperature are 228 DEG C, and three area's temperature are 250 DEG C, four Qu Wen
Degree is 250 DEG C, and five area's temperature are 262 DEG C, screw speed 350r/min.
A kind of cable protection pipe, the cable protection pipe are made by high-intensitive MPP material.
Embodiment 5
A kind of MPP material of high intensity, the raw material including following parts by weight:
The graphene A is few layer graphene oxide, oxygen content 40wt%.
Every part of acrylic resin modified raw material including following parts by weight:
The partial size of the graphene B is 80nm, and the monomer includes cross-linking monomer and soft monomer, and the cross-linking monomer is N-
Hydroxymethyl acrylamide and N- isobutoxymethyl acrylic acid amide are according to the mixture that weight ratio is that 1:1.2 is formed；It is described soft
Monomer is ethyl acrylate and methyl acrylate according to the mixture that weight ratio is that 1:1.2 is formed.
It is described acrylic resin modified to be made by following steps:
1) graphene B, acrylamide, monomer, PP resin, acrylic acid and 40% deionized water are added according to weight part ratio and is stirred
Device is mixed, is heated to stirring 150min under conditions of temperature is 70 DEG C, obtains colostric fluid；
2) balance deionized water being added in reactor and being warming up to temperature is 100 DEG C, and tert-butyl hydroperoxide is added later,
Then colostric fluid obtained in step 1) is slowly added to；
3) solution after reaction in step 2) is cooling, obtain acrylic resin modified first product；
4) acrylic resin modified first product obtained in step 3) is placed under the conditions of temperature is 130 DEG C and is dried, dried
The dry time is 2-4h, finally obtains acrylic resin modified finished product.
The coupling agent is silane coupling agent and titanate coupling agent according to the mixture that weight ratio is that 1.5:1.0 is formed；
The toughener is TPE and EPDM is according to the mixture that weight ratio is that 1:1 is formed；The antioxidant be tetrapentaerythritol ester and
Phenols is according to the mixture that weight ratio is that 0.8:1.0 is formed.
A kind of preparation method of the MPP material of high intensity, includes the following steps:
1) according to parts by weight will nanometer calcium carbonate be added mixing agitator in, be warming up to temperature be 100 DEG C when with
The rate of 150rpm/min carries out first time stirring, and mixing time 90min adds coupling agent later with 100rpm/min's
Rate carries out second and stirs, and mixing time 150min, cooling and standings obtain mixture；
2) then according to parts by weight successively by acrylic resin modified, graphene A, carbon black, toughener, antioxidant and
Calcium stearate is added in the mixture of step 1), continues to stir, and discharges；
3) mixture obtained in step 2) is put into and is granulated by double screw extruder melting extrusion, high intensity is made
MPP material, area's temperature of the extrusion equipment are 220 DEG C, and two area's temperature are 230 DEG C, and three area's temperature are 255 DEG C, four Qu Wen
Degree is 255 DEG C, and five area's temperature are 265 DEG C, screw speed 400r/min.
A kind of cable protection pipe, the cable protection pipe are made by high-intensitive MPP material.
Comparative example 1
A kind of MPP material of high intensity, the raw material including following parts by weight:
The graphene A is few layer graphene oxide, oxygen content 20wt%.
The coupling agent is silane coupling agent and titanate coupling agent according to the mixture that weight ratio is that 1.0:1.0 is formed；
The toughener is POE；The antioxidant is tetrapentaerythritol ester.
A kind of preparation method of the MPP material of high intensity, characterized by the following steps:
1) according to parts by weight will nanometer calcium carbonate be added mixing agitator in, be warming up to temperature be 80 DEG C when with
The rate of 100rpm/min carries out first time stirring, and mixing time 60min adds coupling agent later with 50rpm/min's
Rate carries out second and stirs, and mixing time 120min, cooling and standings obtain mixture；
2) then according to parts by weight successively by acrylic resin, graphene A, carbon black, toughener, antioxidant and tristearin
Sour calcium is added in the mixture of step 1), continues to stir, and discharges；
3) mixture obtained in step 2) is put into and is granulated by double screw extruder melting extrusion, high intensity is made
MPP material, area's temperature of the extrusion equipment are 200 DEG C, and two area's temperature are 215 DEG C, and three area's temperature are 235 DEG C, four Qu Wen
Degree is 230 DEG C, and five area's temperature are 250 DEG C, screw speed 200r/min.
A kind of cable protection pipe, the cable protection pipe are made by high-intensitive MPP material.
Comparative example 2
A kind of MPP material of high intensity, the raw material including following parts by weight:
Every part of acrylic resin modified raw material including following parts by weight:
The cross-linking monomer is that N hydroxymethyl acrylamide and N- isobutoxymethyl acrylic acid amide are according to weight ratio
0.8:1.0 composition mixture；The soft monomer is methyl acrylate.
It is described acrylic resin modified to be made by following steps:
1) graphene, acrylamide, monomer, PP resin, acrylic acid and 40% deionized water are added according to weight part ratio and is stirred
Device is mixed, is heated to stirring 125min under conditions of temperature is 60 DEG C, obtains colostric fluid；
2) balance deionized water being added in reactor and being warming up to temperature is 90 DEG C, and tert-butyl hydroperoxide is added later,
Then colostric fluid obtained in step 1) is slowly added to；
3) solution after reaction in step 2) is cooling, obtain acrylic resin modified first product；
4) acrylic resin modified first product obtained in step 3) is placed under the conditions of temperature is 115 DEG C and is dried, dried
The dry time is 3h, finally obtains acrylic resin modified finished product.
The coupling agent is the mixture that silane coupling agent and titanate coupling agent are 1.3 compositions according to weight ratio；It is described
Toughener is EPDM；The antioxidant is sulfuric acid.
A kind of preparation method of the MPP material of high intensity, characterized by the following steps:
1) according to parts by weight will nanometer calcium carbonate be added mixing agitator in, be warming up to temperature be 90 DEG C when with
The rate of 130rpm/min carries out first time stirring, and mixing time 75min adds coupling agent later with 75rpm/min's
Rate carries out second and stirs, and mixing time 135min, cooling and standings obtain mixture；
2) then according to parts by weight successively by acrylic resin modified, carbon black, toughener, antioxidant and calcium stearate
It is added in the mixture of step 1), continues to stir, discharge；
3) mixture obtained in step 2) is put into and is granulated by double screw extruder melting extrusion, high intensity is made
MPP material, area's temperature of the extrusion equipment are 210 DEG C, and two area's temperature are 225 DEG C, and three area's temperature are 245 DEG C, four Qu Wen
Degree is 245 DEG C, and five area's temperature are 257 DEG C, screw speed 300r/min.
A kind of cable protection pipe, the cable protection pipe are made by high-intensitive MPP material.
Comparative example 3
A kind of MPP material of high intensity, the raw material including following parts by weight:
The graphene is few layer graphene oxide, oxygen content 40wt%.
Every part of acrylic resin modified raw material including following parts by weight:
The monomer includes cross-linking monomer and soft monomer, and the cross-linking monomer is N hydroxymethyl acrylamide and N- isobutyl oxygen
Ylmethyl acrylic acid amide is according to the mixture that weight ratio is that 1:1.2 is formed；The soft monomer is ethyl acrylate and acrylic acid
Methyl esters is according to the mixture that weight ratio is that 1:1.2 is formed.
It is described acrylic resin modified to be made by following steps:
1) acrylamide, monomer, PP resin, acrylic acid and 40% deionized water are added into blender according to weight part ratio, added
Heat to temperature stirs 150min under conditions of being 70 DEG C, obtains colostric fluid；
2) balance deionized water being added in reactor and being warming up to temperature is 100 DEG C, and tert-butyl hydroperoxide is added later,
Then colostric fluid obtained in step 1) is slowly added to；
3) solution after reaction in step 2) is cooling, obtain acrylic resin modified first product；
4) acrylic resin modified first product obtained in step 3) is placed under the conditions of temperature is 130 DEG C and is dried, dried
The dry time is 2-4h, finally obtains acrylic resin modified finished product.
The coupling agent is silane coupling agent and titanate coupling agent according to the mixture that weight ratio is that 1.5:1.0 is formed；
The toughener is TPE and EPDM is according to the mixture that weight ratio is that 1:1 is formed；The antioxidant be tetrapentaerythritol ester and
Phenols is according to the mixture that weight ratio is that 0.8:1.0 is formed.
A kind of preparation method of the MPP material of high intensity, characterized by the following steps:
1) according to parts by weight will nanometer calcium carbonate be added mixing agitator in, be warming up to temperature be 100 DEG C when with
The rate of 150rpm/min carries out first time stirring, and mixing time 90min adds coupling agent later with 100rpm/min's
Rate carries out second and stirs, and mixing time 150min, cooling and standings obtain mixture；
2) then according to parts by weight successively by acrylic resin modified, graphene, carbon black, toughener, antioxidant and
Calcium stearate is added in the mixture of step 1), continues to stir, and discharges；
3) mixture obtained in step 2) is put into and is granulated by double screw extruder melting extrusion, high intensity is made
MPP material, area's temperature of the extrusion equipment are 220 DEG C, and two area's temperature are 230 DEG C, and three area's temperature are 255 DEG C, four Qu Wen
Degree is 255 DEG C, and five area's temperature are 265 DEG C, screw speed 400r/min.
A kind of cable protection pipe, the cable protection pipe are made by high-intensitive MPP material.
MPP material items mechanical performance obtained in specific embodiment 1-5 and comparative example 1-3 is detected respectively, is tied
Fruit is as shown in table 1.
Table 1
From the above results, every mechanical performance of MPP material obtained is more than qualification in 1-5 of the embodiment of the present invention
Index, MPP material melt mobility with higher, while MPP material also has good tensile strength and complete intensity.
Compared with Example 1, in comparative example 1 when preparing MPP material with acrylic resin instead of modified acroleic acid tree
Rouge carries out melt flow rate (MFR), tensile strength, elongation at break and bending strength to MPP material obtained and tests, and analysis is found
Melt flow rate (MFR), tensile strength, elongation at break and the equal relative reduction of bending strength of this MPP material；Illustrate that the present invention exists
Raw material is added special acrylic resin modified can optimize and MPP material items mechanical performance is made, and then makes to utilize its electricity obtained
Cable protection pipe is with corrosion resistance is strong, electric insulating quality is good, high mechanical strength, small heat-resisting, the cold-resistant, long service life of coefficient of friction
The features such as.
Compared with Example 3, in comparative example 2 when preparing MPP material in raw material without be added graphene A, to obtained
MPP material carries out melt flow rate (MFR), tensile strength, elongation at break and bending strength test, analysis and finds this MPP material
Melt flow rate (MFR), tensile strength, elongation at break and bending strength slightly reduce；Illustrate that graphene is added in raw material in the present invention
A can optimize obtained MPP material items mechanical performance, and then make have corrosion resistance strong, electric using its cable protection pipe obtained
The features such as gas good insulating, high mechanical strength, coefficient of friction small heat-resisting, cold-resistant, long service life.
Compared with Example 5, in comparative example 3 in preparation MPP material constantly in raw material that graphene B is not added, to being made
MPP material carry out melt flow rate (MFR), tensile strength, elongation at break and bending strength test, analysis finds this MPP material
Melt flow rate (MFR), tensile strength, elongation at break and the equal relative reduction of bending strength, especially melt flow rate (MFR)；It says
Graphene B, which is added, in raw material in the bright present invention can optimize obtained MPP material items mechanical performance, especially melt flow rate (MFR), into
And make to have using its cable protection pipe obtained that corrosion resistance is strong, electric insulating quality is good, high mechanical strength, coefficient of friction are small resistance to
The features such as hot, cold-resistant, long service life.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way,
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.
Claims (10)
1. a kind of MPP material of high intensity, it is characterised in that: the raw material including following parts by weight:
The graphene A is few layer graphene oxide, oxygen content 20-40wt%.
2. a kind of MPP material of high intensity according to claim 1, it is characterised in that: every part of modified acroleic acid tree
Rouge includes the raw material of following parts by weight:
The partial size of the graphene B is 50-80nm.
3. a kind of MPP material of high intensity according to claim 2, it is characterised in that: the monomer includes cross-linking monomer
And soft monomer, the cross-linking monomer are at least one of N hydroxymethyl acrylamide, N- isobutoxymethyl acrylic acid amide；
The soft monomer is at least one of butyl acrylate, ethyl acrylate or methyl acrylate.
4. a kind of MPP material of high intensity according to claim 2, it is characterised in that: it is described it is acrylic resin modified by
Following steps are made:
1) graphene B, acrylamide, monomer, PP resin, acrylic acid and 40% deionized water are added into stirring according to weight part ratio
Device, heating stirring obtain colostric fluid；
2) balance deionized water is added in reactor and is heated up, tert-butyl hydroperoxide is added later, then will obtained in step 1)
To colostric fluid be slowly added to；
3) solution after reaction in step 2) is cooling, obtain acrylic resin modified first product；
4) acrylic resin modified first product obtained in step 3) is dried, finally obtains acrylic resin modified finished product.
5. a kind of MPP material of high intensity according to claim 4, it is characterised in that: in the step 1) and step 2)
The weight ratio of deionized water used is 1.0-1.2:1.0；In step 1), the heating temperature is 50-70 DEG C, and mixing time is
100-150min；In step 2), being warming up to temperature is 80-100 DEG C；In step 4), drying temperature is 100-130 DEG C, when drying
Between be 2-4h.
6. a kind of MPP material of high intensity according to claim 1, it is characterised in that: the coupling agent is silane coupled
Agent and titanate coupling agent are according to the mixture that weight ratio is that 1.0-1.5:1.0 is formed.
7. a kind of MPP material of high intensity according to claim 1, it is characterised in that: the toughener be POE, TPE and
At least one of EPDM；The antioxidant is at least one of tetrapentaerythritol ester, phosphorous acid, sulfuric acid and phenols.
8. a kind of preparation method of such as MPP material of the described in any item high intensity of claim 1-7, it is characterised in that: including
Following steps:
1) nanometer calcium carbonate is added in mixing agitator according to parts by weight, heating carries out first time stirring, adds later
Coupling agent carries out second and stirs, and cooling and standings obtain mixture；
2) then according to parts by weight successively by acrylic resin modified, graphene A, carbon black, toughener, antioxidant and tristearin
Sour calcium is added in the mixture of step 1), continues to stir, and discharges；
3) mixture obtained in step 2) is put into extrusion equipment to be granulated by melting extrusion, high-intensitive MPP material is made.
9. a kind of preparation method of the MPP material of high intensity according to any one of claims 8, it is characterised in that: in the step 1), rise
Temperature to temperature is 80-100 DEG C, and first time stirring rate is 100-150rpm/min, and first time mixing time is 60-90min, the
Secondary agitation rate is 50-100rpm/min, and second of mixing time is 120-150min；The extrusion equipment squeezes for twin-screw
Machine out, area's temperature of the double screw extruder are 200-220 DEG C, and two area's temperature are 215-230 DEG C, and three area's temperature are 235-
255 DEG C, four area's temperature are 230-255 DEG C, and five area's temperature are 250-265 DEG C, screw speed 200-400r/min.
10. a kind of cable protection pipe, it is characterised in that: the cable protection pipe is by any one of claim 8-9 preparation method system
The high-intensitive MPP material obtained is made.
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