CN103804758A - Modified high-density polyethylene master batch and preparation method thereof - Google Patents
Modified high-density polyethylene master batch and preparation method thereof Download PDFInfo
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- CN103804758A CN103804758A CN201410042353.8A CN201410042353A CN103804758A CN 103804758 A CN103804758 A CN 103804758A CN 201410042353 A CN201410042353 A CN 201410042353A CN 103804758 A CN103804758 A CN 103804758A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/013—Additives applied to the surface of polymers or polymer particles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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Abstract
The invention provides a modified high-density polyethylene master batch and a preparation method thereof. The modified high-density polyethylene master batch comprises high-density polyethylene particles, dry graphene powder, talcum powder, calcium stearate, an antioxidant SONOX1076, maleic anhydride-grafted ethylene-propylene-diene monomer, isopropyl tri(dioctyl pyrophosphate acyloxy)titanate, an ultraviolet absorbent UV-531 and a light stabilizer 744. The preparation method comprises the steps of firstly spraying and modifying the high-density polyethylene particles by virtue of the dry graphene powder carrying static electricity, then uniformly mixing the modified high-density polyethylene particles with the residual components, sending the mixture into a double-screw extruder, carrying out melting blending, and finally carrying out die-head extrusion and granulation. The modified high-density polyethylene master batch has the advantages that not only is the heat-conducting property substantially improved, but also the mechanical property is improved to a certain degree.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of modification high-density polyethylene master batch and preparation method thereof.
Background technology
High density polyethylene(HDPE) is owing to having good insulativity, heat-resisting cold tolerance and good mechanical property, so be widely used in the aspects such as automotive industry, household electrical appliance, tubing, mechanical component making as the conventional engineering plastics of one.But high density polyethylene(HDPE) also has two larger shortcomings, insufficient strength, heat conductivility are general, and in use easily accumulating amount of heat had both affected work-ing life, had limited again its range of application.
Along with the high speed development of microelectronics integrated technology, original paper heat release improves rapidly.Now be badly in need of having the heat conductive insulating polymer composite traditional hot interface of replacement and the packaged material of high reliability, high-cooling property.In filling-type thermal-conducting electric-insulating polymer, thermal conductivity depends on polymer and heat conductive filler synergy.In the time that heat conductive filler has formed similar netted or chain-like structure form (forming heat conduction network chain) in system, thermal conductivity will sharply increase.
It in its structure of Graphene, is a two-dimensional material, itself has high thermal conductivity, for forming, heat conduction network chain is significant, because the heat conduction network chain of its formation is three-dimensional net structure, effectively enhancement of heat transfer of one side, be tridimensional network because it respectively above distributes mutually on the other hand, therefore can reduce because of the different impacts that cause of direction of heat flow.While also can be improved the performances such as the physical strength of macromolecular material.
Summary of the invention
The object of this invention is to provide a kind of modification high-density polyethylene master batch and preparation method thereof.
A kind of modification high-density polyethylene master batch, comprise in weight part: 100 parts, high density polyethylene(HDPE) particle, 0.01～5 part, Graphene dry powder, 5～10 parts of talcum powder, 0.2～1 part of calcium stearate, 1,076 0.5～1 parts of oxidation inhibitor SONOX, 1～5 part of maleic anhydride graft terpolymer EP rubber, 2～5 parts of sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, 0.1～0.5 part of uv-absorbing agent UV-531,744 0.5～1 part of photostabilizer.
As foregoing invention further preferably, described high density polyethylene(HDPE) particle is HDPE310M, granularity is 100 order～5 orders.
As foregoing invention further preferably, described Graphene dry powder thickness is 1～2nm.
The preparation method of above-mentioned modification high-density polyethylene particle, comprises the following steps:
Step 1, to high density polyethylene(HDPE) particle, through the Graphene dry powder spraying modification with static, static output voltage is 10～25KV, and static outward current is 5～15 μ A, and powder outlet quantity is 2～10g/min;
Step 2, step 1 gained high density polyethylene(HDPE) particle is added in high-speed mixer and mixed with talcum powder, calcium stearate, oxidation inhibitor SONOX1076, maleic anhydride graft terpolymer EP rubber, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, uv-absorbing agent UV-531 and photostabilizer 744, then being placed in vacuum drying oven dries, wherein mixing temperature is 60～80 ℃, mixing time is 5～20min, oven temperature is 80～95 ℃, and drying time is 10～24h;
Step 3, step 2 gained material is sent into twin screw extruder and carry out melting mixing, after die head extruding pelletization, obtain the high heat conduction high density polyethylene(HDPE) of the high strength master batch of Graphene modification, wherein, twin screw extruder length-to-diameter ratio is 30:1～70:1, and twin screw temperature setting is set to 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, and forcing machine rotating speed is 160～220rpm.
The present invention by electrostatic applications machine nozzle, makes graphene powder electronegative Graphene, is sprayed on positively charged (and ground connection) macromolecular material in stirring.Because being uses electrostatic spraying, graphene powder and macromolecular material are all electrically charged, can control Graphene and be less than 20nm at the coating thickness of polymer surface, there will not be local inhomogeneous phenomenon.Due to grapheme material and macromolecular material, by while electrostatic means combination, make both in conjunction with very tight simultaneously, formed special structure.Mix compared to common homogenizer, easily keep the clad structure of Graphene to macromolecular material, after extrusion granulator, structure also can keep, thereby has produced special heat conductivility and relative mechanical property preferably.
Compared with prior art, its remarkable advantage is in the present invention: high-density polyethylene material of the present invention not only heat conductivility is greatly improved, and its mechanical property also has certain amplitude to promote simultaneously.And traditional heat conduction modified polymer material, after improving thermal conductivity, often adding impact and reducing its mechanical property because of heat conductive filler.
Embodiment
Embodiment 1
In weight part, the Graphene dry powder that is 1～2nm by 2 parts of thickness is positioned in electrostatic sprayer, setting static output voltage is that 10KV, static outward current are that 5 μ A, powder outlet quantity are controlled at 4g/min, is on 10～15 object HDPE 310M by Graphene dry powder spraying in 100 parts of granularities.
In weight part, gained Graphene modification high-density polyethylene particle, 5 parts of talcum powder, 0.2 part of calcium stearate, 0.5 part of antioxidant 1076,1 part of maleic anhydride graft terpolymer EP rubber, 2 parts of sec.-propyls three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, 0.1 part of uv-absorbing agent UV-531,0.5 part of photostabilizer 744 are added in high-speed mixer and mixed, mixing temperature is 60 ℃, mixing time is 5min, is then placed in 90 ℃ of vacuum drying ovens and dries 10h.The material mixing is sent into twin screw extruder after volume pump, and length-to-diameter ratio is 30: 1, carries out melting mixing, and twin screw temperature setting is set to 170 ℃, and 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, forcing machine rotating speed is 160rpm.Finally by crossing after die head extruding pelletization.
Embodiment 2
In weight part, the Graphene dry powder that is 1～2nm by 0.5 part of thickness is positioned in electrostatic sprayer, setting static output voltage is that 15KV, static outward current are that 8 μ A, powder outlet quantity are controlled at 2g/min, is on 50～60 object HDPE 310M by Graphene dry powder spraying in 100 parts of granularities.
In weight part, gained Graphene modification high-density polyethylene particle, 10 parts of talcum powder, 1 part of calcium stearate, 1 part of antioxidant 1076,5 parts of maleic anhydride graft terpolymer EP rubbers, 5 parts of sec.-propyls three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, 0.5 part of uv-absorbing agent UV-531,1 part of photostabilizer 744 are added in high-speed mixer and mixed, mixing temperature is 80 ℃, mixing time is 8min, is then placed in 90 ℃ of vacuum drying ovens and dries 10h.The material mixing is sent into twin screw extruder after volume pump, and length-to-diameter ratio is 50: 1, carries out melting mixing, and twin screw temperature setting is set to 170 ℃, and 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, forcing machine rotating speed is 170rpm.Finally by crossing after die head extruding pelletization.
Embodiment 3
In weight part, the Graphene dry powder that is 1～2nm by 0.02 part of thickness is positioned in electrostatic sprayer, setting static output voltage is that 12KV, static outward current are that 6 μ A, powder outlet quantity are controlled at 2g/min, is on 100 object HDPE 310M by Graphene dry powder spraying in 100 parts of granularities.
In weight part, gained Graphene modification high-density polyethylene particle, 7.8 parts of talcum powder, 0.69 part of calcium stearate, 0.74 part of antioxidant 1076,2.8 parts of maleic anhydride graft terpolymer EP rubbers, 3 parts of sec.-propyls three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, 0.36 part of uv-absorbing agent UV-531,0.82 part of photostabilizer 744 are added in high-speed mixer and mixed, mixing temperature is 85 ℃, mixing time is 10min, is then placed in 95 ℃ of vacuum drying ovens and dries 14h.The material mixing is sent into twin screw extruder after volume pump, carry out melting mixing, twin screw temperature setting is set to 170 ℃, and 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, forcing machine rotating speed is 220rpm.Finally by crossing after die head extruding pelletization.
Comparative example 1
In the present embodiment, the consumption of Graphene dry powder is 0 part, not cardiac high density polyethylene(HDPE) particle spraying modification, other feed intake and processing step with embodiment 3
Above-described embodiment gained master batch is carried out to performance test, and experimental result is as follows:
From above data, through Graphene modification high-density polyethylene particle compare ratio not only mechanical property significantly risen, and its thermal conductivity is also significantly improved.Its modification reason may be: 1, Graphene exerts an influence for three grades of distributions of polyethylene molecule, and then mechanical property is produced and changed; 2, the structure of Graphene itself and its distribution mode in high-density polyethylene material are conducive to the conduction of heat.
Claims (4)
1. a modification high-density polyethylene master batch, it is characterized in that: comprise in weight part: 100 parts, high density polyethylene(HDPE) particle, 0.01～5 part, Graphene dry powder, 5～10 parts of talcum powder, 0.2～1 part of calcium stearate, 1,076 0.5～1 parts of oxidation inhibitor SONOX, 1～5 part of maleic anhydride graft terpolymer EP rubber, 2～5 parts of sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, 0.1～0.5 part of uv-absorbing agent UV-531,744 0.5～1 part of photostabilizer.
2. a kind of modification high-density polyethylene master batch according to claim 1, is characterized in that: described high density polyethylene(HDPE) particle is HDPE310M, granularity is 100 order～5 orders.
3. a kind of modification high-density polyethylene master batch according to claim 1, is characterized in that: described Graphene dry powder thickness is 1～2nm.
4. the preparation method of any one modification high-density polyethylene particle described in claims 1 to 3, is characterized in that: comprise the following steps:
Step 1, to high density polyethylene(HDPE) particle, through the Graphene dry powder spraying modification with static, static output voltage is 10 ~ 25KV, and static outward current is 5 ~ 15 μ A, and powder outlet quantity is 2 ~ 10g/min;
Step 2, step 1 gained high density polyethylene(HDPE) particle is added in high-speed mixer and mixed with talcum powder, calcium stearate, oxidation inhibitor SONOX1076, maleic anhydride graft terpolymer EP rubber, sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, uv-absorbing agent UV-531 and photostabilizer 744, then being placed in vacuum drying oven dries, wherein mixing temperature is 60～80 ℃, mixing time is 5～20min, oven temperature is 80～95 ℃, and drying time is 10～24h;
Step 3, step 2 gained material is sent into twin screw extruder and carry out melting mixing, after die head extruding pelletization, obtain the high heat conduction high density polyethylene(HDPE) of the high strength master batch of Graphene modification, wherein, twin screw extruder length-to-diameter ratio is 30:1～70:1, and twin screw temperature setting is set to 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, and forcing machine rotating speed is 160～220rpm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104059272A (en) * | 2014-06-11 | 2014-09-24 | 蓝星（成都）新材料有限公司 | High-density polyethylene modified material and preparation method thereof |
| CN105820422A (en) * | 2016-05-03 | 2016-08-03 | 合肥中澜新材料科技有限公司 | High-hardness polyethylene composition and preparing process thereof |
| CN106046485A (en) * | 2016-06-28 | 2016-10-26 | 常州第六元素材料科技股份有限公司 | Ultra-high molecular weight polyethylene/graphene/rubber composite material and preparation technique thereof |
| CN111635574A (en) * | 2020-06-19 | 2020-09-08 | 中北大学 | PP/PE/BN/EPDM heat-conducting insulating material and preparation method thereof |
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| CN104059272A (en) * | 2014-06-11 | 2014-09-24 | 蓝星（成都）新材料有限公司 | High-density polyethylene modified material and preparation method thereof |
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| CN106046485A (en) * | 2016-06-28 | 2016-10-26 | 常州第六元素材料科技股份有限公司 | Ultra-high molecular weight polyethylene/graphene/rubber composite material and preparation technique thereof |
| CN111635574A (en) * | 2020-06-19 | 2020-09-08 | 中北大学 | PP/PE/BN/EPDM heat-conducting insulating material and preparation method thereof |
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