CN103756087A - High-performance graphite oxide reinforced polyethylene composite material and preparation method thereof - Google Patents
High-performance graphite oxide reinforced polyethylene composite material and preparation method thereof Download PDFInfo
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- CN103756087A CN103756087A CN201310707990.8A CN201310707990A CN103756087A CN 103756087 A CN103756087 A CN 103756087A CN 201310707990 A CN201310707990 A CN 201310707990A CN 103756087 A CN103756087 A CN 103756087A
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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Abstract
The invention discloses a preparation method of graphite oxide surface modification and graphite oxide reinforced polyethylene. The graphite oxide is subjected to surface modification by use of octadecylamine and a silane coupling agent, and the graphite oxide reinforced polyethylene is obtained through melt blending extrusion. The graphite oxide reinforced polyethylene comprises the following raw materials in parts by weight: 100 parts of polyethylene resin, 0.3-0.9 part of modified graphite oxide and 0.1-0.3 part of antioxidant 1010. The problem of dispersion of inorganic filler in high-molecular filler is solved by use of the characteristics that the graphite oxide is rich in oxygen-containing functional groups and is easily functionalized. The method is simple to operate, can effectively improve the tensile strength and flexural modulus of polyethylene and reduce the coefficient of linear expansion, and is easy to popularize in industrial production.
Description
Technical field
The invention belongs to materials processing and field of compound material, be specifically related to a kind of high-performance graphite oxide enhanced polyethylene matrix material and preparation method thereof.
Background technology
Polyethylene is the thermoplastic resin being polymerized by vinyl monomer, is one of current modal civilian plastics, has higher degree of crystallinity, chemical resistance and hardness and certain mechanical property.Good processability, is common in tubing, and sheet material is used with goods such as films.Yet its mechanical property is general, tensile strength only has 10-25MPa, and comparing engineering plastics has very large gap, has limited its Application Areas.By additive, its performance being carried out to modification is modal method of modifying, additive can be divided into particulate state according to pattern, and sheet and fibrous, from reinforced effects, laminal filler is compared other two kinds and is had good effect, but its interface performance has limited its application.
Summary of the invention
For the above-mentioned problems in the prior art, the object of the present invention is to provide a kind of high-performance graphite oxide enhanced polyethylene matrix material and preparation method thereof.
Described a kind of high-performance graphite oxide enhanced polyethylene matrix material, is characterized in that being comprised of the component of following weight percent:
100 parts of polyvinyl resins
Modified graphite oxide 0.3-0.9 part
Antioxidant 1010 0.1-0.3 part, is preferably 0.2 part.
Described a kind of high-performance graphite oxide enhanced polyethylene matrix material, is characterized in that described polyvinyl resin is high-density polyethylene resin, and its density is at 0.91-0.96g/cm
3, be a kind of soft and tough polymer materials.
Described a kind of high-performance graphite oxide enhanced polyethylene matrix material, it is characterized in that described modified graphite oxide is oxidized and peels off its surface by hummers method by natural graphite, after oxide treatment, with stearylamine and silane coupling agent, it is carried out to modification respectively, modified graphite oxide lamellar spacing is 10-20 layer, and lamella area is 100nm
2-500nm
2, there is a large amount of oxygen-containing functional groups in its surface, can fine dispersion in polar solvent.
Described a kind of high-performance graphite oxide enhanced polyethylene matrix material, is characterized in that described oxygen-containing functional group comprises hydroxyl, carboxyl, epoxy group(ing) and carbonyl.
Described a kind of high-performance graphite oxide enhanced polyethylene matrix material, is characterized in that described polar solvent is water, ethanol, THF, DMF or NMP.
Described a kind of high-performance graphite oxide enhanced polyethylene matrix material, it is characterized in that described silane coupling agent is vinyl silanes, methacryloyl oxosilane or aminosilane, therein ethylene base silane comprises vinyltrimethoxy silane, vinyltriethoxysilane etc.; Methacryloxypropyl silane comprises γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl group methyl dimethoxysilane; Aminosilane comprises γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane etc.
The preparation method of described a kind of high-performance graphite oxide enhanced polyethylene matrix material, is characterized in that comprising the steps:
1) functional modification of graphite oxide
Graphite oxide is dispersed in sulfur oxychloride liquid, ultrasonic 30min-2h, add DMF, reflux 20-25 hour, excessive sulfur oxychloride is removed in distillation, then the product obtaining is dispersed in DMF solution, add stearylamine and silane coupling agent, 120 ℃ of reaction 6h ~ 4d, filtered while hot is dried, obtain chain alkyl chemistry modified graphite oxide, described stearylamine and the graphite oxide mass ratio that feeds intake is 7-9:1;
2) preparation of graphite oxide modified polyvinyl resin matrix material
The chain alkyl chemistry modified graphite oxide obtaining in step 1) is dispersed in 300ml ethanolic soln, then adds in polyvinyl resin, add antioxidant 1010, after stirring, at 80 ℃, dry, directly use single screw rod to melt extrude, granulation.
The preparation method of described a kind of high-performance graphite oxide enhanced polyethylene matrix material, is characterized in that blend adopts single screw extrusion, and die cavity die head temperature is 190-210 ℃, and rotating speed is turn/s of 30-60.
The preparation method of described a kind of high-performance graphite oxide enhanced polyethylene matrix material, is characterized in that concrete operation method is as follows:
1) 300 ~ 900mg graphite oxide is dispersed in 200ml sulfur oxychloride liquid, ultrasonic 30min-2h, add 5ml DMF, backflow 20-25 hour, excessive sulfur oxychloride is removed in distillation, then the product obtaining is dispersed in 200ml DMF solution, add 2.4 ~ 7.2g stearylamine and silane coupling agent, 120 ℃ of reaction 6h ~ 4d, filtered while hot is dried, and obtains chain alkyl chemistry modified graphite oxide;
2) preparation of graphite oxide modified polyvinyl resin matrix material
The chain alkyl chemistry modified graphite oxide obtaining in step 1) is dispersed in 300ml ethanolic soln, adds in 100g polyvinyl resin, add 0.1-0.3g antioxidant 1010, fully stir, at 80 ℃, dry, directly use single screw rod to melt extrude, granulation.
The preparation method of described a kind of high-performance graphite oxide enhanced polyethylene matrix material, is characterized in that adding after 2.4 ~ 7.2g stearylamine at 120 ℃ of reaction 6h ~ 10h.
By adopting above-mentioned technology, compared with prior art, beneficial effect of the present invention is as follows:
1) the present invention by by natural graphite after peroxidation is peeled off, form the modified graphite oxide of low lamella, improve its mechanical property, and, while preparing due to graphite oxide, added strong oxidizer, the effect of this strong oxidizer makes its rich surface containing oxygen-containing functional group, as hydroxyl, carboxyl, epoxy group(ing), carbon back etc., these oxy radicals have strengthened the surfactivity of graphite oxide greatly, use stearylamine to react the chain alkyl chemistry modified graphite oxide of acquisition with its surperficial carboxyl, increased its dispersing property in polyethylene matrix, by silane coupling agent, carry out surface modification, further improve its scattering problem in polyethylene and increase its interface binding intensity, and its specific surface area is larger, belong to two-dimensional sheet material, can finely in matrix, play the effect that stress conduction disperses, the mechanical property of effective enhanced polyethylene,
2) the present invention is in the graphite oxide slurry and the polyvinyl resin mixing and stirring that directly modification are obtained, and mixed effect is compared direct powder and mixed, and dispersion agent is used ethanol simultaneously, and drying rate is fast, can play good mixing effect in the short period of time;
3) graphite oxide enhanced polyethylene matrix material of the present invention is directly used melt blending, simple to operate, does not add other solvents, has avoided the impact of Contamination On Mechanical Properties of Composite Materials, can obtain better blend effect in the short period of time;
4) the present invention is by joining modified graphite oxide in polyvinyl resin, prepare matrix material, there is good tensile strength and modulus in flexure, compare with existing composite polyethylene material, tensile strength has improved 17-38%, and modulus in flexure has improved 14-34%, and the isochrone coefficient of expansion reduces significantly, for pure poly 11%-37%, linear expansivity 24.9 * 10
-5, compare high density polyethylene(HDPE) 29 * 10
-5reduce by 11%; Because modified graphite oxide amount adds less, the strong successful of matrix material obtaining, cost performance is high, can reduce the consumption of raw material, well reduces costs.
Accompanying drawing explanation
Fig. 1 is the curve synoptic diagram of modified graphite oxide addition and matrix material tensile strength;
Fig. 2 is the curve synoptic diagram of modified graphite oxide addition and matrix material modulus in flexure.
Embodiment
Below in conjunction with Figure of description and embodiment, the invention will be further described:
Embodiment 1
1) preparation of graphite oxide be take natural graphite as raw material, with reference to Hummers legal system for graphite oxide, the graphite oxide of acquisition, thickness is 10-20 layer, size 100nm
2-500nm
2, a large amount of oxygen-containing functional groups is contained on surface, as hydroxyl, and carboxyl, epoxy group(ing), carbonyl etc. (following instance is identical).
2) surface modification of graphite oxide
300mg graphite oxide is added in there-necked flask, add 200ml sulfur oxychloride (SOCL
2) in liquid, ultrasonic 30min, adds 5ml DMF, refluxes 24 hours at 70 ℃, excessive sulfur oxychloride is removed in distillation.Then will obtain product and be dispersed in 200ml DMF solution, add 2.4g stearylamine, 120 ℃ of reaction 6h, filtered while hot is dried, and obtains chain alkyl chemistry modified graphite oxide.Acquisition product is added in 300ml ethanol and adds 15mg vinyltrimethoxy silane, and 80 ℃ of backflows obtained modified graphite oxide slurry after 2 hours;
In the present embodiment, with vinyltriethoxysilane, γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl group methyl dimethoxysilane), γ-aminopropyl triethoxysilane, γ-aminopropyltrimethoxysilane replaces vinyltrimethoxy silane, all can obtain same technique effect.
3) preparation of graphite oxide enhanced polyethylene matrix material
Direct and 100g polyethylene pellet (the extrusion grade high density polyethylene(HDPE) by the modified graphite oxide slurry obtaining, molecular weight 20-30 ten thousand, Dushanzi petrochemical industry, following examples are identical) mix, after mixing, at 80 ℃ of vacuum drying ovens, dry, directly add single screw extrusion machine after raw material stoving, melt blending is extruded (die cavity, 190 ℃ of die head temperatures, turn/s of rotating speed 30) granulation.
Use small injecting machine directly the modification pellet of acquisition to be injection molded into standard batten and carry out performance test, test obtains the composite polyethylene material tensile strength that this embodiment obtains and has improved 17%, and modulus in flexure has promoted 14%, linear expansivity 24.9 * 10
-5, compare high density polyethylene(HDPE) 29 * 10
-5reduce by 11%.
Example 2
1) preparation of graphite oxide is with example one
2) surface modification of graphite oxide
600mg graphite oxide is added in there-necked flask, add 200ml sulfur oxychloride (SOCL
2) in liquid, ultrasonic 30min, adds 5ml DMF, refluxes 24 hours at 70 ℃, excessive sulfur oxychloride is removed in distillation.Then will obtain product and be dispersed in 200ml DMF solution, add 4.8g stearylamine, 120 ℃ of reaction 6h, filtered while hot is dried, and obtains chain alkyl chemistry modified graphite oxide.Acquisition product is added in 300ml ethanol and adds 30mg vinyltrimethoxy silane, and 80 ℃ of backflows obtained modified graphite oxide slurry after 2 hours;
The preparation of graphite oxide enhanced polyethylene matrix material
3) preparation of graphite oxide enhanced polyethylene matrix material
The graphite oxide slurry of the modification obtaining is directly mixed with 100g polyethylene pellet, after mixing, at 80 ℃ of vacuum drying ovens, dry, directly add single screw extrusion machine after raw material stoving, melt blending is extruded (die cavity, 190 ℃ of die head temperatures, turn/s of rotating speed 30) granulation.
The graphite oxide enhanced polyethylene matrix material tensile strength obtaining has improved 28%, and modulus in flexure has promoted 23%.Linear expansivity 21.3 * 10
-5, than pure polyethylene, reduce by 24%.
Example three:
1) graphite oxide material is with example one.
2) surface modification of graphite oxide
900mg graphite oxide is added in there-necked flask, add in 200ml sulfur oxychloride (SOCL2) liquid, ultrasonic 30min, adds 5ml DMF, refluxes 24 hours at 70 ℃, and excessive sulfur oxychloride is removed in distillation.Then will obtain product and be dispersed in 200ml DMF solution, add 7.2g stearylamine, 120 ℃ of reaction 6h, filtered while hot is dried, and obtains chain alkyl chemistry modified graphite oxide.Acquisition product is added in 300ml ethanol and adds 45mg vinyltrimethoxy silane, and 80 ℃ of backflows obtained modified graphite oxide slurry after 2 hours.
3) preparation of graphite oxide enhanced polyethylene matrix material
The graphite oxide slurry of the modification obtaining is directly mixed with 100g polyethylene pellet, after mixing, at 80 ℃ of vacuum drying ovens, dry, directly add single screw extrusion machine after raw material stoving, melt blending is extruded (die cavity, 190 ℃ of die head temperatures, turn/s of rotating speed 30) granulation.
The graphite oxide enhanced polyethylene matrix material tensile strength obtaining has improved 38%, and modulus in flexure has promoted 34%, and linear expansivity 17.6 reduces by 37% than pure polyethylene.
From Fig. 1-2, can find out, when modified graphite oxide addition is polyvinyl resin 0.3-0.9wt %, matrix material tensile strength and modulus in flexure are relatively better, if modified graphite oxide very little, two kinds of intensity all reduce, and the amount adding is too many, and intensity improves few, but cost increases greatly, modified graphite oxide addition is that polyvinyl resin 0.3-0.9wt % is optimum quantity.
Claims (10)
1. a high-performance graphite oxide enhanced polyethylene matrix material, is characterized in that being comprised of the component of following weight percent:
100 parts of polyvinyl resins
Modified graphite oxide 0.3-0.9 part
Antioxidant 1010 0.1-0.3 part.
2. a kind of high-performance graphite oxide enhanced polyethylene matrix material according to claim 1, is characterized in that described polyvinyl resin is high-density polyethylene resin, and its density is at 0.91-0.96g/cm
3, be a kind of soft and tough polymer materials.
3. a kind of high-performance graphite oxide enhanced polyethylene matrix material according to claim 1, it is characterized in that described modified graphite oxide is oxidized and peels off its surface by hummers method by natural graphite, after oxide treatment, with stearylamine and silane coupling agent, it is carried out to modification respectively, modified graphite oxide lamellar spacing is 10-20 layer, and lamella area is 100nm
2-500nm
2, there is a large amount of oxygen-containing functional groups in its surface, can fine dispersion in polar solvent.
4. a kind of high-performance graphite oxide enhanced polyethylene matrix material according to claim 3, is characterized in that described oxygen-containing functional group comprises hydroxyl, carboxyl, epoxy group(ing) and carbonyl.
5. a kind of high-performance graphite oxide enhanced polyethylene matrix material according to claim 3, is characterized in that described polar solvent is water, ethanol, THF, DMF or NMP.
6. a kind of high-performance graphite oxide enhanced polyethylene matrix material according to claim 3, is characterized in that described silane coupling agent is vinyl silanes, methacryloyl oxosilane or aminosilane.
7. a preparation method for high-performance graphite oxide enhanced polyethylene matrix material, is characterized in that comprising the steps:
1) functional modification of graphite oxide
Graphite oxide is dispersed in sulfur oxychloride liquid, ultrasonic 30min-2h, add DMF, reflux 20-25 hour, excessive sulfur oxychloride is removed in distillation, then the product obtaining is dispersed in DMF solution, add stearylamine and silane coupling agent, 120 ℃ of reaction 6h ~ 4d, filtered while hot is dried, obtain chain alkyl chemistry modified graphite oxide, described stearylamine and the graphite oxide mass ratio that feeds intake is 7-9:1;
2) preparation of graphite oxide modified polyvinyl resin matrix material
The chain alkyl chemistry modified graphite oxide obtaining in step 1) is dispersed in 300ml ethanolic soln, then adds in polyvinyl resin, add antioxidant 1010, after stirring, at 80 ℃, dry, directly use single screw rod to melt extrude, granulation.
8. the preparation method of a kind of high-performance graphite oxide enhanced polyethylene matrix material according to claim 7, is characterized in that blend adopts single screw extrusion, and die cavity die head temperature is 190-210 ℃, and rotating speed is turn/s of 30-60.
9. the preparation method of a kind of high-performance graphite oxide enhanced polyethylene matrix material according to claim 7, is characterized in that concrete operation method is as follows:
1) 300 ~ 900mg graphite oxide is dispersed in 200ml sulfur oxychloride liquid, ultrasonic 30min-2h, add 5ml DMF, backflow 20-25 hour, excessive sulfur oxychloride is removed in distillation, then the product obtaining is dispersed in 200ml DMF solution, add 2.4 ~ 7.2g stearylamine and silane coupling agent, 120 ℃ of reaction 6h ~ 4d, filtered while hot is dried, and obtains chain alkyl chemistry modified graphite oxide;
2) preparation of graphite oxide modified polyvinyl resin matrix material
The chain alkyl chemistry modified graphite oxide obtaining in step 1) is dispersed in 300ml ethanolic soln, adds in 100g polyvinyl resin, add 0.1-0.3g antioxidant 1010, fully stir, at 80 ℃, dry, directly use single screw rod to melt extrude, granulation.
10. the preparation method of a kind of high-performance graphite oxide enhanced polyethylene matrix material according to claim 7, is characterized in that adding after 2.4 ~ 7.2g stearylamine at 120 ℃ of reaction 6h ~ 10h.
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