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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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 65
- 239000010439 graphite Substances 0.000 title claims abstract description 65
- -1 polyethylene Polymers 0.000 title claims abstract description 50
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 46
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000012986 modification Methods 0.000 claims abstract description 15
- 230000004048 modification Effects 0.000 claims abstract description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 10
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims abstract description 4
- 239000011159 matrix material Substances 0.000 claims description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 16
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229920001903 high density polyethylene Polymers 0.000 claims description 8
- 239000004700 high-density polyethylene Substances 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910021382 natural graphite Inorganic materials 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- 241000446313 Lamella Species 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 3
- CFOKKLCQKNYOGS-UHFFFAOYSA-N C(C(=C)C)(=O)[SiH]=O Chemical compound C(C(=C)C)(=O)[SiH]=O CFOKKLCQKNYOGS-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N NMP Substances CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical group [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000000945 filler Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000011256 inorganic filler Substances 0.000 abstract 1
- 229910003475 inorganic filler Inorganic materials 0.000 abstract 1
- 229920013716 polyethylene resin Polymers 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 8
- 239000002002 slurry Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- UNIYDALVXFPINL-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propylsilicon Chemical compound CC(=C)C(=O)OCCC[Si] UNIYDALVXFPINL-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000003913 materials processing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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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| CN118878975A (en) * | 2024-09-30 | 2024-11-01 | 山东齐鑫环保材料有限公司 | A kind of environmentally friendly ground film with high mechanical properties and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106115671A (en) * | 2016-06-23 | 2016-11-16 | 常州第六元素材料科技股份有限公司 | A kind of preparation method of alkylation modification Graphene |
| CN106115671B (en) * | 2016-06-23 | 2019-02-19 | 常州第六元素材料科技股份有限公司 | A kind of preparation method of alkylation modification graphene |
| CN118878975A (en) * | 2024-09-30 | 2024-11-01 | 山东齐鑫环保材料有限公司 | A kind of environmentally friendly ground film with high mechanical properties and preparation method thereof |
| CN118878975B (en) * | 2024-09-30 | 2025-01-28 | 山东齐鑫环保材料有限公司 | A kind of environmentally friendly ground film with high mechanical properties and preparation method thereof |
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| CN103756087B (en) | 2017-05-10 |
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