CN105295255A - Graphene oxide and glass-fiber reinforced polyvinyl chloride composite material and preparation method thereof - Google Patents
Graphene oxide and glass-fiber reinforced polyvinyl chloride composite material and preparation method thereof Download PDFInfo
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- CN105295255A CN105295255A CN201510859183.7A CN201510859183A CN105295255A CN 105295255 A CN105295255 A CN 105295255A CN 201510859183 A CN201510859183 A CN 201510859183A CN 105295255 A CN105295255 A CN 105295255A
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Abstract
The invention relates to a graphene oxide and glass-fiber reinforced polyvinyl chloride composite material and a preparation method thereof. The preparation method comprises the following steps: (1) according to a ratio, weighing 0 to 1 part of glass-fiber surface treating agent graphene oxide, preparing into a 0.2 mg/ml solution, weighing 5 to 30 parts of glass fiber, dispersing into the graphene oxide solution, and treating the surface of the glass fiber; (2) according to a ratio, weighing 60 to 90 parts of polyvinyl chloride resin, 5 to 30 parts of the glass fiber treated by the graphene oxide in step (1), 3 to 15 parts of compatilizer, 0 to 1 part of filler graphene oxide, and 1 to 4 parts of other auxiliaries, and mixing evenly in a high temperature mixing mill; (3) extruding and injection-molding the materials mixed evenly in step (2), thus obtaining the graphene oxide and glass-fiber reinforced polyvinyl chloride composite material. Compared with the prior art, the composite material has the advantages of simple preparation method, excellent mechanical property, low cost and the like.
Description
Technical field
The invention belongs to glass fiber compound material technical field, be specifically related to a kind of graphene oxide and reinforced PVC matrix material, the invention still further relates to the preparation method of this matrix material.
Background technology
Polyvinyl chloride has excellent erosion resistance, cheap, applies very extensive.But the shortcomings such as its rigidity is low, poor dimensional stability, use temperature are not high, shock resistance is poor make it again the ranks being difficult to enter engineering plastics.Modification is carried out to polyvinyl chloride (PVC) RESINS, is generally only limited in the past and improves its performance in a certain respect, and also can damage other side, thus can not improve its over-all properties comprehensively.
Resin is the important channel of improving its over-all properties by fiber reinforcement.In recent years; many research was carried out both at home and abroad to preparing reinforced PVC matrix material; such as patent CN102070855B discloses a kind of polyvinyl chloride composite materials and preparation method thereof; but the thermostability of polyvinyl chloride is bad; poor fluidity; the viscosity of glass fibre and polyvinyl chloride mixed system is high, so the reinforced PVC matrix material of excellent performance is difficult to form large-scale production and come into the market always.Preparing in reinforced PVC matrix material, due to the bad adhesion of glass fibre and polyvinyl chloride, so the INTERFACE DESIGN of reinforced PVC is a problem failing to solve very well always.Method that is main or employing coupling agent treatment improves interface at present.
But, the reinforced polyvinyl chloride matrix material prepared with the glass fibre through silane coupling agent process, its mechanics features of dry films be improved significantly, but by material with water soak, the conservation rate of its mechanical property is undesirable, and the moisture resistance properties of illustrative material is not so good.The mainly quantity not sufficient of chemical bond that produces of the interface of fiber and matrix.Generally speaking, modification reinforced polyvinyl chloride is carried out with glass fibre, no matter the preparation method from material, or from the improvement of material property, all achieve many progress, but, at present industrially or several fabricating technologies used in experiment all there is obvious shortcoming, the performance of material also need to improve.In addition, in reinforced PVC matrix material, the interfacial adhesion problem of glass fibre and matrix fails to be well solved always.
Summary of the invention
Object of the present invention is exactly provide to overcome defect that above-mentioned prior art exists the graphene oxide and reinforced PVC matrix material and preparation method thereof that a kind of preparation method is simple, excellent in mechanical performance, cost are low.
Object of the present invention can be achieved through the following technical solutions: a kind of graphene oxide and reinforced PVC matrix material, is characterized in that, the component that said composition comprises following weight part is made:
Polyvinyl chloride: 60-90 part;
Glass fibre: 5-30 part;
Fiberglass surface treating agent graphene oxide: 0-1 part;
Compatilizer: 3-15 part;
Filler graphene oxide: 0-1 part;
Other auxiliary agent: 1-4 part.
Described polyvinyl chloride (PVC) RESINS is universal polyvinyl chloride (PVC) RESINS, polychloroethylene with high polymerization degree resin, crosslinked pvc resin.
The short glass fiber that described glass fibre provides for Taishan glass fiber Ltd, length is 3mm, and diameter is 10 μm.
The thickness of described graphene oxide is 0.9 ~ 1.5nm, and lamella diameter is 2 ~ 5 μm.
Described compatilizer is maleic anhydride grafted polystyrene resin.
Other described auxiliary agent comprise in oxidation inhibitor, softening agent, ultraviolet-resistant absorbent, lubricant, impact modifying agent, thermo-stabilizer, toughner one or more.
Described graphene oxide is that laboratory utilizes the Hummers method preparation improved, and detailed process prepared by graphene oxide is:
A. under room temperature, 0.5 weight part SODIUMNITRATE, 1 parts by weight of graphite powder and the 46 weight part 98wt% vitriol oils are mixed under condition of ice bath, stir 30min, and then slowly add 3 weight part potassium permanganate, stir 30min;
B. the reaction system in step a is heated to 35 DEG C, stirs 2 ~ 48h, obtain brown suspension; In suspension, add 50 parts by weight of deionized water lentamente, stir, be warming up to 98 DEG C and continue reaction 5 ~ 10min, be cooled to room temperature;
C. the reaction solution of step b is poured in 167 parts by weight of deionized water while stirring, add 5 weight part 30wt% hydrogen peroxide, leave standstill 24h;
D. lower sediment is got, with deionized water centrifuge washing three times under 8000rpm condition, each 5 ~ 10min; Precipitate with deionized water is dialysed, until BaCl
2detect without SO
4 2-, add in deionized water by thick liquid after dialysis, supersound process 1h, then by solution centrifugal 5 ~ 10min under the condition of 4000 ~ 8000rpm, gained supernatant liquid is graphene oxide water solution.
To obtain graphene oxide water solution utilizes freeze-drying to obtain graphene oxide powder.Thickness is 0.9 ~ 1.5nm, and lamella diameter is 2 ~ 5 μm.
A preparation method for graphene oxide and reinforced PVC matrix material, is characterized in that, comprises the following steps:
(1) by said ratio, take the solution that surface treatment agent graphene oxide 0-1 part is made into 0.2mg/ml, take the glass fibre of 5-30 part, be distributed in the graphene oxide solution prepared, stir 24 hours with the rotating speed of 200rpm, be put into after evaporate to dryness falls moisture in baking oven, stand-by;
(2) by said ratio, 60-90 part polyvinyl chloride (PVC) RESINS is taken, 5-30 part glass fibre of the graphene oxide process in step (1), 3-15 part compatilizer, 0-1 part filler graphene oxide, other auxiliary agent of part, in high-temperature mixing machine, mix;
(3) raw material that step (2) mixes is joined melt blending in twin screw extruder, extrude, injection moulding obtains graphene oxide and reinforced PVC matrix material.
The twin screw extruder of described step (3) is in the same way or counter rotation twin screw extruder, and extruder temperature is
175-195 DEG C, input speed is 1-10rpm, and screw speed is 5-50rpm, and injection pressure is 50-80MPa.
An object of the present invention is to provide a kind of graphene oxide and reinforced PVC matrix material, this matrix material avoids the complex process of fiberglass surfacing grafted silane coupling agent, and mechanical property improves little shortcoming, reduce environmental pollution and cost; Meanwhile, also there is the advantages such as excellent in mechanical performance; In addition, this matrix material uses graphene oxide not only to fiberglass surfacing modification but also to polyvinyl chloride (PVC) RESINS matrix modification, make fiberglass surfacing and polyvinyl chloride (PVC) RESINS intrinsic silicon crosslinking reaction can occur, and then make the polyvinyl chloride composite materials of glass fiber reinforcement both have high rigidity, higher use temperature, good dimensional stability and notched Izod impact is had again to hit performance, pellet can also be made to produce various injection member, form series product, as being processed into water pipe, cable, waved plate, cooling tower and water tank etc.
Another object of the present invention is to provide the preparation method of a kind of above-mentioned graphene oxide and reinforced PVC matrix material, and this preparation method is simple, and cost is low, has outstanding contribution at aspect of performances such as raising mechanics.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
In following examples, tensile property testing standard is ISO527-2:2012, and bending property testing standard is ISO178:2010, and shock strength testing standard is ISO180:2000.
embodiment 1
Graphene oxide and reinforced PVC matrix material, prepared by the component of following weight percent:
Polyvinyl chloride: 60 parts;
Glass fibre: 30 parts;
Fiberglass surface treating agent graphene oxide: 1 part;
Compatilizer: 7.75 parts;
Filler graphene oxide: 0.25 part;
Other auxiliary agent: 1 part;
Preparation method is as follows:
(1) by said ratio, take the solution that fiberglass surface treating agent graphene oxide is mixed with 0.2mg/ml, short glass fiber is distributed in graphene oxide solution, stir 24 hours with the rotating speed of 200rpm, be put into after evaporate to dryness falls moisture in baking oven, case stand-by;
(2) by proportioning by polyvinyl chloride (PVC) RESINS, the glass fibre of the graphene oxide process in step (1), compatilizer, filler graphene oxide, other auxiliary agent, in high-temperature mixing machine, mixes;
(3) raw material that (2) mix is joined melt blending in twin screw extruder, extrude, injection moulding obtains graphene oxide and reinforced PVC matrix material.Twin screw extruder each district temperature is: 175 DEG C, a district, two 180 DEG C, districts, three 185 DEG C, districts, four 190 DEG C, districts, five 193 DEG C, districts; Head 195 DEG C, input speed is 1-10rpm, and screw speed is 5-50rpm, and injection pressure is 50-80MPa.
embodiment 2
Graphene oxide and reinforced PVC matrix material, prepared by the component of following weight percent:
Polyvinyl chloride: 90 parts;
Glass fibre: 5 parts;
Fiberglass surface treating agent graphene oxide: 0.75 part;
Compatilizer: 3 parts;
Filler graphene oxide: 0 part;
Other auxiliary agent: 1.25 parts;
Preparation method is same as embodiment 1.
embodiment 3
Graphene oxide and reinforced PVC matrix material, prepared by the component of following weight percent:
Polyvinyl chloride: 70 parts;
Glass fibre: 20 parts;
Fiberglass surface treating agent graphene oxide: 0.5 part;
Compatilizer: 5 parts;
Filler graphene oxide: 0.5 part;
Other auxiliary agent: 4 parts;
Preparation method is same as embodiment 1.
embodiment 4
Graphene oxide and reinforced PVC matrix material, prepared by the component of following weight percent:
Polyvinyl chloride: 60 parts;
Glass fibre: 20 parts;
Fiberglass surface treating agent graphene oxide: 0.25 part;
Compatilizer: 15 parts;
Filler graphene oxide: 0.75 part;
Other auxiliary agent: 4 parts;
Preparation method is same as embodiment 1.
embodiment 5
Graphene oxide and reinforced PVC matrix material, prepared by the component of following weight percent:
Polyvinyl chloride: 70 parts;
Glass fibre: 20 parts;
Fiberglass surface treating agent graphene oxide: 0 part;
Compatilizer: 6 parts;
Filler graphene oxide: 1 part;
Other auxiliary agent: 3 parts;
Preparation method is same as embodiment 1.
Each embodiment composite materials property test result is as shown in table 1 below.
Table 1 composite materials property test result
| Test event | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Flexural strength/MPa | 88.3 | 72.3 | 94.6 | 89.3 | 87.6 |
| Tensile strength/MPa | 65.6 | 50.2 | 69.7 | 66.8 | 64.7 |
| Shock strength/KJ/m 2 | 11.2 | 8.7 | 13.8 | 12.2 | 11.1 |
From upper table, mechanical experimental results is analyzed, and adopts the polyvinyl chloride composite materials intensity of graphene oxide and glass fiber reinforcement high, excellent in mechanical performance, meets the occasion higher to performance requriements and uses.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to embodiment, and this General Principle illustrated is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (8)
1. graphene oxide and a reinforced PVC matrix material, is characterized in that, the component comprising following weight part is made:
Polyvinyl chloride: 60-90 part;
Glass fibre: 5-30 part;
Fiberglass surface treating agent graphene oxide: 0-1 part;
Compatilizer: 3-15 part;
Filler graphene oxide: 0-1 part;
Other auxiliary agent: 1-4 part.
2. graphene oxide according to claim 1 and reinforced PVC matrix material, is characterized in that, described polyvinyl chloride (PVC) RESINS is universal polyvinyl chloride (PVC) RESINS, polychloroethylene with high polymerization degree resin, crosslinked pvc resin.
3. graphene oxide according to claim 1 and reinforced PVC matrix material, is characterized in that, the short glass fiber that described glass fibre provides for Taishan glass fiber Ltd, and length is 3mm, and diameter is 10 μm.
4. graphene oxide according to claim 1 and reinforced PVC matrix material, is characterized in that, the thickness of described graphene oxide is 0.9 ~ 1.5nm, and lamella diameter is 2 ~ 5 μm.
5. graphene oxide according to claim 1 and reinforced PVC matrix material, is characterized in that, described compatilizer is maleic anhydride grafted polystyrene resin.
6. graphene oxide according to claim 1 and reinforced PVC matrix material, it is special
Levy and be, other described auxiliary agent comprise oxidation inhibitor, softening agent, ultraviolet-resistant absorbent, lubricant,
One or more in impact modifying agent, thermo-stabilizer, toughner.
7. a preparation method for graphene oxide as claimed in claim 1 and reinforced PVC matrix material, is characterized in that comprising the following steps:
(1) by said ratio, take the solution that surface treatment agent graphene oxide 0-1 part is made into 0.2mg/ml, take the glass fibre of 5-30 part, be distributed in the graphene oxide solution prepared, stir 24 hours with the rotating speed of 200rpm, be put into after evaporate to dryness falls moisture in baking oven, stand-by;
(2) by said ratio, 60-90 part polyvinyl chloride (PVC) RESINS is taken, 5-30 part glass fibre of the graphene oxide process in step (1), 3-15 part compatilizer, 0-1 part filler graphene oxide, other auxiliary agent of 1-4 part, in high-temperature mixing machine, mix;
(3) raw material that step (2) mixes is joined melt blending in twin screw extruder, extrude, injection moulding obtains graphene oxide and reinforced PVC matrix material.
8. the preparation method of graphene oxide according to claim 7 and reinforced PVC matrix material, it is characterized in that, the twin screw extruder of described step (3) is in the same way or counter rotation twin screw extruder, extruder temperature is 175-195 DEG C, input speed is 1-10rpm, screw speed is 5-50rpm, and injection pressure is 50-80MPa.
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| CN106479085A (en) * | 2016-10-17 | 2017-03-08 | 黄宇 | A kind of high-impact Graphene modifying character for PVC material |
| CN106751831A (en) * | 2016-12-02 | 2017-05-31 | 机械科学研究总院青岛分院 | A kind of carbon fibre composite being applied in terms of new-energy automobile and preparation method thereof |
| CN107236224A (en) * | 2017-07-24 | 2017-10-10 | 李响 | A kind of preparation method of graphene modified polyvinyl-chloride composite material |
| CN112063076A (en) * | 2020-09-16 | 2020-12-11 | 博罗县东明新材料研究所 | Graphene polyvinyl chloride composite material and preparation method thereof |
| CN113150330A (en) * | 2021-05-25 | 2021-07-23 | 九江市磐泰复合材料有限公司 | Preparation method of glass fiber reinforced polyvinyl chloride material |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105670329A (en) * | 2016-04-05 | 2016-06-15 | 江苏宏远科技工程有限公司 | Preparation method of graphene-modified glass-fiber-reinforced composite material |
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| CN106479085A (en) * | 2016-10-17 | 2017-03-08 | 黄宇 | A kind of high-impact Graphene modifying character for PVC material |
| CN106751831A (en) * | 2016-12-02 | 2017-05-31 | 机械科学研究总院青岛分院 | A kind of carbon fibre composite being applied in terms of new-energy automobile and preparation method thereof |
| CN107236224A (en) * | 2017-07-24 | 2017-10-10 | 李响 | A kind of preparation method of graphene modified polyvinyl-chloride composite material |
| CN112063076A (en) * | 2020-09-16 | 2020-12-11 | 博罗县东明新材料研究所 | Graphene polyvinyl chloride composite material and preparation method thereof |
| CN112063076B (en) * | 2020-09-16 | 2023-03-28 | 博罗县东明新材料研究所 | Graphene polyvinyl chloride composite material and preparation method thereof |
| CN113150330A (en) * | 2021-05-25 | 2021-07-23 | 九江市磐泰复合材料有限公司 | Preparation method of glass fiber reinforced polyvinyl chloride material |
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