CN105295255A - Graphene oxide and glass-fiber reinforced polyvinyl chloride composite material and preparation method thereof - Google Patents

Abstract

The invention relates to a graphene oxide and glass fiber reinforced polyvinyl chloride composite material and a preparation method thereof, comprising the following steps: (1) according to the proportion, weigh 0-1 part of the glass fiber surface treatment agent graphene oxide to prepare 0.2 mg/ml solution, take by weighing 5-30 parts of glass fiber, be dispersed in the graphene oxide solution, and carry out surface treatment to glass fiber; (2) take by weighing 60-90 parts of polyvinyl chloride resin by proportioning, step (1 5-30 parts of glass fibers treated with graphene oxide in ), 3-15 parts of compatibilizer, 0-1 part of filler graphene oxide, 1-4 parts of other additives, in a high-temperature mixer, mix uniformly; (3) The homogeneously mixed raw materials in step (2) are extruded and injected to obtain a graphene oxide and glass fiber reinforced polyvinyl chloride composite material. Compared with the prior art, the composite material of the invention has the advantages of simple preparation method, excellent mechanical properties, low cost and the like.

Description

A kind of graphene oxide and glass fiber reinforced polyvinyl chloride composite material and preparation method thereof

technical field

The invention belongs to the technical field of glass fiber composite materials, and in particular relates to a graphene oxide and glass fiber reinforced polyvinyl chloride composite material, and also relates to a preparation method of the composite material.

Background technique

Polyvinyl chloride has excellent corrosion resistance, low price, and is widely used. However, its low rigidity, poor dimensional stability, low operating temperature, and poor impact resistance make it difficult to enter the ranks of engineering plastics. The modification of polyvinyl chloride resin was generally limited to improving its performance in one aspect in the past, and it would also damage other aspects, so it could not fully improve its comprehensive performance.

Reinforcement by fiber is an important way to improve its comprehensive performance. In recent years, a lot of research has been done on the preparation of glass fiber reinforced polyvinyl chloride composite materials at home and abroad. For example, patent CN102070855B discloses a polyvinyl chloride composite material and its preparation method, but the thermal stability of polyvinyl chloride is not good, and the flow Poor performance and high viscosity of glass fiber and polyvinyl chloride mixed system, so glass fiber reinforced polyvinyl chloride composite materials with excellent performance have been difficult to form large-scale production and enter the market. In the preparation of glass fiber reinforced polyvinyl chloride composites, due to the poor bonding between glass fibers and polyvinyl chloride, the interface design of glass fiber reinforced polyvinyl chloride has been a problem that has not been well resolved. At present, the method of coupling agent treatment is mainly used to improve the interface.

However, the dry mechanical properties of reinforced polyvinyl chloride composites prepared with glass fibers treated with silane coupling agents have been significantly improved, but the retention rate of the mechanical properties is not ideal when the material is soaked in water, indicating that the moisture resistance of the material not too good. The main reason is that the amount of chemical bonds generated at the interface between the fiber and the matrix is insufficient. In general, the use of glass fiber to modify reinforced polyvinyl chloride has made a lot of progress in terms of the preparation method of the material and the improvement of the performance of the material. However, several methods currently used in industry or experiments All these preparation techniques have obvious shortcomings, and the performance of the material also needs to be improved. In addition, the interface bonding between glass fiber and matrix in glass fiber reinforced polyvinyl chloride composites has not been well resolved.

Contents of the invention

The object of the present invention is to provide a graphene oxide and glass fiber reinforced polyvinyl chloride composite material with simple preparation method, excellent mechanical properties and low cost and a preparation method thereof in order to overcome the above-mentioned defects in the prior art.

The object of the present invention can be achieved through the following technical solutions: a graphene oxide and glass fiber reinforced polyvinyl chloride composite material, is characterized in that, the composition comprises the following components by weight and made:

Polyvinyl chloride: 60-90 parts;

Glass fiber: 5-30 parts;

Glass fiber surface treatment agent graphene oxide: 0-1 part;

Compatibilizer: 3-15 parts;

Filler graphene oxide: 0-1 part;

Other additives: 1-4 parts.

The polyvinyl chloride resin is a general-purpose polyvinyl chloride resin, a high degree of polymerization polyvinyl chloride resin, or a cross-linked polyvinyl chloride resin.

The glass fibers are chopped glass fibers provided by Taishan Glass Fiber Co., Ltd., with a length of 3 mm and a diameter of 10 μm.

The thickness of the graphene oxide is 0.9-1.5 nm, and the sheet diameter is 2-5 μm.

The compatibilizer is maleic anhydride grafted polystyrene resin.

The other additives include one or more of antioxidants, plasticizers, anti-ultraviolet absorbers, lubricants, impact modifiers, heat stabilizers, and tougheners.

Described graphene oxide is that the laboratory utilizes the improved Hummers method to prepare, and the concrete process of graphene oxide preparation is:

a. At room temperature, 0.5 parts by weight of sodium nitrate, 1 part by weight of graphite powder and 46 parts by weight of 98wt% concentrated sulfuric acid were mixed under ice bath conditions, stirred for 30 minutes, then slowly added 3 parts by weight of potassium permanganate, stirred for 30 minutes;

b. Heat the reaction system in step a to 35°C, stir for 2~48h to obtain a brown suspension; slowly add 50 parts by weight of deionized water to the suspension, stir, heat up to 98°C and continue the reaction for 5~10min, Cool to room temperature;

c. Pour the reaction solution of step b into 167 parts by weight of deionized water while stirring, add 5 parts by weight of 30wt% hydrogen peroxide, and let stand for 24h;

d. Remove the lower layer of precipitate, and centrifuge and wash it with deionized water at 8000rpm three times, each time for 5-10 minutes; dialyze the precipitate with deionized water until no SO ₄ ^2- is detected in BaCl ₂ , and add the viscous liquid to the deionized water after dialysis Ultrasonic treatment in ionized water for 1 h, and then centrifuge the solution at 4000-8000 rpm for 5-10 min, and the obtained upper liquid is the graphene oxide aqueous solution.

The obtained graphene oxide aqueous solution is obtained by freeze-drying to obtain graphene oxide powder. The thickness is 0.9~1.5nm, and the sheet diameter is 2~5μm.

A preparation method of graphene oxide and glass fiber reinforced polyvinyl chloride composite material, is characterized in that, comprises the following steps:

(1) According to the above-mentioned proportioning, take 0-1 part of surface treatment agent graphene oxide to be made into the solution of 0.2mg/ml, take by weighing 5-30 parts of glass fiber, be dispersed in the prepared graphene oxide solution, Stir at a speed of 200rpm for 24 hours, put it in an oven to evaporate the water, and set aside;

(2) According to the above-mentioned proportioning, take by weighing 60-90 parts of polyvinyl chloride resin, 5-30 parts of glass fibers handled by graphene oxide in step (1), 3-15 parts of compatibilizer, 0-1 part of filler Graphene oxide and other additives are mixed uniformly in a high-temperature mixer;

(3) Add the homogeneously mixed raw materials in step (2) into a twin-screw extruder for melt blending, extrusion, and injection molding to prepare graphene oxide and glass fiber reinforced polyvinyl chloride composite materials.

The twin-screw extruder of described step (3) is corotating or different direction twin-screw extruder, and extruder temperature is

175-195°C, the feed rate is 1-10rpm, the screw speed is 5-50rpm, and the injection pressure is 50-80MPa.

One of the purposes of the present invention is to provide a graphene oxide and glass fiber reinforced polyvinyl chloride composite material, which avoids the complicated process of grafting silane coupling agent on the surface of glass fiber, and has the disadvantage that the mechanical properties are not greatly improved. Reduces environmental pollution and cost; at the same time, it also has the advantages of excellent mechanical properties; in addition, the composite material uses graphene oxide to modify both the surface of the glass fiber and the matrix of the polyvinyl chloride resin, so that the surface of the glass fiber and the polyvinyl chloride resin are modified. The cross-linking reaction can occur inside the vinyl chloride resin matrix, so that the glass fiber reinforced polyvinyl chloride composite material has high rigidity, high service temperature, good dimensional stability and notched impact resistance, and can also It is made into pellets to produce various injection parts to form a series of products, such as water pipes, cables, corrugated plates, cooling towers and water tanks.

Another object of the present invention is to provide a method for preparing the above-mentioned graphene oxide and glass fiber reinforced polyvinyl chloride composite material. The preparation method is simple, low in cost, and has outstanding contributions in improving mechanical and other properties.

detailed description

The present invention will be described in detail below in conjunction with specific embodiments.

In the following examples, the tensile performance testing standard is ISO527-2:2012, the bending performance testing standard is ISO178:2010, and the impact strength testing standard is ISO180:2000.

Example 1

Graphene oxide and glass fiber reinforced polyvinyl chloride composite material, prepared from the following components by weight percentage:

Polyvinyl chloride: 60 parts;

Glass fiber: 30 parts;

Glass fiber surface treatment agent graphene oxide: 1 part;

Compatibilizer: 7.75 parts;

Filler graphene oxide: 0.25 parts;

Other additives: 1 part;

The preparation method is as follows:

(1) According to the above ratio, take the glass fiber surface treatment agent graphene oxide and be mixed with a solution of 0.2 mg/ml, disperse the chopped glass fibers in the graphene oxide solution, stir for 24 hours at a speed of 200 rpm, and put After the moisture is evaporated in the oven, the box is packed for use;

(2) by proportioning polyvinyl chloride resin, the glass fiber that the graphene oxide in the step (1) handles, compatibilizer, filler graphene oxide, other additives, in high-temperature kneader, mix homogeneously;

(3) Add the homogeneously mixed raw materials of (2) into a twin-screw extruder for melt blending, extrusion, and injection molding to prepare graphene oxide and glass fiber reinforced polyvinyl chloride composite materials. The temperature of each zone of the twin-screw extruder is: zone 1 175°C, zone 2 180°C, zone 3 185°C, zone 4 190°C, zone 5 193°C; head 195°C, feed rate 1-10rpm, screw speed 5-50rpm, the injection pressure is 50-80MPa.

Example 2

Graphene oxide and glass fiber reinforced polyvinyl chloride composite material, prepared from the following components by weight percentage:

Polyvinyl chloride: 90 parts;

Fiberglass: 5 parts;

Glass fiber surface treatment agent graphene oxide: 0.75 parts;

Compatibilizer: 3 parts;

Filler graphene oxide: 0 parts;

Other additives: 1.25 parts;

The preparation method is the same as in Example 1.

Example 3

Graphene oxide and glass fiber reinforced polyvinyl chloride composite material, prepared from the following components by weight percentage:

Polyvinyl chloride: 70 parts;

Glass fiber: 20 parts;

Glass fiber surface treatment agent graphene oxide: 0.5 part;

Compatibilizer: 5 parts;

Filler graphene oxide: 0.5 part;

Other additives: 4 parts;

The preparation method is the same as in Example 1.

Example 4

Graphene oxide and glass fiber reinforced polyvinyl chloride composite material, prepared from the following components by weight percentage:

Polyvinyl chloride: 60 parts;

Glass fiber: 20 parts;

Glass fiber surface treatment agent graphene oxide: 0.25 parts;

Compatibilizer: 15 parts;

Filler graphene oxide: 0.75 parts;

Other additives: 4 parts;

The preparation method is the same as in Example 1.

Example 5

Graphene oxide and glass fiber reinforced polyvinyl chloride composite material, prepared from the following components by weight percentage:

Polyvinyl chloride: 70 parts;

Glass fiber: 20 parts;

Glass fiber surface treatment agent graphene oxide: 0 parts;

Compatibilizer: 6 parts;

Filler graphene oxide: 1 part;

Other additives: 3 parts;

The preparation method is the same as in Example 1.

The test results of the mechanical properties of the composite materials in each example are shown in Table 1 below.

Table 1 Test results of mechanical properties of composite materials

Test items Example 1 Example 2 Example 3 Example 4 Example 5 Bending 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 Impact strength/KJ/m ² 11.2 8.7 13.8 12.2 11.1

From the analysis of the mechanical performance test results in the above table, it can be seen that the polyvinyl chloride composite material reinforced with graphene oxide and glass fiber has high strength and excellent mechanical properties, which is suitable for use in occasions with high performance requirements.

The above description of the embodiments is for those of ordinary skill in the art to understand and apply the present invention. It is obvious that those skilled in the art can easily make various modifications to the embodiment, and apply the general principles described in this description to other embodiments without creative effort. Therefore, the present invention is not limited to the embodiments herein. Improvements and modifications made by those skilled in the art according to the disclosure of the present invention without departing from the scope of the present invention should fall within the 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.