CN103540104A - Graphene oxide reinforced vinyl ester composite material and preparation method thereof - Google Patents
Graphene oxide reinforced vinyl ester composite material and preparation method thereof Download PDFInfo
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- CN103540104A CN103540104A CN201310501959.9A CN201310501959A CN103540104A CN 103540104 A CN103540104 A CN 103540104A CN 201310501959 A CN201310501959 A CN 201310501959A CN 103540104 A CN103540104 A CN 103540104A
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Abstract
The invention discloses a graphene oxide reinforced vinyl ester composite material and a preparation method thereof. The graphene oxide reinforced vinyl ester composite material disclosed by the invention comprises vinyl ester resin, glass fibre, graphene oxide powder, a low profile agent, a thickener, inorganic mineral filler and a curing agent. The graphene oxide reinforced vinyl ester composite material disclosed by the invention has excellent composite performances by utilizing the huge specific surface area of graphene oxide and the abundant functional groups on the surface; graphene oxide and a resin-based composite material are composited, and therefore, the performances in the aspects of heat, force, electric and the like of the material can be obviously improved. The composite material disclosed by the invention is in the form of a sheet moulding compound; the adopted forming process is compression moulding forming or injection forming; the preparation method disclosed by the invention is simple and easy to implement.
Description
Technical field
The present invention relates to polymeric material field, especially a kind of graphene oxide strengthens vinyl ester matrix material and preparation method thereof.
Background technology
Over nearly 10 years, the compound report of existing a large amount of GO and multiple matrix both at home and abroad, but whether graphene oxide realize monolithic and peel off indefinitely, only can be known as GO/ polymer intercalation material.After 2004, along with Graphene monolithic is proved at the stable existence under conventional environment, and the maturation that mechanically peel GO prepares graphene oxide technology uses, and just truly realized the synthetic of graphene oxide/polymer nanocomposites.
Similar with Single Walled Carbon Nanotube (SWCNT), Graphene has the excellent performance such as heat, power, electricity.But polymer molecule is difficult for entering SWCNT internal surface, and the huge abundant functional group of specific surface area and surface of graphene oxide gives its excellent composite performance, after modification and reduction, can in polymeric matrix, form nano level dispersion, thereby make graphene film there are larger potentiality at the aspects such as mechanics, rheology, permeability and stability to degradation that change polymeric matrix.In addition, because graphene oxide is with low cost, raw material is easy to get, and therefore than SWCNT, has more competitive edge.With the Patents of outer existing graphene oxide/polymer composites, report at present, Application Areas has contained the fuel cell hydrogen storage material of energy industry, the microporous catalyst carrier of synthetic chemical industry, conductive plastics, the aspects such as applied fireproofing of electrically conducting coating and building trade.
Summary of the invention
The object of this invention is to provide a kind of graphene oxide and strengthen vinyl ester matrix material and preparation method thereof, the performances such as the excellent heat having due to graphene oxide, power, electricity, GO of the present invention adds in resin paste as strongthener, by ultrasonic dispersion, its SMC mechanical property of materials of preparing in raw material that is uniformly dispersed is obviously strengthened, and there is very high thermostability.
The object of the invention is to be achieved through the following technical solutions:
Strengthen a vinyl ester matrix material, it is characterized in that: the component that described matrix material contains following weight fraction ratio:
Vinylite 5-50
Glass fibre 5-30
Graphene oxide 5-30
Low profile agent 5-25
Inorganic mineral filler 10-70
Thickening material 1-5
Releasing agent 1-10
Solidifying agent 0.1-5
Described Vinylite is epoxy vingl ester resin; Described glass fibre is through silylation coupling agent treatment; Described inorganic mineral filler is any one or several in calcium carbonate, aluminium hydroxide, talcum powder, kaolin, wilkinite or mica.
Described low profile agent is any in PVAc, PS or PMMA.Described inorganic mineral filler is any one or several in calcium carbonate, aluminium hydroxide, talcum powder, kaolin, wilkinite or mica.Described solidifying agent is TBPB or TBPB and TBPO composite initiation system, and wherein the weight proportion of TBPB/TBPO is 0.6-0.9/0.1-0.4.Described releasing agent is any one in Zinic stearas or calcium stearate.
In the present invention, described composite products form is sheet molding compound (SMC).The moulding process of described composite material by adopting is compression molding or injection molding.
Graphene oxide strengthens a preparation method for vinyl ester matrix material, it is characterized in that the concrete preparation process of the method is as follows:
(1) GO is scattered in anhydrous ethanol solvent, through ultra-sonic oscillation 1h, so that it is further peeled off into the graphene oxide of monolithic, then adds vinyl ester resin, ultrasonic 1h;
(2) filler, releasing agent, the solidifying agent that above-mentioned GO are scattered in to vinyl ester resin mixed solution, low profile agent, inorganic mineral drop in high speed shear mixing machine and fully stir by formula ratio, and rotating speed is controlled at 800-1200rpm, stirs 15 minutes;
(3) drop into rapidly magnesium oxide thickening material, at high-speed stirring 1-2 minute;
(4) fast transfer is discarded in two storage paste grooves of SMC unit, the upper and lower polyethylene film of walking is evenly coated with and applies the resin paste that 2-4mm is thick, continuous glass fibre switches to group by circle and is cut into the chopped ultimate fibre of 24mm length and is evenly scattered in lower-layer resin and pastes over, synchronous by pressure rod, resin paste and fiber are soaked into and mix one, then through adjusting rod excluding air;
(5) wrap-up is coiled into SMC volume, then enters 25-40 ℃ of curing chamber and carries out fast thickening, reaches resin and fully soak into glass fibre after 24-200 hour, obtains graphene oxide and strengthens vinyl ester matrix material.
After the present invention uses graphene oxide and polymer matrix composites mutually compound, obviously promoted the performance such as stretching, compression, bending, shock resistance of this material.The matrix material obtaining has excellent mechanical property and has very high thermostability.
Embodiment
Embodiment 1:
(GO) strengthens a vinyl ester matrix material, and its starting material form mark by weight and are:
Vinylite 20
Glass fibre 20
GO 5
Low profile agent 8
Inorganic mineral filler 40
Thickening material 2
Releasing agent 3
Solidifying agent 2
Wherein: Vinylite is epoxy vingl ester resin; Glass fibre is through silylation coupling agent treatment; Low profile agent is PVAc; Inorganic mineral filler is aluminium hydroxide; Solidifying agent is TBPB or TBPB and TBPO composite initiation system, and wherein the weight proportion of TBPB/TBPO is 0.7/0.3; Releasing agent is Zinic stearas.
Concrete preparation process is as follows:
(1) GO is scattered in anhydrous ethanol solvent, through ultra-sonic oscillation 1h, so that it is further peeled off into the graphene oxide of monolithic, then adds vinyl ester resin, ultrasonic 1h.
(2) filler, releasing agent, the solidifying agent that above-mentioned GO are scattered in to vinyl ester resin mixed solution, low profile agent, inorganic mineral drop in high speed shear mixing machine and fully stir by formula ratio, and rotating speed is controlled at 800-1200rpm, stirs 15 minutes.
(3) drop into rapidly magnesium oxide thickening material, at high-speed stirring 1-2 minute.
(4) fast transfer is discarded in two storage paste grooves of SMC unit, the upper and lower polyethylene film of walking is evenly coated with and applies the resin paste that 2-4mm is thick, continuous glass fibre switches to group by circle and is cut into the chopped ultimate fibre of 24mm length and is evenly scattered in lower-layer resin and pastes over, synchronous by pressure rod, resin paste and fiber are soaked into and mix one, then through adjusting rod excluding air.
(5) wrap-up is coiled into SMC volume, then enters 25-40 ℃ of curing chamber and carries out fast thickening, reaches resin and fully soak into glass fibre after 24-200 hour, completes the preparation that graphene oxide of the present invention strengthens vinyl ester matrix material.
The graphene oxide that the present embodiment makes strengthens vinyl ester matrix material, tensile strength 250Mpa, flexural strength 310Mpa, shock strength 8Kj/m
2, 310 ℃ of heat-drawn wires.
Embodiment 2:
(GO) strengthens a vinyl ester matrix material, and its starting material form mark by weight and are:
Vinylite 20
Glass fibre 20
GO 10
Low profile agent 8
Inorganic mineral filler 40
Thickening material 2
Releasing agent 3
Solidifying agent 2
Wherein: Vinylite is epoxy vingl ester resin; Glass fibre is through silylation coupling agent treatment; Low profile agent is PVAc; Inorganic mineral filler is aluminium hydroxide; Solidifying agent is TBPB or TBPB and TBPO composite initiation system, and wherein the weight proportion of TBPB/TBPO is 0.7/0.3; Releasing agent is Zinic stearas.
Concrete preparation process is as follows:
(1) GO is scattered in anhydrous ethanol solvent, through ultra-sonic oscillation 1h, so that it is further peeled off into the graphene oxide of monolithic, then adds vinyl ester resin, ultrasonic 1h.
(2) filler, releasing agent, the solidifying agent that above-mentioned GO are scattered in to vinyl ester resin mixed solution, low profile agent, inorganic mineral drop in high speed shear mixing machine and fully stir by formula ratio, and rotating speed is controlled at 800-1200rpm, stirs 15 minutes.
(3) drop into rapidly magnesium oxide thickening material, at high-speed stirring 1-2 minute.
(4) fast transfer is discarded in two storage paste grooves of SMC unit, the upper and lower polyethylene film of walking is evenly coated with and applies the resin paste that 2-4mm is thick, continuous glass fibre switches to group by circle and is cut into the chopped ultimate fibre of 24mm length and is evenly scattered in lower-layer resin and pastes over, synchronous by pressure rod, resin paste and fiber are soaked into and mix one, then through adjusting rod excluding air.
(5) wrap-up is coiled into SMC volume, then enters 25-40 ℃ of curing chamber and carries out fast thickening, reaches resin and fully soak into glass fibre after 24-200 hour, completes the preparation that graphene oxide of the present invention strengthens vinyl ester matrix material.
The graphene oxide that the present embodiment makes strengthens vinyl ester matrix material, tensile strength 280Mpa, flexural strength 330Mpa, shock strength 10Kj/m
2, 330 ℃ of heat-drawn wires.
Comparative example 1:
A preparation for vinyl ester SMC material, its starting material form mark by weight and are
Vinylite 20
Glass fibre 20
GO 0
Low profile agent 8
Inorganic mineral filler 40
Thickening material 2
Releasing agent 3
Solidifying agent 2
Wherein: Vinylite is epoxy vingl ester resin; Glass fibre is through silylation coupling agent treatment; Low profile agent is PVAc; Inorganic mineral filler is aluminium hydroxide; Thickening material is magnesium oxide; Solidifying agent is TBPB or TBPB and TBPO composite initiation system, and wherein the weight proportion of TBPB/TBPO is 0.7/0.3; Releasing agent is Zinic stearas.
Concrete preparation process is as follows:
(1) filler of vinyl ester resin, low profile agent, inorganic mineral, releasing agent, solidifying agent are pressed to formula ratio and dropped into fully stirring in high speed shear mixing machine, rotating speed is controlled at 800-1200rpm, stirs 15 minutes.
(2) drop into rapidly magnesium oxide thickening material, at high-speed stirring 1-2 minute.
(3) fast transfer is discarded in two storage paste grooves of SMC unit, the upper and lower polyethylene film of walking is evenly coated with and applies the resin paste that 2-4mm is thick, continuous glass fibre switches to group by circle and is cut into the chopped ultimate fibre of 24mm length and is evenly scattered in lower-layer resin and pastes over, synchronous by pressure rod, resin paste and fiber are soaked into and mix one, then through adjusting rod excluding air.
(4) wrap-up is coiled into SMC volume, then enters 25-40 ℃ of curing chamber and carries out fast thickening, reaches resin and fully soak into glass fibre after 24-200 hour, completes a kind of preparation of vinyl ester SMC material.
A kind of vinyl ester SMC material that this comparative example makes, tensile strength 50Mpa, flexural strength 130Mpa, shock strength 2Kj/m
2, 204 ℃ of heat-drawn wires.
Claims (7)
1. graphene oxide strengthens a vinyl ester matrix material, it is characterized in that: the component that described matrix material contains following weight fraction ratio:
Vinylite 5-50
Glass fibre 5-30
Graphene oxide 5-30
Low profile agent 5-25
Inorganic mineral filler 10-70
Thickening material 1-5
Releasing agent 1-10
Solidifying agent 0.1-5
Described Vinylite is epoxy vingl ester resin; Described glass fibre is through silylation coupling agent treatment, and described coupling agent is the response type coupling agent that contains styryl; Described inorganic mineral filler is any one or several in calcium carbonate, aluminium hydroxide, talcum powder, kaolin, wilkinite or mica.
2. graphene oxide according to claim 1 strengthens vinyl ester matrix material, it is characterized in that: described low profile agent is any in PVAc, PS or PMMA.
3. graphene oxide according to claim 1 strengthens vinyl ester composite material and preparation method thereof, it is characterized in that: described thickening material is magnesium oxide or magnesium hydroxide.
4. graphene oxide according to claim 1 strengthens vinyl ester composite material and preparation method thereof, it is characterized in that: described solidifying agent is TBPB or TBPB and TBPO composite initiation system, and wherein the weight proportion of TBPB/TBPO is 0.6-0.9/0.1-0.4.
5. graphene oxide according to claim 1 strengthens vinyl ester composite material and preparation method thereof, it is characterized in that: described releasing agent is any one in Zinic stearas or calcium stearate.
6. graphene oxide according to claim 1 strengthens vinyl ester composite material and preparation method thereof, it is characterized in that: described composite products form is sheet molding compound.
7. graphene oxide claimed in claim 1 strengthens a preparation method for vinyl ester matrix material, it is characterized in that the concrete preparation process of the method is as follows:
(1) GO is scattered in anhydrous ethanol solvent, through ultra-sonic oscillation 1h, so that it is further peeled off into the graphene oxide of monolithic, then adds vinyl ester resin, ultrasonic 1h;
(2) filler, releasing agent, the solidifying agent that above-mentioned GO are scattered in to vinyl ester resin mixed solution, low profile agent, inorganic mineral drop in high speed shear mixing machine and fully stir by formula ratio, and rotating speed is controlled at 800-1200rpm, stirs 15 minutes;
(3) drop into rapidly magnesium oxide thickening material, at high-speed stirring 1-2 minute;
(4) fast transfer is discarded in two storage paste grooves of SMC unit, the upper and lower polyethylene film of walking is evenly coated with and applies the resin paste that 2-4mm is thick, continuous glass fibre switches to group by circle and is cut into the chopped ultimate fibre of 24mm length and is evenly scattered in lower-layer resin and pastes over, synchronous by pressure rod, resin paste and fiber are soaked into and mix one, then through adjusting rod excluding air;
(5) wrap-up is coiled into SMC volume, then enters 25-40 ℃ of curing chamber and carries out fast thickening, reaches resin and fully soak into glass fibre after 24-200 hour, obtains graphene oxide and strengthens vinyl ester matrix material.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104828806A (en) * | 2015-03-25 | 2015-08-12 | 东莞劲胜精密组件股份有限公司 | A graphene modifier, a graphene reinforced composite material and a preparing method of the graphene reinforced composite material |
| CN105175594A (en) * | 2015-09-14 | 2015-12-23 | 南通银湖通讯设备科技有限公司 | Optical cable intensified core material |
| CN105504695A (en) * | 2016-02-01 | 2016-04-20 | 四川远鸣科技有限公司 | High-strength high-mold corrosion-resistant vinyl ester resin SMC sheet molding compound and preparation method thereof |
| CN106800747A (en) * | 2015-11-26 | 2017-06-06 | 江苏天南电力器材有限公司 | A kind of suspension clamp BMC composites and preparation method thereof |
| CN106800746A (en) * | 2015-11-26 | 2017-06-06 | 江苏天南电力器材有限公司 | A kind of conductor spacer Lightweight high-strength composite material and preparation method thereof |
| WO2017136651A1 (en) * | 2016-02-04 | 2017-08-10 | Continental Structural Plastics, Inc. | Molding compositions with functionalized graphene oxide |
| CN108841135A (en) * | 2018-06-01 | 2018-11-20 | 山东圣泉新材料股份有限公司 | A kind of resin combination, SMC composite material and preparation method and application |
| CN109608847A (en) * | 2018-12-14 | 2019-04-12 | 山东金光复合材料股份有限公司 | A kind of conduction SMC sheet and preparation method thereof |
| CN110305567A (en) * | 2019-06-29 | 2019-10-08 | 新疆同业盛远工程技术有限公司 | A kind of graphene oxide flake anticorrosive paint and preparation method |
| WO2020014467A1 (en) * | 2018-07-11 | 2020-01-16 | Magna Exteriors Inc. | Light weight fire resistant smc composition |
| CN112644041A (en) * | 2019-10-12 | 2021-04-13 | 西安新三力汽车零部件有限公司 | Synthetic method suitable for graphene dispersion |
| WO2022140691A1 (en) * | 2020-12-23 | 2022-06-30 | Magna Exteriors Inc. | Graphene enhanced sheet molding compound |
| CN115141461A (en) * | 2022-07-22 | 2022-10-04 | 合肥荣事达电子电器集团有限公司 | SMC material and preparation process thereof |
| CN115449190A (en) * | 2022-08-23 | 2022-12-09 | 东南大学 | Modified resin for fiber reinforced polymer rib and preparation method thereof |
| CN116218150A (en) * | 2023-03-31 | 2023-06-06 | 武汉联影医疗科技有限公司 | Matching material and application and preparation method thereof |
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| CN104828806A (en) * | 2015-03-25 | 2015-08-12 | 东莞劲胜精密组件股份有限公司 | A graphene modifier, a graphene reinforced composite material and a preparing method of the graphene reinforced composite material |
| CN105175594A (en) * | 2015-09-14 | 2015-12-23 | 南通银湖通讯设备科技有限公司 | Optical cable intensified core material |
| CN106800747A (en) * | 2015-11-26 | 2017-06-06 | 江苏天南电力器材有限公司 | A kind of suspension clamp BMC composites and preparation method thereof |
| CN106800746A (en) * | 2015-11-26 | 2017-06-06 | 江苏天南电力器材有限公司 | A kind of conductor spacer Lightweight high-strength composite material and preparation method thereof |
| CN105504695A (en) * | 2016-02-01 | 2016-04-20 | 四川远鸣科技有限公司 | High-strength high-mold corrosion-resistant vinyl ester resin SMC sheet molding compound and preparation method thereof |
| CN105504695B (en) * | 2016-02-01 | 2018-08-28 | 四川远鸣科技有限公司 | A kind of corrosion-resistant vinyl ester resin SMC sheet shape moulding compound of high-strength and high-modulus and preparation method thereof |
| WO2017136651A1 (en) * | 2016-02-04 | 2017-08-10 | Continental Structural Plastics, Inc. | Molding compositions with functionalized graphene oxide |
| CN108841135A (en) * | 2018-06-01 | 2018-11-20 | 山东圣泉新材料股份有限公司 | A kind of resin combination, SMC composite material and preparation method and application |
| WO2020014467A1 (en) * | 2018-07-11 | 2020-01-16 | Magna Exteriors Inc. | Light weight fire resistant smc composition |
| CN109608847A (en) * | 2018-12-14 | 2019-04-12 | 山东金光复合材料股份有限公司 | A kind of conduction SMC sheet and preparation method thereof |
| CN110305567A (en) * | 2019-06-29 | 2019-10-08 | 新疆同业盛远工程技术有限公司 | A kind of graphene oxide flake anticorrosive paint and preparation method |
| CN112644041A (en) * | 2019-10-12 | 2021-04-13 | 西安新三力汽车零部件有限公司 | Synthetic method suitable for graphene dispersion |
| WO2022140691A1 (en) * | 2020-12-23 | 2022-06-30 | Magna Exteriors Inc. | Graphene enhanced sheet molding compound |
| CN115141461A (en) * | 2022-07-22 | 2022-10-04 | 合肥荣事达电子电器集团有限公司 | SMC material and preparation process thereof |
| CN115449190A (en) * | 2022-08-23 | 2022-12-09 | 东南大学 | Modified resin for fiber reinforced polymer rib and preparation method thereof |
| CN116218150A (en) * | 2023-03-31 | 2023-06-06 | 武汉联影医疗科技有限公司 | Matching material and application and preparation method thereof |
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Application publication date: 20140129 |